CN115746514B - Polyglycolic acid resin composition and film, and preparation method and application thereof - Google Patents
Polyglycolic acid resin composition and film, and preparation method and application thereof Download PDFInfo
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- CN115746514B CN115746514B CN202211460960.7A CN202211460960A CN115746514B CN 115746514 B CN115746514 B CN 115746514B CN 202211460960 A CN202211460960 A CN 202211460960A CN 115746514 B CN115746514 B CN 115746514B
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- polyglycolic acid
- resin composition
- acid resin
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- terephthalate
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 195
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 192
- 239000011342 resin composition Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims abstract description 89
- -1 polybutylene adipate terephthalate Polymers 0.000 claims abstract description 82
- 229920001400 block copolymer Polymers 0.000 claims abstract description 72
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 31
- 239000004970 Chain extender Substances 0.000 claims abstract description 28
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 6
- 229920000359 diblock copolymer Polymers 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 47
- 238000001125 extrusion Methods 0.000 claims description 29
- 239000000155 melt Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000010096 film blowing Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 16
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 108700015862 A-B-A triblock copolymer Proteins 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 25
- 238000001291 vacuum drying Methods 0.000 description 13
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- 238000005453 pelletization Methods 0.000 description 12
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 11
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 238000005086 pumping Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229920002961 polybutylene succinate Polymers 0.000 description 9
- 239000004631 polybutylene succinate Substances 0.000 description 9
- 229920001634 Copolyester Polymers 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000012643 polycondensation polymerization Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000272186 Falco columbarius Species 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
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- 239000012779 reinforcing material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 description 1
- NQZRDXDTNFGVMK-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCC(=O)OCCCCO1 NQZRDXDTNFGVMK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
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- 230000000399 orthopedic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
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- 239000004246 zinc acetate Substances 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to a polyglycolic acid resin composition, a film, a preparation method and application. The polyglycolic acid resin composition comprises polyglycolic acid, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, ase:Sub>A chain extender, ase:Sub>A block copolymer and an antioxidant, wherein the block copolymer is an A-B diblock copolymer, an A-B-A triblock copolymer or ase:Sub>A B-A-B triblock copolymer, the block A is ase:Sub>A polymer with polyglycolic acid chain segments on ase:Sub>A main chain or ase:Sub>A side chain, and the block B is polybutylene adipate terephthalate and/or polybutylene succinate terephthalate. The polyglycolic acid film with the processing stability, the mechanical strength and the tensile toughness synergistically improved can be obtained due to the special synergistic effect of the segmented copolymer.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a polyglycolic acid resin composition, a film, a preparation method and application.
Background
Polyglycolic acid (PGA), an alias polyglycolide or polyglycolic acid, is a completely biodegradable material with a melting temperature of 220-225 ℃ and a glass transition temperature of 35-40 ℃. PGA has good biodegradability, biocompatibility, bioresorbability and excellent mechanical properties, and has been widely focused and applied in the fields of medical sutures, drug controlled release carriers, orthopedic fixing materials, tissue engineering scaffolds, reinforcing materials, oil fields and the like. However, PGA has a series of problems such as high melting point, narrow processing temperature, and too high degradation speed, which seriously affect its processing application.
Aiming at the characteristic of hard and brittle PGA, the PGA is commonly subjected to blending modification with high-toughness degradable polyester materials such as polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST) and the like at present, and the performance characteristics of the two materials are complementarily combined.
CN113088055a (a high-performance polyglycolic acid-based composite material and a preparation method thereof) is based on carboxyl or hydroxyl terminated groups of poly-PGA, and adopts ethylene-vinyl acetate-glycidyl methacrylate copolymer and PBAT blending as a reactive compatibilizer to improve the compatibility of PGA and PBAT and obtain blend injection molded bars with improved tensile toughness. However, in the preparation process of the degradable film bag, the reactive compatilizer cannot be degraded in the system, and the overall degradability of the film is affected. Therefore, how to design and prepare a polyglycolic acid resin composition suitable for use in a degradable film bag is extremely important.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problems of poor stability, hard and brittle performance of the film blowing of the pure polyglycolic acid resin in the prior art, and provide a polyglycolic acid resin composition with stable processing capability.
The second technical problem to be solved by the invention is to provide a preparation method for preparing the polyglycolic acid resin composition.
The third object of the present invention is to provide a polyglycolic acid resin composition film which corresponds to one of the objects.
The fourth technical problem to be solved by the present invention is to provide a method for producing a polyglycolic acid resin composition film corresponding to the third technical problem to be solved.
The fifth technical problem to be solved by the invention is to provide a film bag application of polyglycolic acid resin corresponding to one to four of the technical problems.
In order to solve one of the technical problems, an object of the present invention is to provide a polyglycolic acid resin composition with good processability, comprising polyglycolic acid, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, a block copolymer, a chain extender and an antioxidant.
Wherein the block copolymer is a block polymer of polyglycolic acid and polybutylene adipate terephthalate and/or polybutylene succinate terephthalate. Specifically, the block copolymer is an A-B diblock copolymer, an A-B-A triblock copolymer or ase:Sub>A B-A-B triblock copolymer, wherein the block A is polyglycolic acid, ase:Sub>A polymer with ase:Sub>A polyglycolic acid chain segment on the main chain or the side chain, and the block B is polybutylene adipate terephthalate and/or polybutylene succinate terephthalate.
1-50%, preferably 1-30% of polyglycolic acid based on the total mass of polyglycolic acid and polybutylene adipate terephthalate and/or polybutylene succinate terephthalate; the polybutylene adipate and/or polybutylene succinate is 50-99%, preferably 70-99%.
The block copolymer is 0.1 to 10%, preferably 1 to 10%, based on 100% of the total mass of polyglycolic acid and polybutylene adipate terephthalate and/or polybutylene succinate terephthalate; the antioxidant is 0.1-1%, preferably 0.1-0.6%; the chain extender is 0.01 to 10%, preferably 0.01 to 5%.
The weight average molecular weight of the block copolymer is 20000 to 200000g/mol, preferably 70000 to 160000g/mol.
The polydispersity of the block copolymer is 1 to 3, preferably 1 to 2.
In the block copolymer, the weight average molecular weight of the block B is 1000 to 180000g/mol, preferably 20000 to 100000g/mol, more preferably 40000 to 90000g/mol.
In the block copolymer, the content of the block A is 1 to 99%, preferably 65 to 95% by mass relative to the total mass of the block A and the block B; the content of the block B is 1 to 99%, preferably 5 to 35%;
The PGA dispersed phase in the composition has a size of less than 500 nanometers (nm).
The preparation method of the block copolymer can be seen in Chinese patent application 202111230152.7, and Chinese patent application 202111230152.7 is fully incorporated into the present invention.
According to a preferred embodiment of the present invention, the block copolymer may be prepared by the steps of: comprising melt blending the components comprising the desired amounts of glycolide, aliphatic-aromatic copolyesters and catalyst, followed by cooling to obtain the block copolymer.
Wherein, the dosage ratio of glycolide to aliphatic-aromatic copolyester is 100: (1 to 99), preferably 100: (5-40); the dosage ratio of glycolide to the catalyst is 100: (0.005-1), preferably 100: (0.01-0.5).
The weight average molecular weight of the aliphatic-aromatic copolyester is 1000-200000 g/mol, preferably 20000-100000 g/mol, more preferably 40000-90000 g/mol.
The aliphatic-aromatic copolyester is selected from at least one of the following polymers:
polybutylene succinate and/or low molecular weight polymers of polybutylene succinate obtained by alcoholysis; a low molecular weight polymer obtained by alcoholysis of at least one of chain-extended modified polybutylene succinate, terminal-modified polybutylene succinate and polybutylene adipate terephthalate; chain extended modified polybutylene adipate terephthalate and terminal modified polybutylene adipate terephthalate.
The block copolymer is preferably block polymerized from biodegradable PGA and PBAT and/or PBST.
The catalyst is a salt compound corresponding to at least one of IIA-VA group metal element and transition metal element; preferably, the catalyst is a salt compound corresponding to at least one of Sn, bi, mg, al, ca, fe, mn, ti and Zn, and more preferably a Sn salt.
In the preparation step of the block copolymer, the temperature of the melt blending reaction is 180-250 ℃, preferably 210-230 ℃; the reaction time is 3-20 min.
The preparation process of the block copolymer is carried out in a melt mixing device; preferably, the melt mixing device is one or more of a series combination of a kettle reactor, a tubular reactor, an internal mixer, a Farrel continuous mixer, a Banbury mixer, a single screw extruder, a multi-screw extruder, and a reciprocating single screw extruder, preferably an internal mixer or a twin screw extruder.
The preparation process of the block copolymer is carried out in an internal mixer: preferably, the internal mixing temperature is 180-250 ℃, preferably 210-230 ℃, the rotating speed is 5-150 rpm, preferably 20-80 rpm, and the reaction time is 3-15 min, preferably 5-10 min.
The preparation process of the block copolymer is carried out in a twin-screw extruder: preferably, the processing temperature is 180 to 250 ℃, preferably 210 to 230 ℃, the screw speed is 5 to 300rpm, preferably 30 to 100rpm, the aspect ratio is 30 to 80, preferably 40 to 70.
The polyglycolic acid may have an intrinsic viscosity of 0.5 to 5dl/g, for example, an intrinsic viscosity of 0.5dl/g, 1dl/g, 1.5dl/g, 2.0dl/g, 2.5dl/g, 3dl/g, 3.5dl/g, 4dl/g, 4.3dl/g, 4.6dl/g, 4.9dl/g, 5dl/g or a range of values between any two of the above, and particularly further preferably 1 to 3dl/g.
The polyglycolic acid can be prepared by ring-opening polymerization or polycondensation polymerization, and specifically can be obtained by direct condensation polymerization of glycolic acid/ester, or can be obtained by ring-opening polymerization of glycolide or polycondensation polymerization of glycolic acid or methyl glycolate.
The antioxidant is selected from one or more of hindered phenols, hindered amines and phosphite antioxidants.
The chain extender is at least one selected from a polyfunctional compound or polymer containing a plurality of epoxy groups or isocyanate groups.
The polyglycolic acid microscopic phase structure size in the polyglycolic acid resin composition is less than 500nm.
The invention adopts melt blending extrusion, and the polyglycolic acid resin composition is obtained by plasticizing, kneading, compressing, extruding, cooling and granulating each component with required amount.
In order to solve the second technical problem, the second object of the present invention is to provide a method for preparing the polyglycolic acid resin composition, which comprises the following steps:
and (3) melting and blending components comprising polyglycolic acid, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, a block copolymer, a chain extender and an antioxidant, extruding and granulating to obtain the polyglycolic acid resin composition.
The components are preferably thoroughly dried under certain conditions prior to melt blending and then mixed.
Specifically, the preparation method may include the steps of:
the polyglycolic acid resin composition is prepared by fully drying required components comprising polyglycolic acid, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, a block copolymer, a chain extender, an antioxidant and the like under certain conditions, mixing according to a certain proportion, and then carrying out melt blending and continuous extrusion.
Wherein, the drying can be specifically realized by adopting a drying device commonly used in the field such as a blast type drying oven or a vacuum drying oven; preferably, the drying temperature is 40-150 ℃ and the drying time is 3-5 h.
1 to 50 parts of polyglycolic acid, preferably 1 to 30 parts of polyglycolic acid, based on 100 parts by weight of the total mass of polyglycolic acid and polybutylene adipate terephthalate and/or polybutylene succinate terephthalate; the rest is polybutylene adipate terephthalate and/or polybutylene succinate terephthalate.
The block copolymer is 0.1-10% of the total mass of polyglycolic acid and polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, preferably 1-10%; the antioxidant is 0.1 to 1 percent of the total mass of the polyglycolic acid and the polybutylene adipate terephthalate and/or the polybutylene succinate terephthalate, and is preferably 0.1 to 0.6 percent; the chain extender is 0.01-10% of the total mass of poly (glycolic acid), poly (butylene adipate-terephthalate) and/or poly (butylene succinate-terephthalate), and preferably 0.01-5%.
The blending may be accomplished in a blending apparatus commonly used in the art, such as an internal mixer, a single screw extruder, a twin screw extruder, and like processing equipment, preferably a twin screw extruder.
The polyglycolic acid resin composition has good processability, and is characterized in that the melt expansion rate after extrusion of a die by a double screw extruder is less than 200%, for example, 190%, 180%, 170%, 160%, 150%, 140%, 130%, 120% and the like.
Melt swell ratio (MER: melt Expansion Ratio) is defined as melt diameter d 1cm from the die 2 Diameter d of die 1 The ratio, see specifically fig. 1, is calculated as follows:
the extrusion temperature is preferably 190℃to 260℃and more preferably 200℃to 250 ℃.
The extrusion speed is preferably 20rpm to 500rpm, more preferably 50rpm to 250rpm.
In order to solve the fourth problem, it is still another object of the present invention to provide a film of a polyglycolic acid resin composition prepared from the above polyglycolic acid resin composition.
The tensile strength of the film is more than or equal to 10MPa, the elongation at break is more than or equal to 800%, and the modulus is more than or equal to 30MPa.
The fourth object of the present invention is to provide a process for producing the polyglycolic acid resin composition film, which comprises melting and compressing the polyglycolic acid resin composition, extruding, cooling, stretching and winding the polyglycolic acid resin composition to obtain the polyglycolic acid composition film.
The extrusion and film blowing may be performed by means commonly used in the art.
The melting and compressing adopt at least one screw extruder.
The screw extruder is preferably a single screw extruder or a twin screw extruder.
The film forming die is a film blowing die or a casting film die.
In the process for producing a film of the polyglycolic acid resin composition, the temperature of the screw extruder is preferably 190 to 260 ℃, more preferably 200 to 250 ℃; the extrusion speed is preferably 1rpm to 500rpm, more preferably 1rpm to 100rpm.
The polyglycolic acid resin composition melt is continuous and stable in the blending processing process, and the phenomenon of strand breakage does not occur within 60 minutes.
The conditions for film formation include: the film blowing temperature is 100-250 ℃, and the die temperature is 210-240 ℃; the blow-up ratio is (1.5:1) to (6:1), preferably (2:1) to (5:1).
The fifth object of the present invention is to provide the use of the polyglycolic acid resin composition film in a film bag.
The polyglycolic acid resin composition of the present invention can be used for preparing film bags.
The invention provides a polyglycolic acid resin composition, a film, a preparation method and application, wherein the polyglycolic acid resin composition obtained after melt blending, extrusion, cooling and granulation has stable processing performance, and the film of the polyglycolic acid resin composition obtained has stable microstructure, excellent macroscopic mechanical property and synergistically improved mechanical strength and tensile toughness.
Drawings
FIG. 1 is a schematic illustration of a definition of the swell ratio of a polymer melt. In fig. 1, 1 is the extruder die and 2 is the polymer melt.
FIG. 2 is a photograph of the expansion of the PGA/PBAT composition melt during processing of comparative example 1, with the arrow at 1cm from the die, where the melt diameter was 6.9mm.
FIG. 3 is a photograph of the expansion of the PGA/PBAT composition melt during processing of example 6, the arrow being 1cm from the die, where the melt diameter is 3.6mm.
Fig. 4 is an SEM photograph of comparative example 1 at 1k magnification.
Fig. 5 is an SEM photograph of comparative example 1 at 5k magnification.
Fig. 6 is an SEM photograph of example 6 at 1k magnification.
Fig. 7 is an SEM photograph of example 6 at 5k magnification.
Fig. 8 is an SEM photograph of example 8 at 1k magnification.
Fig. 9 is an SEM photograph of comparative example 2 at 1k magnification.
Fig. 10 is an SEM photograph of comparative example 3 at 1k magnification.
Fig. 11 is an SEM photograph of comparative example 3 at 5k magnification.
Fig. 12 is an SEM photograph of comparative example 4 at 1k magnification.
Fig. 13 is an SEM photograph of comparative example 4 at 5k magnification.
FIG. 14 is a graph showing the tensile strength of a 25% PGA/PBAT blend film as a function of the block copolymer content.
FIG. 15 is a graph showing the elongation at break of a 25% PGA/PBAT blend film as a function of the block copolymer content.
FIG. 16 is a graph showing the variation of elastic modulus of a 25% PGA/PBAT blend film with the block copolymer content.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
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 following materials and preparation methods are briefly described as follows:
1. polyglycolic acid
Polyglycolic acid (Polyglycolic acid, PGA), also known as polyglycolic acid, is the thermoplastic linear aliphatic polyester with the simplest structure. PGA can be prepared by melt polycondensation of glycolic acid or ring-opening polymerization of glycolide. Polyglycolic acid is a typical high crystallinity polymer that is lattice stable and has a relatively high melting point. PGA is a hydrophilic resin, and the surface of PGA is liable to absorb moisture and undergo hydrolytic aging, so that the stability of the product is poor, thereby limiting the application thereof.
Polyglycolic acid has excellent biodegradability, can enter a human circulatory system to be degraded in vivo and discharged out of the body, can be degraded in an in-vitro environment, and is mainly applied to the fields of medical suture lines, drug controlled release carriers, fracture fixing materials, tissue engineering scaffolds, reinforcing materials and the like. Through solution spinning and melt spinning, polyglycolic acid can be processed into surgical suture lines, has stronger tensile strength and can maintain enough time, and is suitable for wound suturing of deep tissues.
In the present embodiment, the intrinsic viscosity of the polyglycolic acid may be 0.5 to 5dl/g, for example, the intrinsic viscosity may be 0.5dl/g, 1dl/g, 1.5dl/g, 2.0dl/g, 2.5dl/g, 3dl/g, 3.5dl/g, 4dl/g, 4.3dl/g, 4.6dl/g, 4.9dl/g, 5dl/g, or a range between any two of the above values, and particularly, it may be further preferably 1 to 3dl/g.
The polyglycolic acid can be prepared by ring-opening polymerization or polycondensation polymerization, and specifically can be obtained by direct condensation polymerization of glycolic acid/ester, or can be obtained by ring-opening polymerization of glycolide or polycondensation polymerization of glycolic acid or methyl glycolate.
2. Polybutylene adipate terephthalate
Polybutylene adipate terephthalate (PBAT) is a polyester-based biodegradable plastic, a copolymer consisting of polybutylene adipate (BA) and butylene terephthalate (BA). The PBAT has the degradation performance of the aliphatic Polyester (PBA) and the mechanical property of the aromatic Polyester (PBA), and the excellent softness and ductility enable the PBAT to be suitable for food packaging and agricultural films, so that the PBAT is one of degradation materials which are very actively applied to the market at present. PBAT is a semi-crystalline polymer having a crystallization temperature of about 42 ℃, a crystallinity of about 15% and a melting point of about 120 ℃. The PBAT processability is similar to that of LDPE, can be blow molded, and is one of the few fully degradable materials that can be blow molded. But the degradation rate is relatively slow due to the existence of the aromatic PBT chain segment; the high price, poor mechanical properties and barrier properties limit its popularization and application in the market place.
As a petroleum-based biodegradable high molecular polymer, PBAT has great advantages in terms of production transfer, and in recent years, with the tightening of domestic plastic limiting and inhibiting policies, domestic PBAT is newly built and the build capacity is rapidly enlarged. PBAT and its corresponding complex have a very large application market.
3. Polyglycolic acid resin composition
In the method for preparing the polyglycolic acid resin composition, melt blending reaction extrusion is adopted, and the components with required amounts are uniformly mixed in a molten state to obtain the polyglycolic acid resin composition.
The polyglycolic acid resin composition is prepared from polyglycolic acid resin, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, a block copolymer, a chain extender and an antioxidant.
The block copolymer is formed by the block polymerization of biodegradable PGA, PBAT and/or PBST, and comprises an A-B diblock copolymer, an A-B-A triblock copolymer or ase:Sub>A B-A-B triblock copolymer, wherein the block A is polyglycolic acid or ase:Sub>A polymer with ase:Sub>A polyglycolic acid chain segment in ase:Sub>A main chain or ase:Sub>A side chain, and the block B is polybutylene adipate terephthalate and/or polybutylene succinate terephthalate.
The weight average molecular weight of the block copolymer is 20000-200000 g/mol, preferably 70000-160000 g/mol; the polydispersity of the block copolymer is 1 to 3, preferably 1 to 2.
In the block copolymer, the weight average molecular weight of the block B is 1000 to 180000g/mol, preferably 20000 to 100000g/mol, more preferably 40000 to 90000g/mol.
In the block copolymer, the content of the block A is 1 to 99%, preferably 65 to 95% by mass relative to the total mass of the block A and the block B; the content of the block B is 1 to 99%, preferably 5 to 35%.
The preparation method of the block copolymer can be seen in Chinese patent application 202111230152.7, and Chinese patent application 202111230152.7 is fully incorporated into the present invention.
According to a preferred embodiment of the present invention, the block copolymer may be prepared by the steps of: comprising melt blending the components comprising the desired amounts of glycolide, aliphatic-aromatic copolyesters and catalyst, followed by cooling to obtain the block copolymer.
Wherein, the dosage ratio of glycolide to aliphatic-aromatic copolyester is 100: (1 to 99), preferably 100: (5-40); the dosage ratio of glycolide to the catalyst is 100: (0.005-1), preferably 100: (0.01-0.5).
The weight average molecular weight of the aliphatic-aromatic copolyester is 1000-200000 g/mol, preferably 20000-100000 g/mol, more preferably 40000-90000 g/mol.
The aliphatic-aromatic copolyester is selected from at least one of the following polymers:
polybutylene succinate and/or low molecular weight polymers of polybutylene succinate obtained by alcoholysis; a low molecular weight polymer obtained by alcoholysis of at least one of chain-extended modified polybutylene succinate, terminal-modified polybutylene succinate and polybutylene adipate terephthalate; chain extended modified polybutylene adipate terephthalate and terminal modified polybutylene adipate terephthalate.
The block copolymer is preferably block polymerized from biodegradable PGA and PBAT and/or PBST.
The catalyst is a salt compound corresponding to at least one of IIA-VA group metal element and transition metal element; preferably, the catalyst is a salt compound corresponding to at least one of Sn, bi, mg, al, ca, fe, mn, ti and Zn, and more preferably a Sn salt.
In the preparation step of the block copolymer, the temperature of the melt blending reaction is 180-250 ℃, preferably 210-230 ℃; the reaction time is 3-20 min.
The preparation process of the block copolymer is carried out in a melt mixing device; preferably, the melt mixing device is one or more of a series combination of a kettle reactor, a tubular reactor, an internal mixer, a Farrel continuous mixer, a Banbury mixer, a single screw extruder, a multi-screw extruder, and a reciprocating single screw extruder, preferably an internal mixer or a twin screw extruder.
The preparation process of the block copolymer is carried out in an internal mixer: preferably, the internal mixing temperature is 180-250 ℃, preferably 210-230 ℃, the rotating speed is 5-150 rpm, preferably 20-80 rpm, and the reaction time is 3-15 min, preferably 5-10 min.
The preparation process of the block copolymer is carried out in a twin-screw extruder: preferably, the processing temperature is 180 to 250 ℃, preferably 210 to 230 ℃, the screw speed is 5 to 300rpm, preferably 30 to 100rpm, the aspect ratio is 30 to 80, preferably 40 to 70.
The antioxidant is at least one or more than two selected from hindered phenols, hindered amines and phosphite antioxidants.
The chain extension is selected from at least one of a polyfunctional compound or polymer containing a plurality of epoxy groups or isocyanate groups.
The preparation method is characterized in that polyglycolic acid, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, a block copolymer, a chain extender and an antioxidant are respectively metered into a double-screw extruder according to a certain feeding proportion to be extruded and granulated. The other concrete embodiment is that polyglycolic acid, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, a block copolymer, a chain extender and an antioxidant are mixed according to the required proportion and then added into a double-screw extruder for extrusion granulation.
According to a preferred embodiment of the present invention, the desired amounts of polyglycolic acid, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, block copolymers, chain extenders, antioxidants and other functional auxiliaries are sufficiently dried, and then melted, blended and extruded by a twin screw extruder to obtain the polyglycolic acid resin composition.
Wherein,
the drying can be performed by adopting a blast oven or vacuum drying;
The drying temperature can be selected to be 40-150 ℃, more preferably 60-110 ℃, and the drying time can be controlled to be 3-5 h. For example, the drying temperature may be selected from 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or a range between any two of the above values, and the drying time may be 3, 4, 5 hours or a range between any two of the above values.
The blending may be carried out using other processing equipment commonly used in the art, such as internal mixers, single screw extruders, twin screw extruders, and the like, with twin screw extruders being preferred.
The extrusion temperature may be 200 ℃ to 260 ℃, more preferably 220 ℃ to 250 ℃; the rotation speed of the extruder may be 20rpm to 500rpm, more preferably 50rpm to 250rpm. For example, the extrusion temperature may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃ or a range between any two of the foregoing values; the rotational speed of the extruder may be 20rpm, 50rpm, 60rpm 70rpm, 80rpm, 90rpm, 100rpm, 120rpm, 150rpm, 170rpm, 180rpm, 200rpm, 220rpm, 240rpm, 250rpm, 260rpm, 270rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm or a range of values between any two of the foregoing.
4. Polyglycolic acid resin composition film
Adding the polyglycolic acid resin composition into at least one screw extruder, melting, compressing, extruding through a film-making die, cooling, stretching and rolling to obtain the polyglycolic acid composition film.
In the method for producing a polyglycolic acid resin composition film, the polyglycolic acid resin composition is blown through a single screw extruder to obtain the polyglycolic acid resin composition film.
In the step of preparing the polyglycolic acid resin composition film, the temperature of the extruder suitable for the present invention may be 100 to 260 ℃, more preferably 120 to 250 ℃; the rotation speed of the extruder is 1rpm to 500rpm, more preferably 1rpm to 100rpm.
The melt swell ratio (MER: melt Expansion Ratio) (the ratio of the melt diameter at the position of 1cm of the outlet die to the die diameter) of the polyglycolic acid resin composition after passing through the screw die is less than 200%.
According to the composition of the composition raw materials, the processing process is continuous and stable, and the phenomenon of strand breakage does not occur within 60 minutes.
In the invention, the polyglycolic acid film with the processing stability, the mechanical strength and the tensile toughness are synergistically improved due to the special synergistic effect of the segmented copolymer.
The raw material sources are as follows:
the raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
The raw materials used in examples and comparative examples are all commercially available.
Polyglycolic acid (PGA), produced by Corbion Purac company, having an intrinsic viscosity of 1.0 to 1.4dl/g and a melting point of 200 to 240 ℃;
polybutylene adipate terephthalate (PBAT), manufactured by BASF under the trademark ofF C-1200, melt index: 5.5g/10min.
Antioxidant, phenyl tris (2, 4-di-t-butyl) phosphite (antioxidant 168) was purchased from Sigma-Aldrich.
ADR of chain extenderADR-4468, epoxy equivalent: 310 g/mol) from basf (china) limited.
Glycolide (GA), dai of Shandong, goodyear Biotechnology Co., ltd, purity not less than 99.5%.
Anhydrous stannous chloride (SnCl) 2 ) Zinc acetate (dihydrate), ethylene glycol and dodecanol are purchased from national pharmaceutical chemicals limited. Anhydrous stannous chloride, zinc acetate (dihydrate) and ethylene glycol are both AR grade, and dodecanol is CP grade.
The invention performs performance measurement according to the following method:
gel Permeation Chromatography (GPC): the test instrument was a gel permeation chromatograph model PL-GPC50 from Angilent, USA, and the process software was GPC offine. In the test, the mobile phase is hexafluoroisopropanol containing 5mmol/L sodium trifluoroacetate, the flow rate is 1mL/min, the column temperature is 40 ℃, the sample injection amount is 100 mu L, the standard sample is PMMA, and the sample concentration is 1mg/mL.
Film tensile test: the test was performed according to ISO 527-3 using a model 3344 Universal laboratory machine from INSTRON, and the software was Bluehill version 2.31. The pattern was cut into Type 5 of ISO 527-3 standard, and placed in a Bluecard BPS-100CB constant temperature and humidity cabinet (temperature 23 ℃ C., relative humidity 50%) of Shanghai-Hemsl scientific instruments Co., ltd for 24 hours. When testing, the initial clamp interval is 50mm, the test stretching rate is 500mm/min, each sample is tested 5 times, and the average value is obtained.
SEM test: the test was carried out using a Zeiss Merlin field emission scanning microscope, germany. Firstly, after a polyglycolic acid resin composition material sample is brittle by liquid nitrogen, surface metal spraying treatment is carried out on the section, and the microscopic morphology and the size of different disperse phases at the section of the sample are observed.
Comparative example 1
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation,C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant and 0.5 part chain extender, and adding PolyLab HAAKE from Thermo Fisher technology Co., USA via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
Comparative example 2
75 parts by mass of polyglycolic acid (PGA, corbion Purac) and 25 parts by mass of PBAT (BASF corporation,C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant and 0.5 part chain extender, and adding PolyLab HAAKE from Thermo Fisher technology Co., USA via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ comparative example 3 ]
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation,C1200F Blend, melt index 5.5g/10 min), 0.5 parts antioxidant and 0.5 parts chain extender and 5 parts PGA grafted with 3% BMA monomer were thoroughly premixed and fed into PolyLab HAAKE by ThermoFisher technology Co., USA via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ comparative example 4 ]
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation,C1200F Blend, melt index of 5.5g/10 min), 0.5 parts antioxidant and 0.5 parts chain extender and 5 parts isocyanate-extended PGA/PBAT copolymer composition (prepared according to the method of patent application CN 114075376A: uniformly mixing 30 parts by mass of polyglycolic acid PGA, 70 parts by mass of PBAT and 0.5 part by mass of compatilizer (MDI), then melt-blending at 230 ℃ by a twin-screw extruder, extruding and granulating at 200rpm to obtain an isocyanate-chain-extended PGA/PBAT copolymer composition), fully premixing, and then feeding the mixture into PolyLab HAAKE of Thermo Fisher scientific company in the U.S. through a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from the feeding port to the mouth mold, with the number of 1-11, wherein the 1 st section only has the function of feeding andand cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ example 1 ]
Glycolide (GA), anhydrous stannous chloride and polybutylene succinate terephthalate (PBST) (weight average molecular weight: 60000 g/mol) were prepared according to a ratio of 70:0.021:30 by mass ratio, polyLab HAAKE, thermo Fisher technology Co., USA TM The polymerization was carried out in a Rheomix OS 567-1000 internal mixer (rotor diameter 35mm, rotor length 50 mm). The rotation speed was 50rpm, the temperature was 215℃and the reaction time was 5min. After the reaction, the mixture was allowed to cool in air to obtain a PGA/PBST block copolymer. And dissolving the obtained product with hexafluoroisopropanol, precipitating with a large amount of chloroform, washing, centrifuging, and drying in vacuum to remove the solvent to obtain the purified PGA-PBST triblock copolymer. The weight average molecular weight was 78669g/mol and the PDI was 1.57 as measured by GPC.
[ example 2 ]
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation,C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant, 0.5 part chain extender and 0.5 part of the block copolymer prepared in example 1, and then fed into PolyLab HAAKE of Thermo Fisher technology Co., USA via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and220℃and screw speed was set at 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ example 3 ]
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation, C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant, 0.5 part chain extender, and 1 part of the block copolymer prepared in example 1, were thoroughly premixed and fed into PolyLab HAAKE, thermo Fisher technology Co., USA, via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ example 4 ]
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation,C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant, 0.5 part chain extender, and 2 parts of the block copolymer prepared in example 1 were thoroughly premixed and fed into PolyLab HAAKE, thermo Fisher technology Co., USA, via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder is from11 sections from the feeding port to the die are numbered 1-11, wherein the 1 st section only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ example 5 ]
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation,C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant, 0.5 part chain extender, and 3 parts of the block copolymer prepared in example 1 were thoroughly premixed and fed into PolyLab HAAKE, thermo Fisher technology Co., USA, via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ example 6 ]
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation,C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant, 0.5 part chain extender and 5 parts of the preparation of example 1After fully premixing, the block copolymer of (C) was fed into PolyLab HAAKE, thermo Fisher technology Co., USA, through a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ example 7 ]
25 parts by mass of polyglycolic acid (PGA, corbion Purac) and 75 parts by mass of PBAT (BASF corporation, C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant, 0.5 part chain extender, and 10 parts of the block copolymer prepared in example 1 were thoroughly premixed and fed into PolyLab HAAKE, thermo Fisher technology Co., USA, via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby. />
[ example 8 ]
75 parts by mass of polyglycolic acid (PGA, corbion Purac) and 25 parts by mass of PBAT (B)The ASF company,C1200F Blend, melt index of 5.5g/10 min), 0.5 part antioxidant, 0.5 part chain extender and 0.5 part of the block copolymer prepared in example 1, and then fed into PolyLab HAAKE of Thermo Fisher technology Co., USA via a volumetric feeder TM Rheomer OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D=40) extrusion pelletization. The extruder has 11 sections from a feeding port to a die, and the number of the sections is 1-11, wherein the section 1 only plays a role of feeding and cannot be heated. The temperatures of the sections 2 to 11 of the extruder are respectively as follows: 180 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,225 ℃,225 ℃ and 220 ℃, and the screw rotation speed is set to 200rpm. The torque range is 30-50% during steady operation. The extruder was equipped with a circular die having a diameter of 3mm, and the bars were air-cooled by extruding from the die and then cut into cylindrical pellets of about 3mm by a pelletizer. Collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for standby.
[ example 9 ]
The processing of each of the polyglycolic acid resin compositions of examples 2 to 8 and comparative examples 1 to 4 was recorded in detail, and the melt of the PGA/PBAT blend (FIG. 2, comparative example 1) to which the block copolymer was not added was subjected to significant swelling after die stripping, and adjacent melt-bracing adhesion occurred at a small distance between die openings on the extrusion line for mass production, resulting in difficulty in pelletizing and poor processability. It was unexpectedly found in the experiments that the die swell of the melt (fig. 3, example 6) of the polyglycolic acid resin composition after the addition of the block copolymer prepared in example 1 was significantly reduced. The melt swell ratio (MER) of the polymer after passing through the screw die is the ratio of the diameter of the melt at 1cm of the die to the diameter of the die. Table 1 below shows the variation in melt swell ratio for the different samples.
TABLE 1 melt swell rate variation for different samples
The above table shows that the melt swell ratio of PGA/PBAT decreases significantly with increasing block copolymer addition. When the PGA/PBAT blend with 25% PGA added with 0.5% block copolymer, the melt swell ratio of the blend was reduced from 230% to 180% by 21.7%. After the content of the block copolymer is continuously increased, the melt expansion rate of the blend is further reduced, and after the content of the block copolymer is added by 5%, the melt expansion rate of the blend is only 120%. The melt swell ratio of the blend can also be significantly reduced (example 8) by less than 200% after addition of the block copolymer in a high PGA content system (comparative example 2). The obvious reduction of the expansion rate of the PGA/PBAT melt means that the melts from the multi-channel mouth die cannot adhere to each other in large-scale production, the yield and the processing stability of the large-scale production are ensured, and the method has guiding significance for the actual large-scale production.
[ example 10 ]
The particles of examples 2 to 7 and comparative examples 1, 3 and 4 were sufficiently dried and then HAAKE manufactured in U.S. Thermo Fisher Scientific Inc TM Blown films were prepared on a Rheomex OS single screw extruder having a screw diameter of 19mm and an aspect ratio of 25 equipped with a 3:1 standard metering screw, the single extruder being composed of HAAKE TM PolyLab TM OS torque rheometer platform control. Feeding the materials into an extruder through a feeder, wherein the heating temperatures of the extruder are respectively as follows: 200 ℃,220 ℃,220 ℃,220 ℃,220 ℃,220 ℃ and the torque range is 10-50 percent when the screw rotation speed is set to be 50rpm for stable operation. The extruder was equipped with a circular die (gap 0.5 mm) 19.5mm in diameter, and the melt was extruded, cooled, shaped, drawn, and wound to form a film. The film blowing temperature is 220 ℃ and the die temperature is 230 ℃.
[ example 11 ]
Examples 6, 8 and comparative examples 1-4 were quenched in liquid nitrogen, and after spraying the metal on the cross section, the microscopic phase structure of the blend was observed on a ZEISS MERLIN type Scanning Electron Microscope (SEM) in germany, and the corresponding microscopic morphologies were obtained as shown in fig. 4-13.
FIGS. 4 and 5 are SEM images of 25/75PGA/PBAT blends at 1000 times (1 k) and 5k magnification, respectively, of comparative example 1. It is clear from fig. 4 and 5 that in the PGA low content blending system, PGA is dispersed as spherical particles in the PBAT matrix, exhibiting a distinct sea-island phase structure. And in this case, the PGA is large in size, most of the PGA spheres have a diameter of 1-2 μm and are unevenly dispersed in the PBAT matrix, showing poor compatibility between the PGA and the PBAT phases. FIGS. 6 and 7 are SEM images of 25/75PGA/PBAT blends after addition of 5% block copolymer at 1k and 5k magnification, respectively. Compared with fig. 4 and 5, after the block copolymer is added, the size of the PGA is obviously reduced (< 0.5 mu m, namely < 500 nm), nano-scale dispersion is achieved, the PGA is uniformly dispersed in a PBAT matrix, the whole structure of the blend phase is uniform and compact, and the addition of the block copolymer obviously improves the compatibility between the PGA and the PBAT two phases, and the microstructure of nano-scale dispersion is achieved. Fig. 9 is an SEM image of a 75/25PGA/PBAT blend (comparative example 2) at 1k magnification, showing the two-phase structure with distinct voids in the high PGA content (75%) blend system. After the addition of the block copolymer, the phase structure of the high PGA content system was uniform. Fig. 10 and 11 are SEM images of comparative example 3 at 1k and 5k magnifications, respectively. Fig. 12 and 13 are SEM images of comparative example 4 at 1k and 5k magnifications. It can be clearly seen that the phase size of the PGA in the blend can be significantly reduced by the addition of the non-block compatibilizer, but the overall dispersion uniformity is poor and there are significant voids.
[ example 12 ]
The polyglycolic acid resin composition film obtained in example 10 was subjected to the film stretching method, and the results are shown in the following table.
TABLE 2 mechanical Properties of polyglycolic acid resin composition film
As is evident from a combination of the above table results, the elongation at break of the film was not significantly improved, although the overall strength and elastic modulus of the PGA/PBAT film were significantly improved by the addition of the non-block compatibilizers (comparative example 3 and comparative example 4). The addition of the block copolymer can obviously improve the tensile strength and the elongation at break of the PGA/PBAT blend film. When the addition amount of the block copolymer is 10%, the tensile strength of the PGA/PBAT film is improved from 10MPa to 25MPa, the elongation at break is improved from 760% to 1255%, and 150% and 65% of the elongation at break are respectively increased, so that the synergistic improvement of the mechanical strength and the tensile toughness is realized. Meanwhile, due to the unique characteristics of the block copolymer, the PGA/PBAT blend has very stable performance in the melt processing and film blowing processes, and the formula and the composition have great promotion effect on the expansion of the practical production of PGA resin, thus achieving remarkable technical progress.
Claims (16)
1. ase:Sub>A polyglycolic acid resin composition comprising polyglycolic acid, polybutylene adipate-terephthalate and/or polybutylene succinate-terephthalate, ase:Sub>A block copolymer, ase:Sub>A chain extender and an antioxidant, wherein the block copolymer is an ase:Sub>A-B diblock copolymer, an ase:Sub>A-B-ase:Sub>A triblock copolymer, or ase:Sub>A B-ase:Sub>A-B triblock copolymer, wherein block ase:Sub>A is polyglycolic acid and block B is polybutylene adipate-terephthalate and/or polybutylene succinate-terephthalate.
2. The polyglycolic acid resin composition according to claim 1, wherein:
the weight average molecular weight of the block copolymer is 20000-200000 g/mol; and/or the number of the groups of groups,
the polydispersity of the block copolymer is 1-3; and/or the number of the groups of groups,
the weight average molecular weight of the block B is 1000-180000 g/mol; and/or the number of the groups of groups,
the content of the block A is 1-99% by mass relative to the total mass of the block A and the block B; the content of the block B is 1-99%; and/or the number of the groups of groups,
the polyglycolic acid microscopic phase structure size in the polyglycolic acid resin composition is less than 500nm.
3. The polyglycolic acid resin composition according to claim 2, wherein:
the weight average molecular weight of the block copolymer is 70000-160000 g/mol; and/or the number of the groups of groups,
the polydispersity of the block copolymer is 1-2; and/or the number of the groups of groups,
the weight average molecular weight of the block B is 20000-100000 g/mol; and/or the number of the groups of groups,
the content of the block A is 65-95% relative to the total mass of the block A and the block B; the content of the block B is 5 to 35 percent.
4. The polyglycolic acid resin composition according to claim 1, wherein:
the intrinsic viscosity of the polyglycolic acid is 0.5 to 5dl/g; and/or the number of the groups of groups,
The antioxidant is at least one selected from hindered phenols, hindered amines and phosphites; and/or the number of the groups of groups,
the chain extender is at least one selected from a polyfunctional compound or polymer containing a plurality of epoxy groups or isocyanate groups.
5. The polyglycolic acid resin composition according to claim 4, wherein:
the polyglycolic acid has an intrinsic viscosity of 1 to 3dl/g.
6. The polyglycolic acid resin composition according to claim 1, wherein:
1-50% of polyglycolic acid and 1-50% of polybutylene adipate terephthalate and/or polybutylene succinate terephthalate by total mass; 50-99% of polybutylene adipate terephthalate and/or polybutylene succinate terephthalate;
0.1 to 10 percent of block copolymer based on 100 percent of total mass of polyglycolic acid and polybutylene adipate terephthalate and/or polybutylene succinate terephthalate; 0.1 to 1 percent of antioxidant; the chain extender is 0.01-10%.
7. The polyglycolic acid resin composition according to claim 6, wherein:
1-30% of polyglycolic acid and 1-30% of polybutylene adipate terephthalate and/or polybutylene succinate terephthalate based on the total mass of the polyglycolic acid and the polybutylene adipate terephthalate; 70-99% of polybutylene adipate terephthalate and/or polybutylene succinate terephthalate;
1 to 10 percent of block copolymer based on 100 percent of total mass of polyglycolic acid and polybutylene adipate terephthalate and/or polybutylene succinate terephthalate; 0.1 to 0.6 percent of antioxidant; the chain extender is 0.01-5%.
8. A process for producing the polyglycolic acid resin composition according to any one of claims 1 to 7, wherein the components comprising polyglycolic acid, polybutylene adipate terephthalate and/or polybutylene succinate terephthalate, a block copolymer, a chain extender and an antioxidant are melt-blended, extruded and pelletized.
9. The process for producing a polyglycolic acid resin composition according to claim 8, wherein:
the melt expansion rate of the polyglycolic acid resin composition after extrusion from an die is less than 200%;
the extrusion temperature is 180-260 ℃; the extrusion speed was 20-500 rpm.
10. The process for producing a polyglycolic acid resin composition according to claim 9, wherein:
the extrusion temperature is 220-250 ℃; the extrusion speed was 50 to 250rpm.
11. A polyglycolic acid resin composition film produced from the polyglycolic acid resin composition according to any one of claims 1 to 7.
12. The polyglycolic acid resin composition film of claim 11, wherein:
the tensile strength of the film is more than or equal to 10MPa, the elongation at break is more than or equal to 800%, and the elastic modulus is more than or equal to 30MPa.
13. The method for producing a film of a polyglycolic acid resin composition according to claim 11 or 12, comprising melting the polyglycolic acid resin composition, compressing the composition, extruding the composition, cooling the composition, stretching the composition, and winding the composition to obtain the film of the polyglycolic acid resin composition.
14. The method for producing a film of a polyglycolic acid resin composition according to claim 13, wherein:
the melting and the compression adopt at least one screw extruder, and the temperature of the screw extruder is 190-260 ℃; the rotating speed is 1-500 rpm; and/or the number of the groups of groups,
the extruded film forming die is a film blowing die or a casting film die, and the film blowing conditions comprise: film blowing temperature is 100-250 deg.f o C, die temperature 210-240 o C, performing operation; the blow-up ratio was (1.5:1) to (6:1).
15. The method for producing a film of a polyglycolic acid resin composition according to claim 14, wherein:
the screw extruder is a single screw extruder or a double screw extruder, and the temperature of the screw extruder is 200-250 ℃; the rotating speed is 1-100 rpm; and/or the number of the groups of groups,
The conditions for film blowing include: the blow-up ratio was (2:1) to (5:1).
16. Use of the polyglycolic acid resin composition film of claim 11 or 12 in a film bag.
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