CN115772317A - Polyglycolic acid resin blend and preparation method and application thereof - Google Patents
Polyglycolic acid resin blend and preparation method and application thereof Download PDFInfo
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- CN115772317A CN115772317A CN202111047580.6A CN202111047580A CN115772317A CN 115772317 A CN115772317 A CN 115772317A CN 202111047580 A CN202111047580 A CN 202111047580A CN 115772317 A CN115772317 A CN 115772317A
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 155
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- 238000002360 preparation method Methods 0.000 title abstract description 15
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- 125000001931 aliphatic group Chemical group 0.000 claims description 8
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- 125000003118 aryl group Chemical group 0.000 claims description 8
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
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- 239000002253 acid Substances 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 2
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- 239000005977 Ethylene Substances 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 18
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- 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 abstract description 2
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- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
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- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-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
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 description 1
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Abstract
The invention relates to a polyglycolic acid resin blend, a preparation method and application thereof, belonging to the field of modification and preparation of high molecular materials. Mainly solves the problems of low toughness and poor processability of polyglycolic acid in the prior art. The polyglycolic acid resin blend comprises the following components in parts by weight: (1) 1 to 20 parts of polyglycolic acid; (2) 99 to 80 parts of an aliphatic aromatic copolyester; due to the synergistic effect between the polyglycolic acid/butylene terephthalate components, the polyglycolic acid resin blend with high toughness is obtained, when the polyglycolic acid is added in a small amount, the elongation at break of the blend film and the injection-molded sample bar are both obviously improved, and unexpected effects are achieved.
Description
Technical Field
The invention relates to the field of high molecular materials, in particular to a polyglycolic acid resin blend and a preparation method and application thereof.
Background
Polyglycolic acid (PGA) is a linear aliphatic polyester of the simplest structure, a typical high crystallinity polymer, and has a stable crystal lattice and a high melting point. PGA has the advantages of excellent biodegradability, high degradation speed, good biocompatibility, good biological reabsorbability, higher mechanical strength (certain indexes are for standard engineering plastics) and the like, and is mainly applied to the fields of medical sutures, drug controlled release carriers, fracture fixing materials, tissue engineering scaffolds, reinforcing materials, oil fields and the like. However, the faster crystallization rate and high crystallinity of PGA result in great brittleness, low impact strength, and easy bending deformation, thereby limiting the applications thereof.
At present, the toughness of PGA can be improved into two categories, one is that certain additives, functional groups and other high molecular materials are added into a PGA matrix by methods of plasticization, blending and the like; and the other is to introduce other monomers through copolymerization or to modify the intrinsic structure of the PGA molecular chain segment by adopting a surface modification method. The blending method is the simplest, economical and feasible modification method, and flexible macromolecules or elastomers such as polybutylene succinate (PBS) Polycaprolactone (PCL) and the like are added. Wanwenjun et al in CN108260451A provide a herbicidal biodegradable mulch film, which adds herbicide into multilayer film by blending, one or more of poly adipic acid/butylene terephthalate (PBAT), polylactic acid (PLA), polycaprolactone (PCL), polyglycolic acid (PGA), polypropylene carbonate (PPC), polybutylene succinate (PBS), polyhydroxyalkanoate (PHA), and poly (butylene succinate) are mixed in any ratio and blended with PBAT as one layer for biodegradable mulch film preparation, PGA is one of the components of one layer of multilayer film, but does not mention mechanical property improvement. In CN109762143A, wangexia et al mentioned that PGA and other easily hydrolyzable polyesters are added to biodegradable copolyesters to obtain a hydrolyzable copolyester, and the hydrolyzable copolyester is prepared by utilizing the rapid degradation property of PGA, and the specific application of the hydrolyzable copolyester in films is focused on the rapid degradation capability of the hydrolyzable copolyester.
Disclosure of Invention
The invention aims to solve the technical problems of poor processing performance of polyglycolic acid and poor brittleness and high toughness in the prior art, and provides a polyglycolic acid resin blend with high toughness. The invention discovers that special toughening effect exists between the low PGA content and the aliphatic aromatic copolyester, and at the moment, the blend has good processing performance due to the low PGA content, so that the application of the PGA can be expanded in the fields of packaging films and the like.
The second technical problem to be solved by the invention is to provide a preparation method for preparing the polyglycolic acid resin blend.
The invention also provides a polyglycolic acid resin blend product prepared by the preparation method suitable for polyglycolic acid resin blends.
The fourth technical problem to be solved by the present invention is to provide an application method suitable for polyglycolic acid resin blend corresponding to one or three technical problems.
In order to solve one of the above technical problems, one of the objects of the present invention is to provide a polyglycolic acid resin blend, which comprises the following components in parts by mass:
(1) 1 to 20 parts of polyglycolic acid (PGA);
(2) 99 to 80 parts of aliphatic aromatic copolyester.
Wherein the polyglycolic acid can be prepared by glycolide ring-opening polymerization or glycolic acid or methyl glycolate polycondensation polymerization; preferably, the polyglycolic acid may have an intrinsic viscosity of 0.9 to 1.8dl/g, more preferably 0.9 to 1.4dl/g. The melting point of the polyglycolic acid may be 200 to 240 ℃.
The aliphatic aromatic copolyester can be selected from copolyesters formed by polycondensation of components containing aliphatic diacid, aromatic diacid and aliphatic diol; preferably, the aliphatic aromatic copolyester can be alpha, omega-aliphatic diacid or copolyester formed by polycondensation of aliphatic diacid containing 2-18 main chain carbon atoms, at least one aromatic diacid and at least one aliphatic diol; preferably at least one of polybutylene terephthalate-co-adipate, polyethylene terephthalate-co-succinate and polybutylene terephthalate-co-succinate.
The melt index of the aliphatic aromatic copolyester is 2-20g/10min under the test conditions of 230 ℃ and 1.05kg, and the melt index is further preferably 2-15g/10min.
The polyglycolic acid resin blend may further comprise a processing aid; the processing aid may be used in an amount of 0.1 to 5 parts by mass, based on 100 parts by mass of the total amount of the polyglycolic acid and the aliphatic aromatic copolyester.
The processing aid can be selected from common aids conventionally used in the field, such as one or two or more of chain extender, antioxidant, opening agent and compatibilizer; in a specific use, said chain extender is preferably at least one of a compound or polymer having a reactive group with a carboxyl or hydroxyl group and a compound containing at least two epoxy functional groups; the antioxidant is preferably selected from one or two or more of hindered phenols, hindered amines, phosphites and thiols, and more preferably is a blend of two or more of antioxidant 1010, antioxidant 1076 and antioxidant 3109; the opening agent is preferably at least one of talcum powder, calcium carbonate, silica, oleamide, ethylene bis-oleamide and stearyl erucamide, and more preferably one or two of silica, calcium carbonate, oleamide, ethylene bis-oleamide and stearyl erucamide; the compatibilizer is preferably selected from styrene reactive resins with reactive functional groups, and the reactive functional groups are preferably selected from at least one of epoxy groups, acid anhydrides and carboxylic acids. Wherein the dosage of each processing aid can be adjusted according to actual needs. For example, the opening agent may be used in an amount of 0.2 to 0.5 parts by weight, the chain extender may be used in an amount of 0.3 to 0.8 parts by weight, and the compatibilizer may be used in an amount of 1 to 4 parts by weight.
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 blend, which comprises the following steps:
mixing the components including polyglycolic acid, aliphatic aromatic copolyester and functional processing aid (if any) according to the required amount, and then carrying out melt blending to obtain the polyglycolic acid resin blend.
Wherein the extrusion temperature may be from 180 ℃ to 260 ℃, more preferably from 200 ℃ to 240 ℃; the rotational speed of the extruder may be 50rpm to 500rpm, more preferably 50rpm to 200rpm.
The third purpose of the invention is to provide a polyglycolic acid resin blend product prepared by the preparation method suitable for polyglycolic acid resin blend.
The fourth object of the present invention is to provide the use of the polyglycolic acid resin blend according to one of the objects of the present invention or the third object of the present invention; preferably in the production of injection-molded parts, films.
In a particular embodiment mode of the present invention,
one of the purposes of the invention is to provide a polyglycolic acid resin blend which comprises the following components in parts by weight:
(1) 1 to 20 parts of polyglycolic acid (PGA);
(2) 99 to 80 parts of an aliphatic aromatic copolyester;
(3) 0.1 to 5 parts of a processing aid.
Wherein,
the polyglycolic acid (PGA) may be specifically used in an amount of 1 to 20 parts (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or any value therebetween or a range of values therebetween, e.g., 3 to 18 parts, 5 to 15 parts); the aliphatic aromatic copolyester may be used in an amount of specifically 99 to 80 parts (e.g., may be 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85, 84, 83, 82, 81, 80 or any value therebetween or a range of values therebetween, such as 97 to 82 parts, 95 to 85 parts); the processing aid may be used in an amount of specifically 0.1 to 5 parts (e.g., may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 2.0, 2.5, 3.0, 3.5, 4, 4.5, 5.0, or any value therebetween or a range of values therebetween).
In the above-mentioned embodiment, the polyglycolic acid may be obtained by ring-opening polymerization or polycondensation polymerization, specifically, by direct condensation polymerization of glycolic acid/ester, or by ring-opening polymerization of glycolide or polycondensation polymerization of glycolic acid or methyl glycolate. The PGA is a main modified body, the aliphatic aromatic copolyester is a selected modified base material, and various processing aids can improve the thermal and mechanical properties of the blended particles.
The polyglycolic acid may have an intrinsic viscosity of 0.9 to 1.8dl/g, and more preferably 0.9 to 1.4dl/g.
The polyglycolic acid may have a melting point of 200 to 240 ℃.
In the above technical solution, the aliphatic aromatic copolyester may be a copolyester formed by polycondensation of components including aliphatic diacid, aromatic diacid, and aliphatic diol.
In the above technical scheme, the aliphatic aromatic copolyester may be alpha, omega-aliphatic diacid or copolyester formed by condensing aliphatic diacid containing 2-18 main chain carbon atoms and at least one aromatic dibasic acid with at least one aliphatic diol. Preferably at least one of polybutylene terephthalate-co-adipate, polyethylene terephthalate-co-succinate and polybutylene terephthalate-co-succinate.
The melt index of the aliphatic aromatic copolyester is 2-20g/10min under the test conditions of 230 ℃ and 1.05kg, and the melt index is further preferably 2-15g/10min.
In the above technical solution, the processing aid may be selected from common aids conventionally used in the art, such as at least one (e.g., one or two or more) of chain extender, antioxidant, opening agent and compatibilizer;
wherein,
the chain extender may preferably be at least one of a compound or polymer having a reactive group with a carboxyl group or a hydroxyl group and a compound having at least two epoxy functional groups;
the antioxidant can be preferably one or two or more of hindered phenols, hindered amines, phosphites and thiols, and can be a blend of two or more of antioxidant 1010, antioxidant 1076 and antioxidant 3109;
the opening agent can be preferably one or two of talcum powder, calcium carbonate, silica, oleamide, ethylene bisoleamide and stearyl erucamide; more preferably one or two of silica, calcium carbonate, oleamide, ethylene bisoleamide and stearyl erucamide;
the compatibilizer may preferably be a styrene-based reactive resin having a reactive functional group selected from at least one of an epoxy group, an acid anhydride, and a carboxylic acid.
According to the invention, through the toughening synergistic effect between the blend of the raw material combination, especially the polyglycolic acid/aliphatic aromatic copolyester component, the high-toughness polyglycolic acid resin blend film and injection molding are obtained, and when the polyglycolic acid is added in a small amount, the elongation at break of the product is greater than that of the aliphatic aromatic copolyester material and the simple addition of the aliphatic aromatic copolyester material, so that an unexpected effect is obtained.
The other purpose of the invention is to provide the preparation method of the polyglycolic acid resin blend with high toughness, which can adopt melt blending reaction extrusion, and the required amount of each component is plasticized, kneaded, compressed, extruded, cooled and granulated under a molten state to obtain the polyglycolic acid resin blend with high toughness.
The method specifically comprises the following steps:
mixing the components including polyglycolic acid, aliphatic aromatic copolyester and processing aid in required amount, and then melting, blending and extruding the mixture by a double-screw extruder to obtain the polyglycolic acid resin blend.
Wherein,
the extrusion temperature may be from 180 ℃ to 260 ℃, more preferably from 200 ℃ to 250 ℃; the screw speed of the extruder may be 50rpm to 500rpm, more preferably 50rpm to 200rpm.
The third object of the present invention is to provide a polyglycolic acid resin blend obtained by the preparation method described in the second object of the present invention.
It is a fourth object of the present invention to provide the use of the polyglycolic acid resin blends described as one or three of the above objects of the present invention, especially where high toughness is desired.
In the above technical solutions, the applications are not particularly limited, and include but not limited to wide applications in medicine, daily necessities, oil recovery, and the like. There is also no particular limitation on the type of product, including but not limited to applications such as in the preparation of injection molded parts, films, among others.
The materials and preparation methods used in the present invention are briefly described below:
1. polyglycolic acid
Polyglycolic acid (PGA), also known as Polyglycolic acid, is the simplest structural linear aliphatic polyester. PGA can be produced by a melt polycondensation method of glycolic acid, a ring-opening polymerization method of glycolide, or the like. Polyglycolic acid is a typical high crystallinity polymer that is lattice stable and has a relatively high melting point. The relatively fast crystallization speed and high crystallinity of PGA result in high brittleness, high modulus, but low impact strength, and the products are easily brittle, thus limiting their applications.
Polyglycolic acid has excellent biodegradability, can enter a human body circulatory system for in vivo degradation and discharge out of the body, can also degrade in an in vitro environment, and is mainly applied to the fields of medical sutures, drug controlled release carriers, fracture fixation materials, tissue engineering scaffolds, reinforcing materials and the like. Through solution spinning and melt spinning, the polyglycolic acid can be processed into a surgical suture line, has strong tensile strength and can be maintained for a sufficient time, and is suitable for wound suturing of deep tissues.
2. Aliphatic aromatic copolyester
Considering that polyglycolic acid PGA is a polymer with poor rigidity, toughness and processability, the aliphatic aromatic copolyester is selected to improve the flexibility of the PGA, improve the processability of the PGA and expand the application range.
The aliphatic aromatic copolyester comprises copolyester formed by condensation polymerization of aliphatic diacid, aromatic diacid and aliphatic diol, and can be obtained by copolymerization of at least one alpha, omega-aliphatic diacid or aliphatic diacid containing 2-18 main chain carbon atoms and at least one aromatic dibasic acid condensed with at least one aliphatic diol.
The aliphatic aromatic copolyester suitable for the present invention may be preferably at least one of polybutylene terephthalate-co-adipate, polyethylene terephthalate-co-adipate glycol esterification, polyethylene terephthalate-co-succinate glycol esterification, and polybutylene terephthalate-co-succinate glycol esterification.
3. Method for preparing high-toughness polyglycolic acid resin blend
In the method for preparing the high-toughness polyglycolic acid resin blend, melt blending reaction extrusion is adopted, and required amounts of the components are uniformly mixed in a molten state to obtain the high-toughness polyglycolic acid resin blend.
One concrete embodiment is that the components including polyglycolic acid, aliphatic aromatic copolyester and functional processing aid are respectively metered into a double-screw extruder according to a certain feeding proportion for extrusion granulation. The other concrete embodiment is that the components including the polyglycolic acid, the aliphatic aromatic copolyester and the functional processing aid are blended according to the required proportion and then are added into a double-screw extruder for extrusion granulation.
In the step of preparing the polyglycolic acid resin blend, the extrusion temperature suitable for the present invention may be 180 to 260 c, preferably 200 to 250 c. The rotation speed of the extruder is preferably 50rpm to 500rpm, more preferably 50rpm to 200rpm.
The invention provides a polyglycolic acid resin blend and a preparation method of a film and an injection molding piece thereof, and the polyglycolic acid resin blend with high toughness and the film or the injection molding piece thereof are obtained after melt blending, extrusion, cooling and granulation, so that the processability is effectively improved, the problems of poor toughness and incapability of forming the film of the polyglycolic acid are well solved, and the polyglycolic acid resin blend and the preparation method of the film or the injection molding piece thereof can be applied to various high-toughness packaging materials. In particular, the blend product obtained by the film blowing process or the injection molding process has the toughening synergistic effect of 1+1 >.
Drawings
FIG. 1 is a graph showing the change in elongation at break of injection-molded bars of example 8 according to the PGA content in the blend, and the dotted line in the graph is an addition theoretical value calculated according to the linear addition rule.
FIG. 2 is a graph showing the change in fracture energy depending on the PGA content in the blend, for injection-molded bars of example 8, wherein the dotted line is an addition theoretical value calculated according to the linear addition rule.
FIG. 3 shows the tensile strength test results of the film of example 9.
Where MD indicates the film in the machine blown film stretch direction and CD indicates the film perpendicular to the machine blown film stretch direction.
FIG. 4 shows the results of elongation at break test of the film of example 9.
FIG. 5 is a graph showing the change in elongation at break of the film prepared in example 9 depending on the PGA content in the blend, and the dotted line in the graph is an addition theoretical value calculated according to the linear addition rule.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Source of raw materials
The raw materials used in the examples and comparative examples were all commercially available.
Polyglycolic acid (PGA) produced by Corbion Purac, having an intrinsic viscosity of 1.0 to 1.4dl/g and a melting point of 200 to 230 ℃;
aliphatic aromatic copolyesters available from BASF under the trade name
FC-1200 aliphatic aromatic copolyester PBAT particles with a melt index of 5.5g/10min;
a compatibilizer manufactured by France Akema under the brand number
3210；
Chain extenders, manufactured by Pasteur, germany under the brand name
AR-4370；
A mouth-opening agent, oleamide, jiangxi Zhi plastification science and technology Limited.
The invention carries out performance measurement according to the following method:
specimen tensile test: measured according to ISO 527-2 using a model 3344 product tester from INSTRON, blue hill version 2.31. The sample was cut into Type 2 according to ISO 527-2 standard, and placed in a Bluepard BPS-100CB constant temperature and humidity cabinet (temperature 23 ℃ C., relative humidity 50%) of Shanghai-Hengyu scientific instruments Co., ltd. For 24 hours. During testing, the initial clamp spacing is 50mm, the test tensile rate is 2mm/min, each sample is tested for 5 times, and the average value is taken.
Film tensile test: measured according to ISO 527-3 using a model 3344 product tester from INSTRON, blue hill version 2.31. The sample was cut into Type 5 according to ISO 527-3, and placed in a Bluepard BPS-100CB constant temperature and humidity cabinet (temperature 23 ℃ C., relative humidity 50%) of Shanghai-Hengyu scientific instruments Co., ltd. For 24 hours. During testing, the initial clamp spacing is 50mm, the test tensile rate is 500mm/min, each sample is tested 5 times, and the average value is taken.
The invention is further illustrated by the following specific examples, without restricting the inventive content to the scope of the examples presented.
Comparative example 1
A certain amount of brands are
The aliphatic aromatic copolyester PBAT particles (poly (butylene adipate)/terephthalate) of FC-1200 adopt HAAKE TM And (5) carrying out injection molding by using a Minilab micro injection molding machine. In the experiment process, the temperature of the material cavity is set to be 250 ℃, and the temperature of the die is set to be 60 ℃. Before the test is started, a total of about 15g of samples are loaded into a material cavity by 3-4 times, each time, the samples are compacted by a pressure lever, after the samples are loaded, the experiment is started, a pre-pressing and preheating process is carried out, the pre-pressing set pressure is 500bar, after 20 seconds(s) of pre-pressing and preheating, the pressure of melted particles is maintained for 10s at 100bar, finally, a melted sample strip is extruded into an injection mold through a neck mold, and finally, the mold is opened to take out the sample strip, and the sample strip is packaged and collected for later use.
Comparative example 2
Using a certain amount of Corbion Purac PGA particles as HAAKE TM And (4) carrying out injection molding by using a Minilab micro injection molding machine. In the experiment process, the temperature of the material cavity is set to be 250 ℃, and the temperature of the die is set to be 60 ℃. Before the test is started, a total of about 15g of samples are loaded into a material cavity by 3-4 times, each time, the samples are compacted by a compression bar, after the samples are loaded, the experiment is started, a pre-pressing and preheating process is carried out, the pre-pressing set pressure is 500bar, after 20s of pre-pressing and preheating, the pressure of melted particles is maintained for 10s at 100bar, finally, a melted sample strip is extruded into an injection mold through a mouth mold, and finally, the mold is opened to take out the sample strip, and the sample strip is packaged and collected for later use.
Comparative example 3
A certain amount of Corbion Purac PGA particles manufactured by HAAKE, manufactured by Thermo Fisher Scientific Inc., USA TM The Rheomex OS single-screw extrusion film blowing equipment is used for blowing the film, the screw diameter of the extruder is 19mm, the length-diameter ratio is 25, and the extruder is provided with a standard metering screw of 3. Enters an extruder through a feeder, and the extruderThe heating temperatures of (a) are: the torque ranges from 10 to 50% when the screw is stably operated at 200rpm, at 200 ℃,220 ℃,220 ℃,220 ℃,220 ℃,220 ℃,220 ℃,220 ℃ and 220 ℃. The extruder was fitted with a circular die (gap 0.5 mm) of 19.5mm diameter and the melt was poorly uniform after passing through the screw, and the melt was not stressed and stretched immediately to break. The film can not be blown by adjusting the rotating speed and the blow-up ratio of the screw.
Comparative example 4
A certain number is given as
Poly (butylene adipate terephthalate)/PBAT particles of FC-1200 HAAKE manufactured by Thermo Fisher Scientific Inc. of USA TM The Rheomex OS single-screw extrusion film blowing equipment is used for blowing the film, the screw diameter of the extruder is 19mm, the length-diameter ratio is 25, and the extruder is provided with a standard metering screw of 3. Feeding the mixture into an extruder through a feeder, wherein the heating temperature of the extruder is as follows: the torque ranges from 10 to 50% when the screw is set to run stably at 200rpm, 220 ℃,220 ℃,220 ℃,220 ℃,220 ℃,220 ℃,220 ℃ and the screw speed is set to run stably at 200rpm. The extruder is matched with a circular opening film (the gap is 0.5 mm) with the diameter of 19.5mm, and after the melt is extruded, the melt is subsequently cooled, shaped, drawn and rolled to prepare the thin film.
Comparative example 5
Weighing the following raw materials in proportion: PGA (the company Corbion Purac, melt index of 14g/10 min) 80 parts by weight, PBAT (
FC-1200), 0.3 part of opening agent, 0.5 part of chain extender and 2 parts of compatibilizer.
PolyLab HAAKE by ThermoFisher technologies, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was pelletized by extrusion. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,220 ℃,230 ℃,230 ℃,240 ℃,250 ℃,250 ℃,240 ℃,230 ℃ and 220 ℃ with the screw speed set at 200rpm. When the engine runs stably, the torque ranges from 20% to 60%. The extruder is provided with a circular mouth mold with the diameter of 3mm, and a sample strip is extruded from the mouth mold, is air-cooled and then is cut into cylindrical particles with the diameter of about 3mm by a granulator. The particles were collected, evacuated in a vacuum oven at 60 ℃ for 4 hours (h), and packaged for use.
[ COMPARATIVE EXAMPLE 6 ]
Weighing the following raw materials in proportion: 90 parts by weight of PGA (Corbion Purac, melt index 14g/10 min), PBAT (PBAT)
F C-1200), 0.3 part of opening agent, 0.5 part of chain extender and 2 parts of compatibilizer. PolyLab HAAKE by ThermoFisher technologies, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,220 ℃,230 ℃,230 ℃,240 ℃,250 ℃,250 ℃,240 ℃,230 ℃ and 220 ℃, with the screw speed set at 200rpm. In steady operation, the torque ranges from 20 to 60%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
Comparative example 7
Weighing the following raw materials in proportion: PGA (the company Corbion Purac, melt index of 14g/10 min) 95 parts by weight, PBAT (
F C-1200), 0.3 part of opening agent, 0.5 part of chain extender and 2 parts of compatibilizer. PolyLab HAAKE by ThermoFisher technologies, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was pelletized by extrusion. The extruder has 11 segments from the feeding port to the die, and is numbered from 1 to 11, wherein segment 1 only starts to feedThe material is heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,220 ℃,230 ℃,230 ℃,240 ℃,250 ℃,250 ℃,240 ℃,230 ℃ and 220 ℃, with the screw speed set at 200rpm. When the engine runs stably, the torque ranges from 20% to 60%. The extruder is provided with a circular mouth mold with the diameter of 3mm, and a sample strip is extruded from the mouth mold, is air-cooled and then is cut into cylindrical particles with the diameter of about 3mm by a granulator. And collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for later use.
[ example 1 ]
Weighing the following raw materials in proportion: PGA (Corbion Purac, 14g/10min melt index) 3 parts by weight, PBAT (
FC-1200) 97 parts by weight, an opening agent oleamide 0.3 parts by weight, a chain extender 0.5 parts by weight, and a compatibilizer 2 parts by weight. PolyLab HAAKE by ThermoFisher technologies, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,220 ℃,230 ℃,230 ℃,240 ℃,250 ℃,250 ℃,240 ℃,230 ℃ and 220 ℃, with the screw speed set at 200rpm. In steady operation, the torque ranges from 20 to 60%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
[ example 2 ]
Weighing the following raw materials in proportion: PGA (the company Corbion Purac, melt index of 14g/10 min) 5 parts by weight of PBAT (B A:)
FC-1200), 0.3 part of opening agent, 0.5 part of chain extender and 2 parts of compatibilizer. PolyLab HAAKE by ThermoFisher technologies, USA TM Rheomex OS PTW16 co-rotating twin screw extruder (screw diameter)16mm, l/D = 40) extrusion granulation. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, where section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,220 ℃,230 ℃,230 ℃,240 ℃,250 ℃,250 ℃,240 ℃,230 ℃ and 220 ℃, with the screw speed set at 200rpm. In steady operation, the torque ranges from 20 to 60%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
[ example 3 ]
Weighing the following raw materials in proportion: PGA (Corbion Purac corporation, melt index of 14g/10 min) 10 parts by weight of PBAT (B A)
F C-1200), the opening agent by weight part is 0.3, the chain extender by weight part is 0.5, and the compatibilizer by weight part is 2. PolyLab HAAKE by ThermoFisher technologies, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was pelletized by extrusion. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, where section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,220 ℃,230 ℃,230 ℃,240 ℃,250 ℃,250 ℃,240 ℃,230 ℃ and 220 ℃, with the screw speed set at 200rpm. In steady operation, the torque ranges from 20 to 60%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
[ example 4 ]
Weighing the following raw materials in proportion: PGA (the company Corbion Purac, melt index of 14g/10 min) 15 parts by weight, PBAT (
FC-1200) 85 parts by weight, opening agent 0.3 parts by weight, chain extender 0.5 parts by weight, and compatibilizer 2 parts by weight. From the United statesPolyLabHAAKE from ThermoFisher technologies Inc TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was pelletized by extrusion. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,220 ℃,230 ℃,230 ℃,240 ℃,250 ℃,250 ℃,240 ℃,230 ℃ and 220 ℃, with the screw speed set at 200rpm. When the engine runs stably, the torque ranges from 20% to 60%. The extruder is provided with a circular mouth mold with the diameter of 3mm, and a sample strip is extruded from the mouth mold, is air-cooled and then is cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
[ example 5 ]
Weighing the following raw materials in proportion: 20 parts by weight of PGA (Corbion Purac, melt index 14g/10 min), PBAT (PBAT)
FC-1200), 0.3 part of opening agent, 0.5 part of chain extender and 2 parts of compatibilizer. PolyLab HAAKE by ThermoFisher technologies, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,220 ℃,230 ℃,230 ℃,240 ℃,250 ℃,250 ℃,240 ℃,230 ℃ and 220 ℃, with the screw speed set at 200rpm. When the engine runs stably, the torque ranges from 20% to 60%. The extruder is provided with a circular mouth mold with the diameter of 3mm, and a sample strip is extruded from the mouth mold, is air-cooled and then is cut into cylindrical particles with the diameter of about 3mm by a granulator. And collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for later use.
[ example 6 ] A method for producing a polycarbonate
A total of 9 particles from examples 1 to 4 and comparative examples 1, 2, 5, 6 and 7 were placed in an INSTRON melt flow Rate tester, CEAST MF20, at a temperature of 230 ℃ and a pressure of 1.05 kg. The results are shown in table 1 below.
TABLE 1 melt index of the blended particles
[ example 7 ]
Examples 1 to 4 and comparative examples 5, 6 and 7, a total of 7 particles, were subjected to spline injection by HAAKE Minilab mini injection molding according to the procedure of comparative example 1. In the experiment process, the temperature of the material cavity is set to be 250 ℃, and the temperature of the die is set to be 60 ℃. Before the test is started, a total of about 15g of samples are loaded into a material cavity by 3-4 times, each time, the samples are compacted by a compression bar, after the samples are loaded, the experiment is started, a pre-pressing and preheating process is carried out, the pre-pressing set pressure is 500bar, after 20s of pre-pressing and preheating, the pressure of melted particles is maintained for 10s at 100bar, finally, a melted sample strip is extruded into an injection mold through a mouth mold, and finally, the mold is opened to take out the sample strip, and the sample strip is packaged and collected for later use.
[ example 8 ]
The 7 types of test pieces prepared in example 7 and the test pieces of comparative examples 1 and 2 were first subjected to a constant temperature and humidity pretreatment at 23 ℃ and 50% RH for 24 hours, and tensile properties of the test pieces were measured according to the procedure described above, and the values are shown in Table 2. FIG. 1 is a graph showing the relationship between elongation at break and the PGA content in an injection-molded bar, and FIG. 2 is a graph showing the relationship between fracture energy and the PGA content in an injection-molded bar.
TABLE 2 mechanical Properties of injection-molded specimens
Comparing the mechanical properties of the PGA/PBAT injection molded bars in Table 2, FIG. 1 and FIG. 2, it was found that at high PGA contents (comparative examples 5-7), the toughness of the PGA/PBAT blend injection molded parts was lower than that of the less tough PGA in PBAT and PGA, in particular, the elongation at break and energy at break of the blend injection molded parts containing 5% to 20% of PBAT were lower than those of the lower one of PBAT and PGA (i.e., PGA), and these results showed an anti-synergistic effect, showing that the properties of the injection molded parts obtained by blending were worse than that of the pure PGA, and that the blends prepared by both were not suitable for injection molding applications.
It has been unexpectedly found that when PBAT is blended with a small amount of PGA (< 20%) (examples 1-4) to produce injection molded parts having higher elongation to break values than PBAT and PGA, the elongation to break values of the example 1 splines exceed those of the comparative example 1 pure PBAT splines by as much as 181% (791% -610% = 181%). Examples 1-4 have fracture energies in excess of that of pure PBAT bars by 8-12MJ/m 2 Since PGA itself is an extremely brittle material, the toughness of the PBAT component after addition is definitely higher than that of the high toughness, which is a totally unexpected synergistic toughening phenomenon found at specific PGA contents. This unexpected result improves the performance and application range of PGA/PBAT blend injection molded articles containing less than 20% PGA.
[ example 9 ]
The particles of examples 1 to 5 and comparative examples 5 to 7 were sufficiently dried, and then HAAKE manufactured by Thermo Fisher Scientific Inc. of the United states TM Blown films were prepared on a Rheomex OS single screw extruder with a screw diameter of 19mm and a length to diameter ratio of 25 equipped with a 3 TM PolyLab TM OS torque rheometer platform control. Feeding the mixture into an extruder through a feeder, wherein the heating temperature of the extruder is as follows: 200 ℃,220 ℃,220 ℃,220 ℃,220 ℃,220 ℃ and 220 ℃, the screw rotation speed is set to be 200rpm, and when the screw is in steady operation, the torque range is 10-50%. The extruder is provided with a circular opening film (with the gap of 0.5 mm) with the diameter of 19.5mm, and after the melt is extruded, the melt is cooled, shaped, pulled and rolled to prepare the thin film.
Table 3 film blowing of example 9
In Table 3, "-" indicates that film formation was impossible.
While the pure PGA in comparative example 3 and the high content PGA blends of comparative examples 5 to 7 could not be made into films due to poor processability, the blend modified by melt blending had better film forming property, and the elongation at break property of the blend was superior to that of the pure PBAT film at low PGA content, and the specific film mechanical parameters are shown in FIG. 3, FIG. 4 and FIG. 5.
From the experimental results, it was found that the toughness of the blend was close to that of PGA itself and the processability was significantly deteriorated (stable blown film production could not be performed) at a high PGA content, whereas excellent toughness-enhancing change of the blend was found at a low PGA content within the range specified in the present application.
It is not difficult to find out the comparison of the mechanical properties of the PGA/PBAT film, when the PBAT and a small amount of PGA (less than or equal to 20 percent) are blended, the prepared film has the elongation at break which is larger than that of the PBAT film with high toughness in the PBAT and the PGA, and the PGA is a material with extremely high brittleness, and after the small amount of PGA is added, the synergistic toughening effect under the special PGA content is unexpectedly found, and the toughness and the application range of the PBAT/PGA blend film containing the PGA of about 20 percent or less are improved.
The theoretical properties of some polymer blends can be generally presumed by using the rule of linear addition, which can be expressed by the following formula: y = x 1 Y 1 +x 2 Y 2 Wherein Y is a property of the blend, x 1 And Y 1 Is the concentration and nature of component 1; x is a radical of a fluorine atom 2 And Y 2 Is the concentration and nature of component 2. The elongation at break, the energy at break and the like of the polyglycolic acid alcohol and PBAT composition can be calculated out theoretically predicted values by utilizing addition rules, namely, the theoretically predicted values are defined as 'theoretical addition values', and the values can be compared with the experimentally detected values of elongation at break, energy at break and the like. The concentration of the components can be expressed by mass fraction or volume fraction, the mass fraction is selected to calculate a theoretical value, and the dotted line in fig. 1 and 2 is an addition theoretical value calculated according to a linear addition rule.
Compared with the theoretical prediction value of the PGA/PBAT blend, the experimental results shown in figures 1, 2 and 5 show that the injection-molded splines and films of the polyglycolic acid resin blend prepared by the invention have special effects beyond the theoretical prediction value under the condition of low PGA content (less than or equal to 20%), the elongation at break of the splines and film products is even far higher than the simple linear addition of the PBAT and the PGA, and the obvious toughening synergistic effect is shown, so that the application value of the PGA/PBAT blend within the range of the PGA content less than or equal to 20% is greatly expanded.
Claims (10)
1. A polyglycolic acid resin blend comprises the following components in parts by mass:
(1) 1 to 20 parts of polyglycolic acid;
(2) 99 to 80 parts of aliphatic aromatic copolyester.
2. The polyglycolic acid resin blend according to claim 1, wherein:
the polyglycolic acid is prepared by glycolide ring-opening polymerization or glycolic acid or methyl glycolate polycondensation polymerization;
preferably, ,
the polyglycolic acid has an intrinsic viscosity of 0.9 to 1.8dl/g, more preferably 0.9 to 1.4dl/g.
3. The polyglycolic acid resin blend according to claim 1, wherein:
the aliphatic aromatic copolyester is formed by polycondensation of components including aliphatic diacid, aromatic diacid and aliphatic diol;
the aliphatic aromatic copolyester is preferably alpha, omega-aliphatic diacid or copolyester formed by condensing aliphatic diacid containing 2-18 main chain carbon atoms and at least one aromatic dibasic acid and at least one aliphatic diol; more preferably at least one of poly (butylene terephthalate-co-adipate), poly (ethylene terephthalate-co-succinate) and poly (butylene terephthalate-co-succinate).
4. The polyglycolic acid resin blend according to claim 1, wherein:
the melt index of the aliphatic aromatic copolyester is 2-20g/10min under the test conditions of 230 ℃ and 1.05kg, and the melt index is further preferably 2-15g/10min.
5. The polyglycolic acid resin blend according to claim 1, which comprises a processing aid;
the processing aid is used in an amount of 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the polyglycolic acid and the aliphatic aromatic copolyester.
6. The polyglycolic acid resin blend according to claim 5, wherein:
the processing aid is selected from one or two or more of a chain extender, an antioxidant, an opening agent and a compatibilizer; the chain extender is preferably at least one of a compound or polymer having a reactive group with a carboxyl group or a hydroxyl group and a compound having at least two epoxy functional groups; the antioxidant is preferably selected from one or two or more of hindered phenols, hindered amines, phosphites and thiols; the opening agent is preferably at least one of talcum powder, calcium carbonate, silica, oleamide, ethylene bisoleamide and stearyl erucamide; the compatibilizer is preferably a styrene-based reactive resin having a reactive functional group, and the reactive functional group is preferably at least one selected from an epoxy group, an acid anhydride, and a carboxylic acid.
7. The method for preparing polyglycolic acid resin blend according to any one of claims 1 to 6, comprising the steps of:
mixing the components including polyglycolic acid and aliphatic aromatic copolyester in required amount, and then performing melt blending and extrusion to obtain the polyglycolic acid resin blend.
8. The method for preparing polyglycolic acid resin blend according to claim 7, wherein:
the extrusion temperature is 180 ℃ to 260 ℃, and more preferably 200 ℃ to 250 ℃; the rotational speed of the extruder is 50 to 500rpm, preferably 50 to 200rpm.
9. The polyglycolic acid resin blend obtained by the production method according to claim 7 or 8.
10. Use of a polyglycolic acid resin blend according to any one of claims 1 to 6, 9 or a polyglycolic acid resin blend produced by the production method according to claim 7 or 8; preferably in the production of injection-molded parts, films.
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| CN202111047580.6A Pending CN115772317A (en) | 2021-09-08 | 2021-09-08 | Polyglycolic acid resin blend and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118146619A (en) * | 2024-04-03 | 2024-06-07 | 海南大学 | A PBAT/PGA/talcum powder composite material and preparation method thereof |
| CN118834506A (en) * | 2023-04-24 | 2024-10-25 | 中国石油化工股份有限公司 | Polyglycolic acid-based film and its preparation method and application |
| WO2025082201A1 (en) * | 2023-10-18 | 2025-04-24 | 中国石油化工股份有限公司 | Polymer composition, preparation method therefor and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105793040A (en) * | 2013-12-10 | 2016-07-20 | 巴斯夫欧洲公司 | Polymer mixture for barrier film |
| CN112280257A (en) * | 2020-11-02 | 2021-01-29 | 兰州鑫银环橡塑制品有限公司 | Full-biodegradable mulching film for dry-land corn and preparation method thereof |
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2021
- 2021-09-08 CN CN202111047580.6A patent/CN115772317A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105793040A (en) * | 2013-12-10 | 2016-07-20 | 巴斯夫欧洲公司 | Polymer mixture for barrier film |
| CN112280257A (en) * | 2020-11-02 | 2021-01-29 | 兰州鑫银环橡塑制品有限公司 | Full-biodegradable mulching film for dry-land corn and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 冯申 等: "PGA/PBAT复合材料的性能及研究应用", 《中国塑料》, vol. 34, no. 11, pages 36 - 40 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118834506A (en) * | 2023-04-24 | 2024-10-25 | 中国石油化工股份有限公司 | Polyglycolic acid-based film and its preparation method and application |
| WO2025082201A1 (en) * | 2023-10-18 | 2025-04-24 | 中国石油化工股份有限公司 | Polymer composition, preparation method therefor and use thereof |
| CN118146619A (en) * | 2024-04-03 | 2024-06-07 | 海南大学 | A PBAT/PGA/talcum powder composite material and preparation method thereof |
| CN118146619B (en) * | 2024-04-03 | 2025-05-16 | 海南大学 | PBAT/PGA/talcum powder composite material and preparation method thereof |
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