CN116003765A - Block copolymer of aliphatic-aromatic copolyester and polyglycolic acid, and preparation method and application thereof - Google Patents
Block copolymer of aliphatic-aromatic copolyester and polyglycolic acid, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the modification of aliphatic-aromatic copolyester and polyglycolic acid blend, and discloses a block copolymer of aliphatic-aromatic copolyester and polyglycolic acid, a preparation method and application thereof, wherein the block copolymer comprises a polyglycolic acid block and an aliphatic-aromatic copolyester block; the block copolymer contains an A-B diblock copolymer or an A-B-A triblock copolymer, wherein the block A is polyglycolic acid and the block B is aliphatic-aromatic copolyester. The block copolymer of the present invention can improve the compatibility of PGA and aliphatic-aromatic copolyester blend, and improve the mechanical properties of the blend, for example, the toughness and tensile strength of the PGA and aliphatic-aromatic copolyester blend, in application as a compatibilizer.
Description
Technical Field
The invention relates to polymer blending modification, in particular to a polymer containing a segmented copolymer of aliphatic-aromatic copolyester and polyglycolic acid, a preparation method and application thereof.
Background
Polyglycolic acid (PGA), also known as polyglycolide or polyglycolic acid, has been widely used in the fields of medical sutures, drug controlled release carriers, fracture fixation materials, tissue engineering scaffolds, reinforcing materials, etc., because of its excellent biodegradability, biocompatibility and high mechanical strength. In addition, the material has good water/oxygen barrier performance, is one of materials with the best comprehensive barrier performance, and has the barrier performance to water vapor which is about 100 times higher than that of polylactic acid (PLA) and is similar to that of Polyethylene (PE). However, the high crystallinity of polyglycolic acid results in not only a relatively high melting point, but also poor toughness at room temperature, which greatly limits its use in a wider range of applications.
The aliphatic-aromatic copolyester is used as a copolymer of aliphatic polyester and aromatic polyester, combines the advantages of the two components, and has high toughness and good degradability of the aliphatic polyester, and high strength and excellent thermal performance of the aromatic polyester. The most typical aliphatic-aromatic copolyesters are polybutylene adipate terephthalate (PBAT) which is a random copolymer of polybutylene adipate (BA) and polybutylene terephthalate (BT) and polybutylene succinate (PBST) which is a random copolymer of polybutylene succinate (BS) and polybutylene terephthalate (BT). Under the drive of environmental protection policy, PBAT has been widely used in shopping bags, packaging, mulching films, textiles and other fields. Compared with PBAT, the PBST has the same excellent thermal and mechanical properties, and the succinic acid can be obtained from the bio-based raw material through a fermentation method, so that partial bio-based PBAT or PBST is synthesized, and the reduction of carbon emission is facilitated.
Therefore, if polyglycolic acid can be combined with aliphatic-aromatic copolyesters, it is expected to obtain a material having excellent biodegradability, barrier properties and mechanical properties at the same time. However, because the polyglycolic acid and the aliphatic-aromatic copolyester have poor compatibility, the direct blending effect is not ideal, and the mechanical properties cannot be improved.
Chinese patent application CN 111647144A (Shanghai Pu Jing chemical industry, 2020.9.11) discloses a method for adjusting the molecular chain structure of polyglycolic acid, by adding some functional groups (hydrophilic-hydrophobic groups-OH, -COOR, etc.) or chain segments (branching, copolymerization, etc.) with special properties to change the molecular structure, thereby changing the original molecular characteristics of polyglycolic acid. However, it is a low temperature nitrogen-protected reaction, the reaction conditions are severe, the reaction time is long, at least 50 minutes, and long reaction time can lead to thermal decomposition or degradation of PGA to form by-products with color or odor.
Chinese patent application CN 112358708A (Shenzhen Co., ltd., 2021.02.12) discloses a biodegradable blown film modified material with high starch content and a preparation method thereof. In the method, PBAT-g-MAH and PLA-GMA are adopted as compatilizers of PBAT and PGA to improve the mechanical properties of the obtained blend, but the improvement effect still needs to be further improved.
There is a continuing need in the art to address the problem of poor compatibility between polyglycolic acid and aliphatic-aromatic copolyesters. Therefore, how to further increase the compatibility of both aliphatic-aromatic copolyesters and polyglycolic acid blends is a problem that currently needs to be addressed.
Disclosure of Invention
Aiming at the technical problems that the polyglycolic acid and the aliphatic-aromatic copolyester in the prior art have poor compatibility, ideal performance is difficult to obtain by direct blending, and mechanical properties such as toughness cannot be effectively improved. The invention provides a polymer containing a block copolymer of aliphatic-aromatic copolyester and polyglycolic acid, a preparation method and application thereof, wherein the block copolymer can improve the compatibility of PGA and aliphatic-aromatic copolyester blend and improve the mechanical property of the blend in the application of the block copolymer as a compatilizer.
It is an object of the present invention to provide a block copolymer comprising a polyglycolic acid block and an aliphatic-aromatic copolyester block; the block copolymer contains an A-B diblock copolymer or an A-B-A triblock copolymer, wherein the block A is polyglycolic acid and the block B is aliphatic-aromatic copolyester.
The content of the block a and the block B is selected to be wide, and in a preferred embodiment of the present invention, the content of the block a is 1 to 99 mass%, preferably 65 to 95 mass% with respect to the total mass of the block a and the block B; the content of the block B is 1 to 99% by mass, preferably 5 to 40% by mass.
In a preferred embodiment of the invention, the block B is a copolyester comprising an aliphatic diacid and/or an aromatic diacid, and an aliphatic diol, subjected to polycondensation.
In a more preferred embodiment of the present invention, the block B is a copolyester of at least one of an α, ω -aliphatic diacid and an aromatic diacid having 2 to 18 main chain carbon atoms, condensed with at least one aliphatic diol.
In a still more preferred embodiment of the present invention, the block B is at least one of poly (butylene adipate-co-terephthalate), poly (ethylene terephthalate) and poly (butylene terephthalate).
In a preferred embodiment of the invention, the blocks B are polybutylene adipate terephthalate and/or polybutylene succinate terephthalate. In a preferred embodiment of the invention, the weight average molecular weight of the block B is from 1000 to 200000g/mol, preferably from 20000 to 100000g/mol, more preferably from 40000 to 90000g/mol. In this preferred embodiment, the preparation is more convenient.
In a preferred embodiment of the present invention, the block copolymer comprises a copolymer of the formula (I) and/or (II):
wherein R in formula (I) and formula (II) 1 Each independently is
Or alternatively
In a preferred embodiment of the invention, the weight average molecular weight of the block copolymer is 20000 to 200000g/mol, preferably 80000 to 160000g/mol, and may be, for example, 80000, 90000, 100000, 110000, 120000, 130000, 140000, 150000, 160000g/mol, and any interval or any value between any two.
In a preferred embodiment of the invention, the block copolymer has a polydispersity of 1 to 3, preferably 1 to 2.
In a preferred embodiment of the present invention, the block copolymer is prepared by copolymerizing raw materials including glycolide and aliphatic-aromatic copolyesters.
It is a further object of the present invention to provide a process for preparing the block copolymer described above, which comprises melt blending the components comprising the desired amounts of glycolide, aliphatic-aromatic copolyester and catalyst, followed by cooling to obtain the block copolymer.
In a preferred embodiment of the present invention, the ratio of glycolide to aliphatic-aromatic copolyester is 100 by mass: 1-99, preferably 100:5-40.
In a preferred embodiment of the invention, the ratio of glycolide to catalyst is 100 by mass: (0.005-1), preferably 100: (0.01-0.5).
In a preferred embodiment of the present invention, the weight average molecular weight of the aliphatic-aromatic copolyester is 1000 to 200000g/mol, preferably 20000 to 100000g/mol, more preferably 40000 to 90000g/mol; in a preferred embodiment of the present invention, 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.
In a preferred embodiment of the present invention, the catalyst is a salt compound corresponding to at least one of a group IIA-VA metal element and a 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 a preferred embodiment of the present invention, the temperature of the melt blending reaction is 180-250 ℃, preferably 210-230 ℃; the reaction time is 3-20min.
In a preferred embodiment of the invention, the preparation process 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.
In a preferred embodiment of the invention, the preparation process is carried out in an internal mixer; preferably, the internal mixing temperature is 180-250 ℃, preferably 210-230 ℃, the rotating speed is 5-150rpm, preferably 20-80rpm, and the reaction time is 3-15min, preferably 5-10min.
In a preferred embodiment of the invention, the preparation process is carried out in a twin-screw extruder; preferably, the processing temperature is 180-250 ℃, preferably 210-230 ℃, the screw speed is 5-300rpm, preferably 30-100rpm, the aspect ratio is 30-80, preferably 40-70.
Banbury mixer arrangements suitable for use in the present invention include Banbury mixers of different designs, for example PolyLab HAAKE manufactured by Thermo Fisher, U.S.A TM Rheomix OS 567-1000 internal mixer modules, etc. Continuous twin-screw extrusion apparatus suitable for use in the present invention include twin-screw extruders of different designs, such as ZSK Mcc18 or ZSK 40 equidirectional parallel twin-screw extruders produced by Coperion, germany, and the like.
It is a further object of the present invention to provide a block copolymer prepared by the above-described preparation method.
It is a fourth object of the present invention to provide the use of the block copolymer as described above as a compatibilizer in injection molded articles of aliphatic-aromatic copolyesters and polyglycolic acid blends.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the polybutylene succinate is directly used as an initiator to initiate the ring-opening polymerization of glycolide, and the aliphatic-aromatic copolyester and polyglycolic acid segmented copolymer are directly prepared by a one-step method, so that the preparation method is simpler.
(2) Compared with the traditional polyglycolic acid preparation method, the method has the advantages that the reaction condition is loose, the preparation can be performed under the condition of normal pressure and no nitrogen protection, the reaction time is short, and the continuous preparation can be realized.
(3) The block copolymer of the present invention is useful as a compatibilizer in applications in which the aliphatic-aromatic copolyester block can ensure a segment of a certain length, can improve the compatibility of PGA with aliphatic-aromatic copolyester blends, and can improve the mechanical properties of the blends, for example, can improve the toughness and tensile strength of PGA with aliphatic-aromatic copolyester blends.
Drawings
The strong peaks at 2.5ppm and 3.3ppm in FIG. 1 are absorption peaks of solvent DMSO. The methylene proton absorption peak of PGA was-5.0 ppm, and after block copolymerization, a multimodal appearance was observed, with the main peak shifted from 0.1 to 0.2ppm toward the high field. The absorption peaks at 1.5-2.0ppm and 4.0-4.5ppm are proton absorption peaks for hydrogen on alkanes in PBST, while the absorption peak at 8.0ppm corresponds to hydrogen on benzene rings in PBST. Thus, the product of example 2 still contained the PBST component after purification (product of example 6), indicating that PGA and PBST of example 2 were bonded by chemical bonds, rather than physical blends.
FIG. 2 is an infrared signature curve of pure PGA in example 6, pure PBST and comparative example 3; in FIG. 2, about 1750cm-1 represents the absorption peak of carbonyl group in PGA, and the absorption peak of carbonyl group in PBST is 1715cm -1 About, while both absorption peaks appear in example 6, as evidenced by the results of the nuclear magnetic hydrogen spectrum, the block copolymer, rather than the physical blend, in example 6 is demonstrated.
FIG. 3 is a DSC characterization curve of example 6 and comparative example 2; as can be seen from fig. 3, the melting point and crystallization temperature of example 6 were slightly lower than those of comparative example 2, while the interval between the two glass transition temperatures of example 6 was smaller than that of comparative example 2.
FIGS. 4 and 5 are sectional scanning electron micrographs (magnification: 1.00 kx) of liquid nitrogen low temperature brittle fracture of example 5 and comparative example 1, respectively; as can be seen from comparing fig. 4 and 5, the cross section of example 5 (corresponding to fig. 4) is significantly smoother and more uniform than that of comparative example 1, indicating that the compatibility of PGA phase and PBST in example 5 is better than that of comparative example 1; the uneven cross-section and partial holes in fig. 5 further illustrate that PGA is mechanically blended poorly with aliphatic-aromatic copolyesters (PBXT) itself, and that the addition of compatibilizers is necessary. As can be seen from comparison of fig. 4 and 5, the compatibilizing agent PGA phase and PBXT (PBAT or PBST) phase in the present invention not only can improve the compatibility of two phases per se after being connected by covalent bonds, but also can be added as a compatibilizing agent to the PGA and PBXT blend to improve the compatibility of two phases in the blend, thereby improving the mechanical properties of the blend.
Detailed Description
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall 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 raw material sources are as follows:
the raw materials used in the invention are all commercially available.
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. ADR of chain extender
ADR-4468, epoxy equivalent: 310 g/mol) from basf (china) limited.
Polybutylene succinate terephthalate (PBST), china petrochemical instrumentation and chemical fiber Limited liability company, with the brand TS159. Polyglycolide (PGA) was purchased from Bien-Prague, heilaceae, as GMP grade glycolide homopolymer having an average intrinsic viscosity of 1.2dl/g.
The invention performs performance measurement according to the following method:
nuclear magnetic hydrogen spectrum @ 1 H-NMR): the test instrument was a JNM-ECZ500R/S1 nuclear magnetic resonance spectrometer from JEOL corporation of Japan. Tetramethylsilane (TMS) was used as an internal standard and deuterated DMSO was used as solvent.
Fourier transform infrared spectroscopy (FTIR): the test instrument is a front Fourier transform infrared spectrometer from Perkinelmer, inc. of USA. Absorption signals were obtained using Attenuated Total Refraction (ATR) accessories at 650-4000cm per sample -1 Scan in range 4 times.
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.
Differential Scanning Calorimeter (DSC): the test instrument was a Discovery series scanning calorimeter from TA corporation in the united states. During testing, 5-10mg of samples are weighed in a sample tray, the testing temperature is in the range of 0-240 ℃, all samples are subjected to once heating to eliminate heat history, meanwhile, the cooling curve is recorded, the heating and cooling rates are 10 ℃/min, the stable time of the highest temperature and the lowest temperature is 2min, and the testing atmosphere is nitrogen.
Scanning Electron Microscope (SEM) photograph of the section: the injection-molded tensile bars are completely cooled in liquid nitrogen and then brittle-cut at low temperature, after the surface is sprayed with metal, the sections are photographed by a Merlin field emission scanning electron microscope of Zeiss company, germany.
[ example 1 ]
Glycolide (GA), anhydrous stannous chloride and polybutylene succinate terephthalate (PBST) (weight average molecular weight 60000 g/mol) were prepared according to 80:0.024:20 by mass ratio of 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.
[ example 2 ]
According to example 1, except that the ratio of Glycolide (GA), anhydrous stannous chloride and polybutylene succinate (PBST) was changed to 70:0.021:30 to give a PGA/PBST block copolymer.
[ example 3 ]
According to example 1, except that polybutylene succinate (PBST) was changed to polybutylene adipate terephthalate (PBAT) (weight average molecular weight 40000), a PGA/PBAT block copolymer was obtained.
[ example 4 ]
According to the difference from example 3, PBAT was changed to PBAT modified by chain extension (weight average molecular weight: 50000 g/mol), to obtain a PGA/PBAT block copolymer.
The general preparation of the chain-extended modified PBAT is as follows: PBAT and chain extender ADR-4368 were mixed according to 1000:3, and extruding and granulating by using a Labtech parallel co-rotating double screw extruder (screw diameter: 16mm, length-diameter ratio: 40). 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: 110 ℃,160 ℃,210 ℃,220 ℃,220 ℃,220 ℃,220 ℃, and 210 ℃.
[ example 5 ]
According to example 4, except that PBAT was changed to α, ω -dihydroxyPBAT (weight average molecular weight: 20000 g/mol) obtained by the alcoholysis reaction, a PGA-PBAT-PGA ternary block copolymer was obtained.
The general preparation of the alcoholysis PBAT is as follows: PBAT, zinc acetate and ethylene glycol were mixed according to 1000:4:50, and extruding and granulating by using a Labtech parallel co-rotating twin-screw extruder (screw diameter: 16mm, length-diameter ratio: 40). 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: 110 ℃,150 ℃,190 ℃,190 ℃,190 ℃,190 ℃,190 ℃,190 ℃,190 ℃ and 190 ℃.
[ example 6 ]
The product obtained in example 2 was dissolved in hexafluoroisopropanol, precipitated with a large amount of chloroform, washed, centrifuged, and dried in vacuo to remove the solvent, thereby obtaining a purified PGA-PBST block copolymer.
Example 6 was used to verify that the product of example 1 was a block copolymer.
Comparative example 1
The synthesis was similar to example 1, but the initiator in example 1 was changed from polybutylene succinate (PBST) to dodecanol, the ratio of Glycolide (GA), anhydrous stannous chloride and dodecanol was 80:0.024:0.16, and 20phr of polybutylene succinate (PBST) are added after the reaction is completed, and stirred for 1min under heat. The product of comparative example 1 was obtained.
Comparative example 2
The product of comparative example 1 was purified by the same purification method as in example 6 to obtain a purified blend of comparative example 2.
[ comparative example 3 ]
Polyglycolide (PGA) (weight average molecular weight 160000 g/mol) available from Bien-Prague, hollaceae.
[ comparative example 4 ]
The polyglycolide and polybutylene adipate terephthalate (PBAT) of comparative example 3 (weight-average molecular weight 40000 g/mol) were prepared in an amount of 80:20 by mass ratio, with PolyLab HAAKE from Thermo Fisher technology Co., USA TM A Rheomix OS 567-1000 internal mixer (rotor diameter: 35mm, rotor length: 50 mm) was melt mixed. The rotation speed was 50rpm, the temperature was 230℃and the mixing time was 5min. After the reaction was completed, it was directly allowed to cool in air to obtain a PGA/PBST blend.
The experimental parameters of some examples and comparative examples are shown in table 1, PBXT refers to PBST or PBAT.
TABLE 1
Detection example 1
The pure PGA of example 6 and comparative example 3 was characterized by nuclear magnetic hydrogen spectroscopy, the solvent was deuterated DMSO, and the resulting comparative diagram is shown in fig. 1.
Detection example 2
The pure PGA of example 6, pure PBST and comparative example 3 were infrared characterized by Attenuated Total Reflectance (ATR) and the resulting pictures were 1900-1600cm -1 An enlarged partial contrast diagram in the range is shown in fig. 2.
Detection example 3
Molecular weight characterization by GPC was performed for example 1, example 2, example 6, comparative example 1 and comparative example 2, and the results are shown in table 2.
As can be seen from Table 2, the molecular weights and the distribution thereof of the examples and the comparative examples are not very different, and the weight average molecular weight is between 70000 and 100000g/mol.
TABLE 2
Detection example 4
DSC characterization was performed for example 6 and comparative example 2, and the results are shown in Table 3 and FIG. 3.
The block copolymer will exhibit a reduction in the distance between the glass transition temperatures compared to the distance between the glass transition temperatures of two simple copolymer starting materials (PGA and PBXT in the examples of the invention), the smaller the distance between the glass transition temperatures, indicating better compatibility between the two components in the block copolymer. However, since the glass transition temperature of the polymer itself may also be related to its molecular weight and purity, this test example was compared with comparative example 2 and example 6, which have similar molecular weights and were also subjected to purification operations.
As can be seen from comparative examples 6 and 2 (fig. 3), the melting point and crystallization temperature of example 6 are slightly lower than those of comparative example 2, while the interval between the two glass transition temperatures of example 6 is smaller than that of comparative example 2, as can be seen from fig. 3.
TABLE 3 Table 3
T g: Glass transition temperature; t (T) m Melting point; ΔH m Enthalpy of fusion; t (T) c Crystallization temperature
Detection example 5
The results of the scanning electron micrographs of sections taken after surface-spraying of the samples of example 5 and comparative example 1, i.e., the sectional photographs of the PGA/PBST block copolymer and the PGA/PBST blend, after injection molding into tensile test bars, were shown in FIGS. 4 and 5, respectively.
Application example
The PGA/PBAT block copolymer obtained in example 5 was added as a compatibilizer to the PGA/PBST blend obtained in comparative example 4, and PolyLab HAAKE, a Thermo Fisher technology company of America was used TM A Rheomix OS 567-1000 internal mixer (rotor diameter 35mm, rotor length 50 mm) was melt mixed. The ratio of example 5 to comparative example 4 is 5:100, rotation speed 50rpm, temperature 230 ℃, mixing time 5min. To obtain a product containing the copolymer of the invention.
The mechanical properties of the products of application example and comparative example 4 were examined, and samples were injection-molded into 5A-type tensile bars (thickness: 2 mm) according to GB/T1040.2-2006 on a HAAKE MiniJet microinjection molding machine, with cylinder temperature and mold temperature of 230℃and 50℃respectively, injection molding pressure and time of 300bar and 5s respectively, and holding pressure and time of 100bar and 30s respectively. Tensile testing was then performed on an Instron model 3344 material tester, U.S. at a 20mm/min tensile rate and 50mm fixture spacing. The results are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 4, the mechanical properties of the product obtained in application example 7, which contains the block copolymer of the present invention, are significantly improved compared with those of the product obtained in comparative example 4, which contains no compatibilizer by simple physical blending, and both the tensile strength and the elongation at break are higher than those of the product without the compatibilizer. It was demonstrated that the compatibility of the physically blended PGA/PBAT was significantly improved by the addition of the compatibilizing agent of the present invention (a block copolymer of PGA and PBAT). Meanwhile, the increase in elongation at break illustrates the increased toughness of the PGA/PBAT blend after the addition of the compatibilizing agent of the present invention.
It was confirmed that after the products of examples 1-2 were added as compatibilizers to the physically blended PGA/PBST, respectively, and the products of examples 3-4 were added as compatibilizers to the physically blended PGA/PBAT, respectively, the mechanical properties of the corresponding obtained products also exhibited similar properties to those of the product of application example 7. The PGA/PBST blend or the PGA/PBAT blend has improved mechanical properties, obviously improved compatibility between PGA and PBST or between PGA and PBAT, and enhanced toughness.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (15)
1. A block copolymer comprising a polyglycolic acid block and an aliphatic-aromatic copolyester block;
the block copolymer contains an A-B diblock copolymer or an A-B-A triblock copolymer, wherein the block A is polyglycolic acid and the block B is aliphatic-aromatic copolyester.
2. The block copolymer of claim 1, wherein:
the content of the block A is 1 to 99 mass%, preferably 65 to 95 mass%, relative to the total mass of the block A and the block B; the content of the block B is 1 to 99% by mass, preferably 5 to 40% by mass.
3. The block copolymer of claim 1, wherein:
the block B is a copolyester formed by polycondensation of aliphatic diacid and/or aromatic diacid and aliphatic diol;
preferably, the block B is a copolyester formed by condensing at least one of alpha, omega-aliphatic diacid and aromatic diacid containing 2-18 main chain carbon atoms and at least one aliphatic diol;
further preferably, the block B is at least one of poly (butylene adipate-co-terephthalate), poly (ethylene terephthalate-co-succinate), and poly (butylene terephthalate-co-succinate).
4. The block copolymer of claim 1, wherein:
the block B is polybutylene adipate terephthalate and/or polybutylene succinate terephthalate; and/or the number of the groups of groups,
the weight average molecular weight of the block B is 1000-200000g/mol, preferably 20000-100000g/mol.
5. The block copolymer of claim 4, wherein:
the block copolymer contains a copolymer with a structural formula shown as a formula (I) and/or a formula (II):
wherein R in formula (I) and formula (II) 1 Each independently is
6. The block copolymer of any of claims 1-5, wherein:
the weight average molecular weight of the block copolymer is 20000-200000g/mol, preferably 80000-160000g/mol; and/or the number of the groups of groups,
the polydispersity of the block copolymer is from 1 to 3, preferably from 1 to 2; and/or the number of the groups of groups,
the block copolymer is prepared by copolymerizing raw materials including glycolide and aliphatic-aromatic copolyester.
7. A process for the preparation of a block copolymer according to any one of claims 1 to 6, comprising melt blending the components comprising the desired amounts of glycolide, aliphatic-aromatic copolyesters and catalyst, followed by cooling to obtain the block copolymer.
8. The method of manufacturing according to claim 7, wherein:
the dosage ratio of glycolide to aliphatic-aromatic copolyester is 100:1-99, preferably 100:5-40 parts; and/or the number of the groups of groups,
the dosage ratio of glycolide to the catalyst is 100: (0.005-1), preferably 100: (0.01-0.5).
9. The method of manufacturing according to claim 7, wherein:
the weight average molecular weight of the aliphatic-aromatic copolyester is 1000-200000g/mol, preferably 20000-100000g/mol, more preferably 40000-90000g/mol;
and/or, 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.
10. The method of manufacturing according to claim 7, wherein:
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.
11. The preparation method according to any one of claims 7 to 10, characterized in that:
the temperature of the melt blending reaction is 180-250 ℃, preferably 210-230 ℃; the reaction time is 3-20min; and/or the number of the groups of groups,
the preparation process 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.
12. The preparation method according to any one of claims 7 to 10, characterized in that:
the preparation process is carried out in an internal mixer;
preferably, the internal mixing temperature is 180-250 ℃, preferably 210-230 ℃, the rotating speed is 5-150rpm, preferably 20-80rpm, and the reaction time is 3-15min, preferably 5-10min.
13. The preparation method according to any one of claims 7 to 10, characterized in that:
the preparation process is carried out in a double-screw extruder;
preferably, the processing temperature is 180-250 ℃, preferably 210-230 ℃, the screw speed is 5-300rpm, preferably 30-100rpm, the aspect ratio is 30-80, preferably 40-70.
14. A block copolymer prepared by the preparation method of any one of claims 7 to 13.
15. Use of a block copolymer according to any one of claims 1-6, 14 as a compatibilizer in injection molded articles of aliphatic-aromatic copolyesters and polyglycolic acid blends.
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|---|---|---|---|
| CN202111230152.7A CN116003765A (en) | 2021-10-22 | 2021-10-22 | Block copolymer of aliphatic-aromatic copolyester and polyglycolic acid, and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111230152.7A CN116003765A (en) | 2021-10-22 | 2021-10-22 | Block copolymer of aliphatic-aromatic copolyester and polyglycolic acid, and preparation method and application thereof |
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| CN116003765A true CN116003765A (en) | 2023-04-25 |
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