CN111004483A - Degradable composite material and preparation method thereof - Google Patents
Degradable composite material and preparation method thereof Download PDFInfo
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- CN111004483A CN111004483A CN201811295122.2A CN201811295122A CN111004483A CN 111004483 A CN111004483 A CN 111004483A CN 201811295122 A CN201811295122 A CN 201811295122A CN 111004483 A CN111004483 A CN 111004483A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a degradable composite material and a preparation method thereof, belonging to the technical field of polymer processing and modification. The material comprises 50-90 parts of polylactic acid A, 0.1-10 parts of polylactic acid B (the polylactic acid A and the polylactic acid B are optical isomers), 1-20 parts of degradable polyester C, 1-50 parts of polylactic acid B-degradable polyester C copolymer and 0.1-5 parts of functional auxiliary agent. The composite material disclosed by the invention not only has excellent toughness, but also has excellent heat resistance, is completely biodegradable, and can be widely applied to the fields of plastic structural members, plastic packages, automotive interior parts, medical consumables and the like.
Description
Technical Field
The invention relates to a degradable composite material and a preparation method thereof, belonging to the technical field of polymer processing and modification.
Background
Due to the shortage of petroleum resources and the increasingly prominent problem of serious environmental pollution, environment-friendly materials are increasingly favored by people. Polylactic acid (PLA) is a bio-based and biodegradable material, and the synthetic raw materials of the PLA are derived from plant resources such as corn and the like, and the PLA is sufficiently and renewable. In addition, the polylactic acid also has good biocompatibility, processability and mechanical strength, and is an ideal green high polymer material. Polylactic acid (PLA) includes levorotatory polylactic acid (PLLA), dextrorotatory polylactic acid (PDLA), and racemic polylactic acid (PDLLA). PLLA and PDLA have opposite optical rotation, when the two are blended, a structure complementary phenomenon can occur between molecular chains, and a stable hydrogen bond C-H can be formed between methyl and carbonyl: and O ═ C, so that intermolecular force is enhanced, and finally, polylactic acid Stereocomplex (SC) crystals are formed, and the melting point of the crystals is about 50 ℃ higher than that of crystals formed by single components of L-polylactic acid or D-polylactic acid.
At present, PLA is difficult to be widely used in the fields of general-purpose plastics and engineering plastics, mainly because the defects of high brittleness and slow crystallization rate of PLA exist. The too slow crystallization rate causes the PLA to be almost amorphous in the product obtained by the conventional melt processing and forming method, while the amorphous PLA has poor heat resistance, and the heat distortion temperature is close to the glass transition temperature (about 60 ℃) and is obviously lower than that of the traditional petroleum-based polymer products such as polyethylene, polypropylene and the like.
Blending with flexible polymers (e.g., elastomers) is a simple, economical method of improving the toughness of PLA. However, the compatibility of the flexible polymer with PLA is generally poor, resulting in weak interfacial forces between the two phases, which results in the inability of the flexible polymer to effectively toughen PLA. For example, toughening of PLA with styrene-butadiene-styrene terpolymer (SBS) results in little improvement in the toughness, especially impact toughness, of PLA due to the weak interfacial interaction of PLA with SBS (European Polymer journal,2016,85: 92-104). Therefore, a key point to improving the toughening efficiency of the flexible polymer to PLA is to improve the interfacial interaction force between the two.
In addition, the flexible polymer is usually dispersed in the PLA matrix as spherical particles, forming a general sea-island structure, and the toughening efficiency is often inferior to the "bicontinuous" or "bicontinuous-like" phase morphology. Thus, transitioning the phase morphology of the PLA/flexible polymer blend from an islands-in-the-sea structure to a bicontinuous phase is another key to achieving effective toughening.
Although effective toughening of PLA can be achieved by improving the interfacial interaction of the flexible polymer with PLA or changing the phase morphology, the slow crystallization rate of PLA cannot be simultaneously solved. Patent CN105713361A discloses an impact-resistant polylactic acid and a preparation method thereof, the method adopts an epoxidized thermoplastic elastomer to toughen PLA, and utilizes the reaction of epoxy groups on the elastomer and the end groups of PLA to improve the compatibility between PLA and elastomer, thereby obtaining PLA with good toughness. In patent CN 102276965A, natural rubber is adopted to toughen PLA, and peroxide initiator is added to initiate crosslinking of the blending system, so as to improve compatibility between PLA and natural rubber, thereby improving toughness of PLA. The introduction of silica nanoparticles into a PLA/polyurethane blending system can transform the blend from a sea-island structure to a quasi-bicontinuous structure, thereby obviously improving the impact toughness of PLA (Polymer,2014,55(6): 1593-1600). However, the above inventions only consider the toughening of PLA, but fail to improve the crystallization rate of PLA, i.e., fail to improve the heat resistance of PLA. In addition, the flexible polymer added to the polylactic acid composite material of the above invention is not biodegradable. Therefore, it is highly desirable to develop a composite material that is high in toughness, heat resistant, and fully biodegradable.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the composite material which has excellent toughness and crystallization property, so that the composite material with high toughness and heat resistance can be obtained after short-time thermal annealing treatment, is completely biodegradable, and can be widely applied to the fields of plastic structural members, plastic packages, automotive interior parts and medical consumables.
The invention provides a degradable composite material and a preparation method thereof, which are characterized in that polylactic acid B, degradable polyester C and polyfunctional compounds are melted and blended to prepare a reactive blend of polylactic acid B/degradable polyester C. In the melt blending process, functional groups on the polyfunctional compound react with terminal carboxyl groups or terminal hydroxyl groups on the polylactic acid B and the degradable polyester C to generate the polylactic acid B-degradable polyester C copolymer. Therefore, the polylactic acid B/degradable polyester C reactive blend contains polylactic acid B, degradable polyester C and polylactic acid B-degradable polyester C copolymer. In the subsequent process of melt blending of the reactive blend of polylactic acid B/degradable polyester C and the polylactic acid A matrix, the polylactic acid B molecular chain segment and the free polylactic acid B molecular chain on the copolymer of polylactic acid B and degradable polyester C can interact with the polylactic acid A matrix molecular chain with opposite optical rotation, and high melting point Stereocomplex (SC) crystals respectively distributed on the two-phase interface and the matrix are formed in situ. The SC crystal can improve the interfacial interaction force between the polylactic acid A matrix and the degradable polyester C and the viscosity of the matrix, thereby changing the phase form of the blend from a sea-island structure to a bicontinuous phase structure. In addition, the SC crystal can also be used as an efficient nucleating agent of a polylactic acid matrix, and the crystallization rate of the matrix is obviously improved, so that the super-tough heat-resistant degradable composite material can be obtained after short-time thermal annealing treatment. Or directly melting and blending the polylactic acid A, the polylactic acid B, the degradable polyester C and the polylactic acid B-degradable polyester C copolymer, wherein the polylactic acid B-degradable polyester C copolymer is obtained by polymerizing a monomer of the polylactic acid B and a monomer of the degradable polyester C.
The invention aims to provide a degradable composite material, which comprises the following components in parts by weight: 50-90 parts of polylactic acid A, 0.1-10 parts of polylactic acid B, 1-20 parts of degradable polyester C, 1-50 parts of polylactic acid B-degradable polyester C copolymer and 0.1-5 parts of functional auxiliary agent; the polylactic acid A is levorotatory polylactic acid and the polylactic acid B is dextrorotatory polylactic acid, or the polylactic acid A is dextrorotatory polylactic acid and the polylactic acid B is levorotatory polylactic acid.
In one embodiment of the present invention, the polylactic acid B-degradable polyester C copolymer comprises a graft or block copolymer.
In one embodiment of the present invention, in the polylactic acid B-degradable polyester C copolymer, the mass content of the polylactic acid B segment is 5% to 95%.
In one embodiment of the present invention, the method for preparing the degradable composite material comprises:
(1) melting and blending 0.2-57.5 parts of polylactic acid B, 5-67.5 parts of degradable polyester C and 0.01-5 parts of polyfunctional group compound at 1-50 ℃ above the melting point of the polylactic acid to obtain a reactive blend of the polylactic acid B and the degradable polyester C; the polylactic acid B/degradable polyester C reactive blend contains polylactic acid B, degradable polyester C and polylactic acid B-degradable polyester C copolymer;
(2) carrying out melt blending on the polylactic acid A, the polylactic acid B/degradable polyester C reactive blend and the functional additive according to the weight part ratio, and forming to obtain a degradable composite material;
or mixing the polylactic acid A, the polylactic acid B, the degradable polyester C, the polylactic acid B-degradable polyester C copolymer and the functional auxiliary agent according to the weight part ratio, carrying out melt extrusion, and then molding to obtain the degradable composite material.
In one embodiment of the invention, the minimum weight fraction of polylactic acid B required in preparing a reactive blend of polylactic acid B-degradable polyester C should be ≥ 0.15 parts of the minimum fraction (1 part) of polylactic acid B-degradable polyester C copolymer x the minimum mass content (5%) of polylactic acid B segment + 0.1 part of polylactic acid B; similarly, the minimum weight part of the needed degradable polyester C is more than or equal to 1.05 parts.
In one embodiment of the invention, the maximum weight fraction of polylactic acid B required to prepare a polylactic acid B/degradable polyester C reactive blend should be equal to the maximum fraction (50 parts) of polylactic acid B-degradable polyester C copolymer x the maximum mass content of the polylactic acid B segment (95%) + the maximum fraction (10 parts) of polylactic acid B to 57.5 parts; similarly, the maximum required weight portion of degradable polyester C should be equal to 67.5 parts.
In one embodiment of the present invention, the multi-functional compound includes one or more of a compound containing a plurality of epoxy groups and a compound containing a plurality of isocyanate groups.
In one embodiment of the invention, the degradable polyester C comprises one or more of polybutylene terephthalate-adipate copolymer (PBAT), Polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate-adipate copolymer (PBSA), and Polyhydroxyalkanoate (PHA).
In one embodiment of the present invention, the functional additives include one or more of an anti-hydrolysis agent, an antioxidant, a nucleating agent, a chain extender, and a plasticizer.
The second purpose of the invention is to apply the degradable composite material to the field of medical consumables.
A third object of the present invention is to provide a plastic structural member comprising the above degradable composite material.
A fourth object of the present invention is to provide a plastic package comprising the above degradable composite material.
The fifth object of the invention is to provide an automotive interior part, which comprises the degradable composite material.
The invention has the beneficial effects that:
1. the polylactic acid B chain segment in the polylactic acid B-degradable polyester C copolymer in the composite material component interacts with the molecular chain of the polylactic acid A matrix to form SC dispersed on the interface in situ, so that the interface interaction force between the matrix and the degradable polyester C is obviously improved.
2. The invention simultaneously plays the triple functions of the SC crystal, and firstly, the interface acting force is improved; secondly, the viscosity of the matrix is improved, so that the phase form of the blend is changed from a sea-island structure to a bicontinuous phase structure; and thirdly, the polylactic acid is used as a nucleating agent, so that the crystallization rate of the polylactic acid matrix is obviously improved.
3. The composite material of the invention can obtain high-toughness and heat-resistant material only by short-time thermal annealing treatment, thereby greatly shortening the production period and reducing the production cost.
4. The preparation method provided by the invention is simple and efficient, and is easy to realize industrial production.
5. The composite material mainly comprises polylactic acid and degradable polyester which are biodegradable materials, and accords with the concept of environmental protection.
Detailed Description
The present invention will be described in detail below with reference to examples and comparative examples, but the examples should not be construed as limiting the scope of the present invention.
Example 1
First, 10 parts of PDLA (number average molecular weight 9 ten thousand, optical purity 98.8%), 20 parts of PBAT (number average molecular weight 15 ten thousand) and 43700.2 parts of ADR were added into an internal mixer to be melt-blended for 5 minutes (blending temperature 200 ℃) to obtain a PDLA/PBAT reactive blend (characterized by containing 3 parts of PDLA, 10 parts of PBAT and 17 parts of PDLA-PBAT copolymer).
70 parts of PLLA (the number average molecular weight is 13 ten thousand, and the optical purity is 99.0 percent), 30 parts of PDLA/PBAT reactive blend and 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are added into an internal mixer to be melted and blended for 4 minutes (the blending temperature is 190 ℃), the obtained blend is hot-pressed at the temperature of 200 ℃ and then is annealed at the temperature of 100 ℃ for 2 minutes, and the degradable composite material is obtained.
Example 2
First, 12 parts of PDLA (number average molecular weight 12 ten thousand, optical purity 97.5%), 20 parts of PCL (number average molecular weight 12 ten thousand) and 0.4 part of hexamethylene diisocyanate were added to an internal mixer to be melt-blended for 5 minutes (blending temperature 205 ℃) to obtain a PDLA/PCL reactive blend (characterized by containing 5 parts of PDLA, 9 parts of PCL and 18 parts of PDLA-PCL copolymer).
Then 60 parts of PLLA (the number average molecular weight is 15 ten thousand, the optical purity is 98.2%), 40 parts of PDLA/PCL reactive blend, 0.2 part of tris [2, 4-di-tert-butylphenyl ] phosphite and 0.2 part of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate are added into an internal mixer to be melted and blended for 5 minutes (the blending temperature is 200 ℃), the obtained blend is hot-pressed at the temperature of 210 ℃ and then is annealed at the temperature of 90 ℃ for 2 minutes, and the degradable composite material is obtained.
Example 3
First, 8 parts of PLLA (number average molecular weight 9 ten thousand, optical purity 98.8%), 20 parts of PCL (number average molecular weight 10 ten thousand) and 0.3 part of diphenylmethane diisocyanate were added to an internal mixer to conduct melt blending for 6 minutes (blending temperature 190 ℃) to obtain a PLLA/PCL reactive blend (characterized by containing 4 parts of PLLA, 12 parts of PCL and 12 parts of PLLA-PCL copolymer).
Then 72 parts of PDLA (number average molecular weight 12 ten thousand, optical purity 97.5%), 28 parts of PLLA/PCL reactive blend and 0.3 part of N, N' -bis (2, 6-diisopropylphenyl) carbodiimide were added to an internal mixer to carry out melt blending for 4 minutes (blending temperature 190 ℃); and hot-pressing the obtained blend at the temperature of 200 ℃, and annealing at the temperature of 110 ℃ for 3 minutes to obtain the degradable composite material.
Example 4
Firstly, 6 parts of PDLA (with the number average molecular weight of 9 ten thousand and the optical purity of 98.8 percent), 20 parts of PBS (with the number average molecular weight of 15 ten thousand) and 44680.3 parts of ADR are premixed uniformly at room temperature, and then are melt-extruded by a double-screw extruder, wherein the melt-extrusion temperature is 200 ℃ and the screw rotation speed is 250rpm, so that a PDLA/PBS reactive blend (characterized by containing 2 parts of PDLA, 7 parts of PBS and 17 parts of PDLA-PBS copolymer) is obtained.
Then 74 parts of PLLA (the number average molecular weight is 13 ten thousand, the optical purity is 99.0%), 26 parts of PDLA/PBS reactive blend, 0.15 part of [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.15 part of tris [2, 4-di-tert-butylphenyl ] phosphite are premixed uniformly at room temperature, then the mixture is melted and extruded by a double-screw extruder, wherein the melting and extrusion temperature is 200 ℃, the rotating speed of a screw is 200rpm, the obtained extrudate is melted in an injection molding machine at the temperature of 210 ℃, then injection molding is carried out, and annealing is carried out for 2.5 minutes at the temperature of 100 ℃, thus obtaining the degradable composite material.
Example 5
Firstly, 4 parts of PDLA (the number average molecular weight is 11 ten thousand, and the optical purity is 98.5 percent), 20 parts of PBSA (the number average molecular weight is 16 ten thousand) and 0.35 part of hexamethylene diisocyanate are premixed uniformly at room temperature, and then melt-extruded by a double-screw extruder, wherein the melt-extrusion temperature is 210 ℃, and the screw rotating speed is 200rpm, so as to obtain a PDLA/PBSA reactive blend (the reactive blend is characterized by containing 2 parts of PDLA, 15 parts of PBSA and 7 parts of PDLA-PBSA copolymer).
Then 64 parts of PLLA (the number average molecular weight is 16 ten thousand, the optical purity is 98.4%), 36 parts of PDLA/PBSA reactive blend, 0.2 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.5 part of N, N' -bis (2, 6-diisopropylphenyl) carbodiimide are premixed uniformly at room temperature, then melt-extruded by a double-screw extruder, wherein the melt-extrusion temperature is 205 ℃, the screw rotation speed is 200rpm, the obtained extrudate is melted in an injection molding machine at the temperature of 210 ℃ and then injection molded, and the mixture is annealed for 2 minutes at the temperature of 90 ℃, so that the degradable composite material can be obtained.
Example 6
75 parts of PLLA (with the number average molecular weight of 16 ten thousand and the optical purity of 98.4 percent), 3 parts of PDLA (with the number average molecular weight of 15 ten thousand and the optical purity of 98.8 percent), 10 parts of PBS (with the number average molecular weight of 12 ten thousand), 12 parts of PDLA-PBS block copolymer (with the mass content of PDLA of 17 percent), 0.4 part of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1 part of talcum powder are premixed uniformly at room temperature, and then melt-extruded by a double-screw extruder, wherein the melt-extrusion temperature is 195 ℃, the screw rotation speed is 180rpm, the obtained extrudate is melted in an injection molding machine at the temperature of 200 ℃, injection-molded, and annealed for 4 minutes at the temperature of 95 ℃, so that the degradable composite material is obtained.
Comparative example 1
100 parts of PLLA (the number average molecular weight is 13 ten thousand, the optical purity is 99.0%) and 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are added into an internal mixer to be melted and blended for 4 minutes (the blending temperature is 190 ℃), the obtained blend is hot pressed at the temperature of 200 ℃, and then is annealed for 2 minutes at the temperature of 100 ℃, thus obtaining the polylactic acid material.
Comparative example 2
80 parts of PLLA (the number average molecular weight is 13 ten thousand and the optical purity is 99.0 percent), 20 parts of PBAT (the number average molecular weight is 15 ten thousand) and 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are added into an internal mixer to be melted and blended for 4 minutes (the blending temperature is 190 ℃), the obtained blend is hot-pressed at the temperature of 200 ℃ and then is annealed at the temperature of 100 ℃ for 2 minutes, and the composite material is obtained.
Comparative example 3
First, 10 parts of PDLA (number average molecular weight: 9 ten thousand, optical purity: 98.8%) and 20 parts of PBAT (number average molecular weight: 15 ten thousand) were added to an internal mixer to conduct melt blending for 5 minutes (blending temperature: 200 ℃) to obtain a PDLA/PBAT non-reactive blend.
70 parts of PLLA (the number average molecular weight is 13 ten thousand, and the optical purity is 99.0%), 30 parts of PDLA/PBAT non-reactive blend and 0.3 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester are added into an internal mixer to be melted and blended for 4 minutes (the blending temperature is 190 ℃), the obtained blend is hot pressed at the temperature of 200 ℃ and then is annealed at the temperature of 100 ℃ for 2 minutes, and the composite material is obtained.
In order to examine the mechanical properties, crystallinity and heat resistance of the composite materials prepared by the method of the present invention, tensile properties, notched impact strength, DSC crystallinity and heat distortion temperature tests were performed on the samples obtained in examples 1 to 6 and comparative examples 1 to 3, and the results are shown in Table 1.
TABLE 1 composite Performance test
Tensile properties (tensile strength and elongation at break) in examples and comparative examples were measured according to GB/T1040-1992 standard at a tensile rate of 50 mm/min; the notch impact strength is tested according to the GB/T1043 + 1993 standard, and before the test, a sample bar is placed in an environment at 23 ℃ for 24 hours; the crystallinity is measured by DSC, and the heating rate is 10 ℃/min; the heat distortion temperature was measured according to GB/T1634.2-2004 standard.
As can be seen from the data in Table 1, polylactic acid (comparative example 1) is very brittle (elongation at break and notched impact strength are only 5% and 1.6kJ/m2, respectively), and has low crystallinity after a short time (2 minutes) of thermal annealing treatment due to slow crystallization rate, so that the heat distortion temperature is less than 60 ℃; the toughness of the blend with PBAT (comparative example 2) was slightly improved, but the crystallinity was still low and the heat distortion temperature was lower. The composite material disclosed in the invention (as example 1) not only remarkably improves the interface interaction force, but also greatly improves the viscosity of the matrix due to the existence of the stereo composite crystal in the phase interface and the matrix, so that the phase morphology of the blend is changed from a common sea-island structure to a bicontinuous phase structure; meanwhile, the stereo composite crystal can also be used as a nucleating agent, and is obviousThe crystallization of the polylactic acid matrix is promoted. Therefore, the composite material obtained after the short-time thermal annealing treatment not only has excellent toughness (the elongation at break reaches 220 percent, and the notch impact strength reaches 38.3 kJ/m)2) It also has excellent heat resistance (heat distortion temperature up to 129.3 ℃) and can keep higher tensile strength (42.5 MPa). However, the composite material obtained by blending PLLA and PDLA/PBAT non-reactive blend (comparative example 3) has high crystallinity and heat resistance, but the toughness is far inferior to that of the composite material prepared by the present invention, because the PDLA/PBAT non-reactive blend does not contain PDLA-PBAT copolymer, SC cannot be selectively dispersed at the phase interface of PLLA and PBAT, so that the interfacial force is weak, and thus high toughness cannot be obtained. Therefore, the composite material obtained by the invention has excellent mechanical properties (including toughness and strength), excellent heat resistance and complete biodegradability, and can be widely applied to the fields of plastic structural parts, plastic packages, automotive interior parts, medical consumables and the like.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also technical features in the above embodiments or in different embodiments may be combined and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The degradable composite material is characterized by comprising the following components in parts by weight: 50-90 parts of polylactic acid A, 0.1-10 parts of polylactic acid B, 1-20 parts of degradable polyester C, 1-50 parts of polylactic acid B-degradable polyester C copolymer and 0.1-5 parts of functional auxiliary agent; the polylactic acid A is levorotatory polylactic acid and the polylactic acid B is dextrorotatory polylactic acid, or the polylactic acid A is dextrorotatory polylactic acid and the polylactic acid B is levorotatory polylactic acid.
2. The composite material of claim 1, wherein the polylactic acid B-degradable polyester C copolymer comprises a graft or block copolymer.
3. The composite material according to claim 1 or 2, wherein the polylactic acid B-degradable polyester C copolymer has a polylactic acid B segment content of 5-95% by mass.
4. The composite material of claim 1, wherein the degradable composite material is prepared by a method comprising:
(1) melting and blending 0.2-57.5 parts of polylactic acid B, 5-67.5 parts of degradable polyester C and 0.01-5 parts of polyfunctional group compound at 1-50 ℃ above the melting point of the polylactic acid to obtain a reactive blend of polylactic acid B and degradable polyester C; the polylactic acid B-degradable polyester C reactive blend contains polylactic acid B, degradable polyester C and polylactic acid B-degradable polyester C copolymer;
(2) carrying out melt blending on the reactive blend of polylactic acid A, polylactic acid B-degradable polyester C and the functional additive according to the weight part ratio, and forming to obtain the degradable composite material;
or mixing the polylactic acid A, the polylactic acid B, the degradable polyester C, the polylactic acid B-degradable polyester C copolymer and the functional aid according to the weight part ratio, carrying out melt extrusion, and then forming to obtain the degradable composite material.
5. The composite material of claim 4, wherein the multi-functional compound comprises one or more of a compound containing a plurality of epoxy groups and a compound containing a plurality of isocyanate groups.
6. The composite material of any one of claims 1-5, wherein the degradable polyester C comprises one or more of polybutylene terephthalate-adipate copolymer, polycaprolactone, polybutylene succinate-adipate copolymer, and polyhydroxyalkanoate.
7. Use of the degradable composite material according to any one of claims 1 to 6 in the field of medical consumables.
8. A plastic structure comprising the degradable composite material of any one of claims 1 to 6.
9. A plastic package comprising the degradable composite material of any one of claims 1-6.
10. An automotive interior trim part comprising the degradable composite material according to any one of claims 1 to 6.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112076022A (en) * | 2020-09-29 | 2020-12-15 | 苏州永沁泉智能设备有限公司 | Wound dressing paste and preparation method thereof |
| CN112694730A (en) * | 2021-01-07 | 2021-04-23 | 江南大学 | Method for preparing high-performance high-fluidity polylactic acid based on hyperbranched polymer |
| CN113185810A (en) * | 2021-04-15 | 2021-07-30 | 江南大学 | Renewable high-barrier polyester packaging material and preparation method thereof |
| CN114031913A (en) * | 2021-12-13 | 2022-02-11 | 杭州卓普新材料科技有限公司 | Anti-aging heat-resistant polylactic acid injection molding material and preparation method thereof |
| CN114292503A (en) * | 2022-01-10 | 2022-04-08 | 海信容声(广东)冰箱有限公司 | Puncture-resistant biodegradable material and preparation method and application thereof |
| CN114395224A (en) * | 2021-12-28 | 2022-04-26 | 浙江普利特新材料有限公司 | Degradable antibacterial flocking-imitating composite material for automobile and preparation method thereof |
| CN114410094A (en) * | 2022-03-03 | 2022-04-29 | 郑州轻工业大学 | Polylactic acid composite material and preparation method thereof |
| CN115139424A (en) * | 2022-07-05 | 2022-10-04 | 普立思生物科技有限公司 | Synthesis and forming process of thin-wall injection molding lactic acid resin |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005255806A (en) * | 2004-03-10 | 2005-09-22 | Toyota Central Res & Dev Lab Inc | Polylactic acid resin composition and molded product of the same |
| US20120245292A1 (en) * | 2011-03-25 | 2012-09-27 | Hyundai Motor Company | Manufacturing method of polylactic acid composite composition |
| US20120270979A1 (en) * | 2011-04-25 | 2012-10-25 | University Of Massachusetts | Blend composition, flexible tubing material and method of making the blend |
| CN102924892A (en) * | 2012-10-29 | 2013-02-13 | 中国科学院长春应用化学研究所 | Polylactic resin composition with high heat resistance and high flexibility and preparation method of composition |
| CN103571158A (en) * | 2012-07-19 | 2014-02-12 | 上海杰事杰新材料(集团)股份有限公司 | High interfacial compatibility PLA/PBAT blend and preparation method |
| CN103937184A (en) * | 2014-05-07 | 2014-07-23 | 江苏科技大学 | High-strength and high-toughness full-degradation polylactic acid composition and reaction extrusion preparation method thereof |
| CN104910598A (en) * | 2015-05-28 | 2015-09-16 | 四川大学 | Super-tough high heat-resistant polylactic acid / elastomer blended material or article and preparation method thereof |
| CN106349667A (en) * | 2016-08-31 | 2017-01-25 | 深圳市虹彩新材料科技有限公司 | High strength and high heat resistance polylactic acid composite material and preparation method thereof |
| CN106916424A (en) * | 2017-04-07 | 2017-07-04 | 常州大学 | A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof |
-
2018
- 2018-11-01 CN CN201811295122.2A patent/CN111004483B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005255806A (en) * | 2004-03-10 | 2005-09-22 | Toyota Central Res & Dev Lab Inc | Polylactic acid resin composition and molded product of the same |
| US20120245292A1 (en) * | 2011-03-25 | 2012-09-27 | Hyundai Motor Company | Manufacturing method of polylactic acid composite composition |
| US20120270979A1 (en) * | 2011-04-25 | 2012-10-25 | University Of Massachusetts | Blend composition, flexible tubing material and method of making the blend |
| CN103571158A (en) * | 2012-07-19 | 2014-02-12 | 上海杰事杰新材料(集团)股份有限公司 | High interfacial compatibility PLA/PBAT blend and preparation method |
| CN102924892A (en) * | 2012-10-29 | 2013-02-13 | 中国科学院长春应用化学研究所 | Polylactic resin composition with high heat resistance and high flexibility and preparation method of composition |
| CN103937184A (en) * | 2014-05-07 | 2014-07-23 | 江苏科技大学 | High-strength and high-toughness full-degradation polylactic acid composition and reaction extrusion preparation method thereof |
| CN104910598A (en) * | 2015-05-28 | 2015-09-16 | 四川大学 | Super-tough high heat-resistant polylactic acid / elastomer blended material or article and preparation method thereof |
| CN106349667A (en) * | 2016-08-31 | 2017-01-25 | 深圳市虹彩新材料科技有限公司 | High strength and high heat resistance polylactic acid composite material and preparation method thereof |
| CN106916424A (en) * | 2017-04-07 | 2017-07-04 | 常州大学 | A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| YANLONG LIU，等: "Toughening effect of poly(D-lactide)-b-poly(butylene succinate)-b-poly(D-lactide) copolymers on poly(L-lactic acid) by solution casting method", 《MATERIALSLETTERS》 * |
| 李琦: "PDLA-r-PCL对PLLA的结构调控及性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技I辑》 * |
| 赵正达，等: "Joncryl增容PLA/PBAT共混体系结构及性能研究", 《材料导报》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112076022A (en) * | 2020-09-29 | 2020-12-15 | 苏州永沁泉智能设备有限公司 | Wound dressing paste and preparation method thereof |
| CN112694730A (en) * | 2021-01-07 | 2021-04-23 | 江南大学 | Method for preparing high-performance high-fluidity polylactic acid based on hyperbranched polymer |
| CN113185810A (en) * | 2021-04-15 | 2021-07-30 | 江南大学 | Renewable high-barrier polyester packaging material and preparation method thereof |
| CN113185810B (en) * | 2021-04-15 | 2022-03-25 | 江南大学 | Renewable high-barrier polyester packaging material and preparation method thereof |
| CN114031913A (en) * | 2021-12-13 | 2022-02-11 | 杭州卓普新材料科技有限公司 | Anti-aging heat-resistant polylactic acid injection molding material and preparation method thereof |
| CN114395224A (en) * | 2021-12-28 | 2022-04-26 | 浙江普利特新材料有限公司 | Degradable antibacterial flocking-imitating composite material for automobile and preparation method thereof |
| CN114292503A (en) * | 2022-01-10 | 2022-04-08 | 海信容声(广东)冰箱有限公司 | Puncture-resistant biodegradable material and preparation method and application thereof |
| CN114292503B (en) * | 2022-01-10 | 2023-05-02 | 海信容声(广东)冰箱有限公司 | Puncture-resistant biodegradable material and preparation method and application thereof |
| CN114410094A (en) * | 2022-03-03 | 2022-04-29 | 郑州轻工业大学 | Polylactic acid composite material and preparation method thereof |
| CN114410094B (en) * | 2022-03-03 | 2024-03-19 | 郑州轻工业大学 | Polylactic acid composite material and preparation method thereof |
| CN115139424A (en) * | 2022-07-05 | 2022-10-04 | 普立思生物科技有限公司 | Synthesis and forming process of thin-wall injection molding lactic acid resin |
| CN116285243A (en) * | 2023-02-22 | 2023-06-23 | 江苏仁信作物保护技术有限公司 | Degradable plastic bottle, preparation method thereof and degradation process |
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