CN113698748A - Partially crosslinked epoxy natural rubber modified polylactic acid and preparation method thereof - Google Patents
Partially crosslinked epoxy natural rubber modified polylactic acid and preparation method thereof Download PDFInfo
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Abstract
The invention provides partially crosslinked epoxy natural rubber modified polylactic acid and a preparation method thereof, wherein the partially crosslinked epoxy natural rubber modified polylactic acid is prepared by the following steps: firstly, banburying reaction is carried out on epoxy natural rubber, dibasic acid and a catalyst for 5-120 minutes at 30-100 ℃ to prepare partially crosslinked epoxy rubber; then the partially crosslinked epoxy rubber and the polylactic acid are melted and blended at the temperature of 160-200 ℃ to obtain the product. Can improve the impact toughness and the tensile toughness of the polylactic acid, and can realize the regulation and control of the toughness. The preparation method is simple and convenient to operate, does not need to use special instruments and equipment, and has strong operability.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to partially crosslinked epoxy natural rubber modified polylactic acid and a preparation method thereof.
Background
Most of the widely used traditional petroleum-based plastics are difficult to degrade in nature, which causes environmental pollution and resource waste to a certain extent. Polylactic acid (PLA) is a thermoplastic polyester plastic which is commercially produced, has renewable raw material sources, good biocompatibility and biodegradability, can be gradually degraded in human bodies and natural environments, and is finally decomposed into carbon dioxide and water. Therefore, the polylactic acid has good industrial prospect, can replace the traditional petroleum-based polymer material, and can be widely applied to the fields of medical treatment, pharmacy, agriculture, packaging and the like.
Polylactic acid has the advantages of excellent biocompatibility, good processability, excellent mechanical strength and modulus and the like, but the polylactic acid has poor flexibility and impact resistance, and the wide application of the polylactic acid is limited to a great extent, so that the polylactic acid needs to be toughened and modified to expand the application field of the polylactic acid.
In order to make polylactic acid have wider application prospect, methods for improving the mechanical property of the polylactic acid, such as a forming process, copolymerization modification, blending modification and the like, are provided.
Chinese patent CN 1367189A grafts polyvinyl alcohol, acrylic acid and the like onto the main chain of polylactic acid by a self-based grafting method, and obviously improves the toughness of the polylactic acid. However, the method belongs to chemical modification and has the defects of complex process, high cost and the like.
Melt blending is the most convenient, economical and practical method for modifying polymers, and toughening modification of PLA can be achieved by blending tough polymers, rubbers or elastomers with PLA. From the viewpoint of sustainable development, Natural Rubber (NR) derived from renewable resources and its derivative Epoxidized Natural Rubber (ENR) are considered as one of the most desirable materials for toughening PLA.
CN102276965B discloses a method for toughening and modifying polylactic acid, which uses peroxide as an initiator to initiate a system to generate crosslinking and enhance the toughening effect of natural rubber on the polylactic acid, but the organic peroxide molecule composition contains peroxy (-O-O-), is flammable and explosive, is easy to decompose, is extremely sensitive to heat, vibration and friction, and has potential safety hazard.
Polymer Testing,2018,65, 249-shaped 255 directly blends PLA and NR according to the mass ratio of 80:20, and the prepared blend alloy has the elongation at break lower than 10 percent and the notched impact strength of only 72.1J/m.
Materials & Design,2013,45, 198-.
Polymer Testing,2017,64,200-206 reported that high impact strength products could be obtained by preparing PLA/ENR blends using dynamic vulcanization, but the elongation at break was still low.
Disclosure of Invention
In view of the problems of the prior art, the first objective of the present invention is to provide a preparation method of partially crosslinked epoxidized natural rubber modified polylactic acid, and the other objective is to provide partially crosslinked epoxidized natural rubber modified polylactic acid obtained by the preparation method. Can improve the impact toughness and the tensile toughness of the polylactic acid, and can realize the regulation and control of the toughness.
In order to achieve the first object, the invention is realized by the following technical scheme: the preparation method of the partially crosslinked epoxy natural rubber modified polylactic acid is characterized by comprising the following steps: firstly, banburying epoxy natural rubber, dibasic acid and a catalyst at 30-100 ℃ for 5-120 minutes to prepare partially crosslinked epoxy rubber; then the partially crosslinked epoxy rubber and the polylactic acid are melted and blended at the temperature of 160-200 ℃.
The invention is prepared by melting and blending the partially cross-linked mENR prepared by binary acid modified ENR and polylactic acid, utilizes the reaction of residual carboxyl and epoxy groups on the molecules of the partial cross-linked ENR and PLA end groups to produce graft copolymer in situ at an interface, can also regulate and control the particle size of a disperse phase of the blend through the cross-linking degree (gel fraction) of the partially cross-linked ENR, and can prepare the PLA/ENR blend alloy with excellent impact toughness and tensile toughness through regulating and controlling the particle size of the disperse phase and interfacial compatibilization, thereby meeting the application requirements of more fields.
In the scheme, the method comprises the following steps: the dibasic acid is any one of malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, octadecanedioic acid and hydrogenated dimer acid.
In the scheme, the method comprises the following steps: the amount of the dibasic acid added is 100:1-100:20 according to the molar ratio of the epoxy group to the carboxyl group. The gel fraction of the mENR is 5-80%
In the scheme, the method comprises the following steps: the catalyst is any one of 1-methylimidazole, 2-methylimidazole, 1, 2-dimethylimidazole and 4-dimethylaminopyridine.
In the scheme, the method comprises the following steps: the addition amount of the catalyst is 0.01-3% of the total mass of the epoxy natural rubber and the dibasic acid.
In the scheme, the method comprises the following steps: the epoxy natural rubber is any one of epoxy rubbers of ENR25, ENR30, ENR40 and ENR 50.
In the scheme, the method comprises the following steps: the mass ratio of the polylactic acid to the partially crosslinked epoxy rubber is 95:5-60: 40.
A modified polylactic acid prepared by the preparation method of the partially crosslinked epoxy natural rubber modified polylactic acid.
Has the advantages that: the invention is obtained by melt blending of partially crosslinked mENR prepared by binary acid modified ENR and polylactic acid, the notch impact strength of PLA/mENR is 51.2-540.0J/m, the elongation at break is 117-526%, the tensile strength is 23.6-57.1MPa, and the invention has good mechanical property and thermoforming processability. The reaction of the dibasic acid and the ENR to form mENR with a partial cross-linking structure can regulate and control the particle size of a dispersed phase in the blend and improve the deformation resistance of the ENR under the action of external force, and on the other hand, the residual carboxyl and epoxy groups of the mENR can react with PLA to form a graft copolymer in situ at a two-phase interface, so that the compatibility among alloy components and the transmission of stress at the interface are improved, the toughening efficiency is greatly improved, the improvement of the impact toughness and the tensile toughness is realized, the toughness of the blend can be regulated and controlled in a wider range, and the modified polylactic acid with different impact strengths and elongation at break is obtained, thereby meeting the application requirements in more fields. In addition, the preparation method provided by the invention is simple and convenient to operate, does not need to use special instruments and equipment, and has strong operability.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Adding ENR25 and malonic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups being 100:1, adding catalyst 4-dimethylaminopyridine accounting for 0.01 percent of the total mass of ENR25 and malonic acid, and reacting at the rotating speed of 50rpm and the temperature of 30 ℃ for 120 minutes to obtain partially crosslinked epoxy natural rubber mENR-1; and (2) melting and blending the polylactic acid and the mENR-1 in an internal mixer for 5 minutes at 160 ℃ according to the mass ratio of 95:5 to obtain modified polylactic acid (PLA/mENR-1).
Performance testing
Putting the mENR-1 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-1, wherein the gel fraction is 5%; the notched impact strength of PLA/mENR-1 was determined to be 51.2. + -. 3.4J/m, the elongation at break was 240.5. + -. 37.5% and the tensile strength was 57.1. + -. 0.5MPa according to ASTM D256 and ASTM D638.
Example 2
Adding ENR30 and succinic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups being 100:2, adding ENR30 and 1, 2-dimethylimidazole which is a catalyst and accounts for 0.1 percent of the total mass of the succinic acid, and reacting for 100 minutes at the rotation speed of 50rpm and the temperature of 40 ℃ to obtain partially crosslinked epoxy natural rubber mENR-2; melting and blending polylactic acid and mENR-2 in an internal mixer according to the mass ratio of 90:10 at 170 ℃ for 5 minutes to obtain modified polylactic acid (PLA/mENR-2)
Performance testing
Putting the mENR-2 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-2, which is 10%; the notched impact strength of PLA/mENR-2 was determined to be 130.7. + -. 13.4J/m, the elongation at break was 397.4. + -. 33.8% and the tensile strength was 46.3. + -. 0.6MPa according to ASTM D256 and ASTM D638.
Example 3
Adding ENR40 and adipic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups being 100:3, adding 2-methylimidazole which is a catalyst and accounts for 0.5 percent of the total mass of ENR40 and the adipic acid, and reacting for 80 minutes at the rotation speed of 50rpm and the temperature of 50 ℃ to obtain partially crosslinked epoxy natural rubber mENR-3; and (2) melting and blending the polylactic acid and the mENR-3 in an internal mixer at 170 ℃ for 5 minutes according to the mass ratio of 85:15 to obtain modified polylactic acid (PLA/mENR-3).
Performance testing
Putting the mENR-3 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-3, which is 33%; the notched impact strength of PLA/mENR-3 was 288.7. + -. 16.9J/m, the elongation at break was 412.2. + -. 42.0% and the tensile strength was 38.8. + -. 0.9MPa as measured according to ASTM D256 and ASTM D638.
Example 4
Adding ENR50 and sebacic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups of 100:4, adding catalyst 1-methylimidazole accounting for 1% of the total mass of ENR50 and sebacic acid, and reacting for 60 minutes at the conditions of the rotating speed of 50rpm and the temperature of 60 ℃ to obtain partially crosslinked epoxy natural rubber mENR-4; and (2) melting and blending the polylactic acid and the mENR-4 in an internal mixer at 180 ℃ for 5 minutes according to the mass ratio of 80:20 to obtain modified polylactic acid (PLA/mENR-4).
Performance testing
Putting the mENR-4 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-4, which is 51%; the notched impact strength of PLA/mENR-4 was determined to be 534.0 + -19.1J/m, the elongation at break was 525.8 + -60.1%, and the tensile strength was 34.0 + -0.5 MPa according to ASTM D256 and ASTM D638.
Example 5
Adding ENR25 and dodecanedioic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups of 100:8, adding 1, 2-dimethylimidazole which is a catalyst accounting for 1.5 percent of the total mass of ENR25 and dodecanedioic acid, and reacting for 40 minutes at the conditions of the rotating speed of 50rpm and the temperature of 70 ℃ to obtain partially crosslinked epoxy natural rubber mENR-5; and (2) melting and blending the polylactic acid and the mENR-5 in an internal mixer at 200 ℃ for 5 minutes according to the mass ratio of 70:30 to obtain modified polylactic acid (PLA/mENR-4).
Performance testing
Putting the mENR-5 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-5, which is 63%; the notched impact strength of PLA/mENR-5 was 394.3. + -. 33.4J/m, the elongation at break was 304.6. + -. 27.6% and the tensile strength was 27.8. + -. 0.5MPa as measured according to ASTM D256 and ASTM D638.
Example 6
Adding ENR30 and octadecanedioic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups of 100:12, adding 4-dimethylaminopyridine which is a catalyst accounting for 2 percent of the total mass of ENR30 and octadecanedioic acid, and reacting for 20 minutes at the rotation speed of 50rpm and the temperature of 80 ℃ to obtain partially crosslinked epoxy natural rubber mENR-6; and (2) melting and blending the polylactic acid and the mENR-6 in an internal mixer at 180 ℃ for 5 minutes according to the mass ratio of 60:40 to obtain modified polylactic acid (PLA/mENR-6).
Performance testing
Putting the mENR-6 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-6, which is 71%; the notched impact strength of PLA/mENR-6 was determined to be 288.2 + -19.7J/m, the elongation at break was 317.8 + -35.8%, and the tensile strength was 23.6 + -0.7 MPa according to ASTM D256 and ASTM D638.
Example 7
Adding ENR40 and hydrogenated dimer acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups being 100:20, adding 2-methylimidazole which is a catalyst accounting for 3 percent of the total mass of ENR40 and the hydrogenated dimer acid, and reacting for 5 minutes at the rotating speed of 50rpm and the temperature of 100 ℃ to obtain partially crosslinked epoxy natural rubber mENR-7; and (2) melting and blending the polylactic acid and the mENR-7 in an internal mixer at 180 ℃ for 5 minutes according to the mass ratio of 60:40 to obtain modified polylactic acid (PLA/mENR-7).
Performance testing
Putting the mENR-7 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-7, wherein the gel fraction is 80%; the notched impact strength of PLA/mENR-7 was determined to be 90.6. + -. 19.7J/m, the elongation at break was 116.8. + -. 30.3% and the tensile strength was 25.3. + -. 0.5MPa according to ASTM D256 and ASTM D638.
Example 8
Adding ENR50 and sebacic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups of 100:4, adding 2-methylimidazole which is a catalyst accounting for 1 percent of the total mass of ENR50 and sebacic acid, and reacting for 15 minutes at the rotation speed of 50rpm and the temperature of 60 ℃ to obtain partially crosslinked epoxy natural rubber mENR-8; and (2) melting and blending the polylactic acid and the mENR-8 in an internal mixer at 180 ℃ for 5 minutes according to the mass ratio of 80:20 to obtain modified polylactic acid (PLA/mENR-8).
Performance testing
Putting the mENR-8 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-8, which is 22%; the notched impact strength of PLA/mENR-8 was 403.8. + -. 11.9J/m, the elongation at break was 356.8. + -. 28.1% and the tensile strength was 33.6. + -. 0.7MPa, as measured according to ASTM D256 and ASTM D638.
Example 9
Adding ENR50 and adipic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups being 100:4, adding catalyst 1-methylimidazole accounting for 1 percent of the total mass of ENR50 and the adipic acid, and reacting for 60 minutes at the conditions of the rotating speed of 50rpm and the temperature of 40 ℃ to obtain partially crosslinked epoxy natural rubber mENR-9; and (2) melting and blending the polylactic acid and the mENR-9 in an internal mixer at 170 ℃ for 5 minutes according to the mass ratio of 80:20 to obtain modified polylactic acid (PLA/mENR-9).
Performance testing
Putting the mENR-9 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-9, wherein the gel fraction is 41%; the notched impact strength of PLA/mENR-9 was 412.6. + -. 31.7J/m, the elongation at break was 436.8. + -. 30.7% and the tensile strength was 35.3. + -. 0.5MPa as measured according to ASTM D256 and ASTM D638.
Example 10
Adding ENR50 and sebacic acid into an internal mixer according to the molar ratio of epoxy groups to carboxyl groups of 100:4, adding 2-methylimidazole which is a catalyst accounting for 1 percent of the total mass of ENR50 and sebacic acid, and reacting for 60 minutes at the conditions of the rotating speed of 50rpm and the temperature of 60 ℃ to obtain partially crosslinked epoxy natural rubber mENR-10; and (2) melting and blending the polylactic acid and the mENR-10 for 5 minutes at 180 ℃ in an internal mixer according to the mass ratio of 80:20 to obtain modified polylactic acid (PLA/mENR-10).
Performance testing
Putting the mENR-10 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-10, wherein the gel fraction is 50%; the notched impact strength of PLA/mENR-10 was 540.0. + -. 15.7J/m, the elongation at break was 523.8. + -. 46.5%, and the tensile strength was 33.5. + -. 0.5MPa, as measured according to ASTM D256 and ASTM D638.
Example 11
Adding ENR50 and capric acid into an internal mixer according to the molar ratio of epoxy group to carboxyl group of 100:4, adding catalyst 1-methylimidazole accounting for 1% of the total mass of ENR50 and capric acid, and reacting for 60 minutes at the rotation speed of 50rpm and the temperature of 60 ℃ to obtain epoxy natural rubber mENR-11; the polylactic acid and the mENR-11 are melted and blended for 5 minutes at 180 ℃ in an internal mixer according to the mass ratio of 80:20 to obtain the modified polylactic acid (PLA/mENR-11).
Performance testing
Putting the mENR-11 into a toluene solvent, taking toluene as the solvent, refluxing for 24 hours at 110 ℃, taking out and drying to obtain the gel fraction of the mENR-11, which is 0%; the notched impact strength of PLA/mENR-11 was 155.4. + -. 20.5J/m, the elongation at break was 40.7. + -. 6.6% and the tensile strength was 34.0. + -. 0.5MPa as measured according to ASTM D256 and ASTM D638.
Example 12
The polylactic acid and ENR50 are melted and blended for 5 minutes at 180 ℃ in an internal mixer according to the mass ratio of 80:20 to obtain the modified polylactic acid (PLA/ENR-1).
Performance testing
The notched impact strength of PLA/ENR-1 was 143.6. + -. 12.0J/m, the elongation at break was 35. + -. 7% and the tensile strength was 34.6. + -. 1.4MPa as measured according to ASTM D256 and ASTM D638.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the partially crosslinked epoxy natural rubber modified polylactic acid is characterized by comprising the following steps: firstly, banburying epoxy natural rubber, dibasic acid and a catalyst at 30-100 ℃ for 5-120 minutes to prepare partially crosslinked epoxy rubber; then the partially crosslinked epoxy rubber and the polylactic acid are melted and blended at the temperature of 160-200 ℃.
2. The method for preparing partially crosslinked epoxy natural rubber modified polylactic acid according to claim 1, wherein the dibasic acid is any one of malonic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, octadecanedioic acid and hydrogenated dimer acid.
3. The method for preparing partially crosslinked epoxidized natural rubber modified polylactic acid according to claim 2, wherein the amount of the dibasic acid added is such that the molar ratio of the epoxy group to the carboxyl group is 100:1 to 100: 20.
4. The method for producing a partially crosslinked epoxidized natural rubber modified polylactic acid according to any one of claims 1 to 3, wherein: the catalyst is any one of 1-methylimidazole, 2-methylimidazole, 1, 2-dimethylimidazole and 4-dimethylaminopyridine.
5. The method for preparing partially crosslinked epoxy natural rubber modified polylactic acid according to claim 4, wherein: the addition amount of the catalyst is 0.01-3% of the total mass of the epoxy natural rubber and the dibasic acid.
6. The method for preparing partially crosslinked epoxy natural rubber modified polylactic acid according to claim 5, wherein: the epoxy natural rubber is any one of epoxy rubbers of ENR25, ENR30, ENR40 and ENR 50.
7. The method for preparing partially crosslinked epoxy natural rubber modified polylactic acid according to claim 6, wherein: the mass ratio of the polylactic acid to the partially crosslinked epoxy rubber is 95:5-60: 40.
8. A modified polylactic acid obtained by the method for preparing a partially crosslinked epoxy natural rubber modified polylactic acid according to any one of claims 1 to 7.
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