CN114410091B - High-temperature-resistant impact-resistant high-strength modified polylactic acid material and preparation method thereof - Google Patents
High-temperature-resistant impact-resistant high-strength modified polylactic acid material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-temperature-resistant impact-resistant high-strength modified polylactic acid material and a preparation method thereof. The modified polylactic acid material is prepared from the following raw material components in percentage by weight: 88-98%, preferably 92-97% of polylactic acid material; epoxy-terminated silicone oil, 0.5-5%, preferably 1-4%; silane coupling agent, 0.1-3%, preferably 0.3-2%; 0.5 to 5%, preferably 1 to 4% of filler. The modified polylactic acid material with high thermal deformation temperature, good impact resistance, high strength, good formability and high degradability can be obtained.
Description
Technical Field
The invention relates to a modified polylactic acid material, in particular to a high-temperature-resistant impact-resistant high-strength modified polylactic acid material and a preparation method thereof.
Background
Polylactic acid (PLA), also called as polylactide, is a polyester polymer obtained by polymerizing lactic acid as a raw material, and is a completely biodegradable material. The polylactic acid has good thermal stability, wide processing window of 170-230 ℃ and good solvent resistance, can be processed in various modes, such as extrusion, spinning, biaxial stretching, injection blow molding and the like, and has wide application prospect in various fields of daily necessities, packaging, medical treatment, spinning, electronic appliances and the like. However, since PLA itself has a large brittleness (about 5% elongation at break, IZOD notched impact strength of less than 4 kJ/m) 2 ) And high Wen Xingcha (glass transition temperature 50-80 ℃ C., heat distortion temperature less than 60 ℃ C.), which limits the use thereof in the fields where high temperature resistance and impact are required, such as disposable straws, cutlery boxes, fiber spinning, etc.
The common method for solving the problems of high temperature resistance and impact resistance of polylactic acid is to add a nucleating agent, a filler, blend with a polymer with high heat distortion temperature, crosslink, add an elastomer and the like, but the simple addition of the nucleating agent and the filler does not obviously improve the heat distortion temperature, the blending with the polymer with high heat distortion temperature can cause the problem of PLA degradation difficulty due to overlarge addition, the crosslinking can cause the problem of PLA fluidity reduction, and the problem of poor impact resistance cannot be solved by the scheme; the addition of the elastomer increases the addition amount on one hand, affects the degradation of PLA, and reduces the heat distortion temperature of PLA on the other hand. Therefore, the problem of balancing the high heat distortion temperature, high strength and high impact resistance of degradable PLA materials is still a troublesome research topic in the industry.
The patent CN102206406a prepares a modified polylactic acid material having a heat distortion temperature exceeding 100 ℃ by a method of changing the crystallization state of polylactic acid using a nucleating agent, changing the molecular state by crosslinking a chain extender, and blending PLA with a high glass transition temperature polymer. However, the method cannot improve the problem of poor impact resistance of polylactic acid, and can lead to difficult molding of polylactic acid products and lower degradation degree.
Patent CN113717510a prepares polylactic acid/rubber alloy by melt blending of l-polylactic acid, d-polylactic acid and rubber particles, but on one hand, currently, d-PLA cannot be produced in mass, and on the other hand, the preparation process of the used rubber is complex, and the addition proportion is up to 30%, which seriously affects the degradation of polylactic acid material.
The patent CN103724958A adopts butadiene/butyl acrylate segmented copolymer as a toughening agent, so that the comprehensive mechanical property of the polylactic acid composite material can be improved. However, the existence of the toughening agent in a system in a covalent crosslinking mode can seriously affect the degradation capability of PLA, and the addition amount is up to 20 percent, so that the degradability of the whole material can be affected. In addition, the fluidity of the PLA melt after crosslinking is reduced, the molding of the product is affected, and a large amount of filler is required to be additionally added to compensate the reduction of the strength, and the problem of low heat distortion temperature of the PLA is not solved.
The modified polylactic acid material prepared by the technology cannot solve the problems of high heat distortion temperature and high impact resistance, too high elastomer consumption, PLA degradation, complex preparation process, product molding influence and the like, and a new solution is needed to be found to solve the problems of low heat distortion temperature, poor impact resistance and the like of the modified polylactic acid material while maintaining high strength of PLA.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-temperature-resistant impact-resistant high-strength modified polylactic acid material and a preparation method thereof. According to the invention, the epoxy-terminated silicone oil and the polylactic acid material are blended and extruded, silicone oil molecules can be grafted into polylactic acid molecular chains through the reaction of the epoxy-terminated silicone oil and the hydroxyl, and the movement of the polylactic acid molecular chains is limited through the winding action of the silicone oil molecules, so that the heat deformation temperature of the polylactic acid molecular chains is increased; on the other hand, when the external impact force is received, the entangled silicone oil molecules can absorb part of impact energy, so that the impact resistance of the polylactic acid material is improved, the mode is used for limiting the movement of polylactic acid molecular chains only through the physical winding action of the silicone oil molecules, cross-linking bonds are not introduced, the degradability of the polylactic acid is not influenced, and the entanglement can be carried out under the high-temperature operation condition of injection molding so as to recover the forming capability of the polylactic acid, so that the obtained polylactic acid material has high heat deformation temperature, good impact resistance, good formability and high degradability.
Furthermore, the silane coupling agent is grafted into the polylactic acid molecular chain through the reactive functional group, and the filler and the polylactic acid are connected together by utilizing the coupling effect of the silane coupling agent on the filler, so that on one hand, the movement of the polylactic acid molecular chain is further limited, the thermal deformation temperature of the polylactic acid is improved, and on the other hand, when the external impact force is received, the filler is introduced, the shearing yield zone is formed, and part of impact energy is absorbed, so that the impact resistance of the polylactic acid is improved.
Further, as the used silica filler has better compatibility with silicone oil molecules, the filler at two ends of the polylactic acid molecular chain and the silicone oil molecules have a trend of approaching each other, the polylactic acid molecular chain can be more easily bent, mutual entanglement among the polylactic acid molecular chains is formed, thus the movement capacity of the polylactic acid molecular chain is further limited, the heat distortion temperature and the impact strength are improved, and the strength of the modified polylactic acid is improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the modified polylactic acid material with high temperature resistance, impact resistance and high strength is prepared from the following raw material components in percentage by weight:
88-98%, preferably 92-97% of polylactic acid material;
epoxy-terminated silicone oil, 0.5-5%, preferably 1-4%;
silane coupling agent, 0.1-3%, preferably 0.3-2%;
0.5 to 5%, preferably 1 to 4% of filler.
Further, the melt index (190 ℃ C., 2.16 kg) of the polylactic acid material is 3-30 g/10min, preferably 5-25 g/10min.
Further, the molecular weight of the epoxy-terminated silicone oil is 1000 to 12000, preferably 2000 to 10000.
Further, the silane coupling agent is a silane coupling agent containing carboxyl reactive functional groups, preferably one or more of 3-isocyanatopropyl triethoxysilane and 3-isocyanatopropyl trimethoxysilane.
Further, the filler is silica, and the particle diameter thereof is preferably 5nm to 2um, more preferably 10nm to 1um.
The invention also provides a preparation method of the modified polylactic acid material with high temperature resistance, impact resistance and high strength, which comprises the following steps:
1) Uniformly mixing polylactic acid, epoxy silicone oil and a silane coupling agent in a high-speed mixer;
2) Premixing the mixture obtained in the step 1) and the filler by a high-speed mixer, and extruding and granulating by a double-screw extruder to obtain the modified polylactic acid material.
Further, the mixing conditions of the high-speed mixer in the step 1) are as follows: the temperature is 10-50 ℃, the rotating speed is 100-500 rpm, preferably 200-400 rpm, and the mixing time is 3-10 min, preferably 4-8 min.
Further, in step 2), the mixing conditions of the high-speed mixer are as follows: the temperature is 10-50 ℃, the rotating speed is 100-500 rpm, preferably 200-400 rpm, and the mixing time is 2-8 min, preferably 3-6 min.
Further, in step 2), the operation conditions of the twin-screw extruder are: the screw temperature is 170-200 ℃, preferably 175-195 ℃, and the rotation speed is 150-500 rpm, preferably 200-400 rpm.
The invention effectively solves the problem that the prior modified polylactic acid material can not realize the simultaneous improvement of the heat distortion temperature, the impact resistance and the material strength under the condition of ensuring the material strength, the formability and the degradability, and can obtain the modified polylactic acid material with high heat distortion temperature, good impact resistance, high strength, good formability and high degradability.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The raw material information used in the examples and comparative examples is shown in table 1:
TABLE 1 Main raw Material information
The test method adopted by the invention is as follows:
(1) Heat distortion temperature: the heat distortion temperature is tested according to the standard ISO 75, the load is 0.45MPa, the spline size is 80mm multiplied by 10mm multiplied by 4mm, and the heating rate is 120 ℃/h;
(2) Impact strength: impact strength according to standard ISO 179, cantilever beam, spline size 80mm x 10mm x 4mm, type A notch;
(3) Tensile strength: tensile strength according to standard ISO 527, spline dimensions of 170mm by 10mm by 4mm, tensile rate 500mm/min;
(4) Melt index (MFR) test: MFR measured according to ISO1133 at 190℃under a load of 2.16kg;
(5) Disintegration experiment: the disintegration test is carried out according to the standard GB/T19277.1 under the conditions of humidity of 60 percent and temperature of 58 ℃ for 12 weeks, and whether the number of particles with the size less than 2mm is more than 90 percent is judged as the standard.
The invention adopts the following equipment:
high-speed mixer: 120L pot type high-speed mixer, suzhou Song Yuan environmental protection technology Co., ltd;
twin screw extruder: the twin-screw extruder used was a product of Keplon mechanical Co., ltd, model ZSK 32Mc;
injection molding machine: ningbo sea plastic machine group Co., ltd, model MA600 IIS/130.
Example 1
The raw materials with the total mass of 100kg are prepared according to the following weight percentages:
PLA L130，95％；
molecular weight 5000,2.5% of epoxy-terminated silicone oil;
silane coupling agent 3-isocyanatopropyl trimethoxy silane, 1%;
silica particle size XFF31-1,1.5%.
Uniformly mixing the weighed polylactic acid, epoxy silicone oil and silane coupling agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 35 ℃, the rotating speed is 300rpm, and the mixing time is 6min to obtain a PLA mixture;
premixing the PLA mixture and the silicon dioxide by a high-speed mixer, wherein the premixing temperature is 35 ℃, the rotating speed is 200rpm, and the mixing time is 4min; and extruding by a double-screw extruder, and granulating to obtain the modified polylactic acid material. Wherein, the liquid crystal display device comprises a liquid crystal display device, the temperature of the screw rod is set to 60 ℃, 180 ℃ and 180 ℃ from the feed inlet to the machine head section by section 180 ℃, 175 ℃, 170 ℃, the rotation speed was 300rpm.
Example 2
The raw materials with the total mass of 100kg are prepared according to the following weight percentages:
PLA LX575，88％；
molecular weight 12000,5% of epoxy-terminated silicone oil;
3% of silane coupling agent 3-isocyanatopropyl triethoxysilane;
silica particle size XFF31-3,4%.
Uniformly mixing the weighed polylactic acid, epoxy silicone oil and silane coupling agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 50 ℃, the rotating speed is 500rpm, and the mixing time is 10min, so as to obtain a PLA mixture;
premixing the PLA mixture and the silicon dioxide by a high-speed mixer, wherein the premixing temperature is 50 ℃, the rotating speed is 500rpm, and the mixing time is 8min; extruding by a double-screw extruder, and granulating to obtain the modified polylactic acid material. Wherein the screw temperature was set at 60 ℃, 200 ℃, 195 ℃, 175 ℃, 170 ℃ from the feed inlet to the head section at a rotational speed of 150rpm.
Example 3
The raw materials with the total mass of 100kg are prepared according to the following weight percentages:
PLA REVODE110，91％；
molecular weight 10000,4% of epoxy-terminated silicone oil;
3-isocyanatopropyl trimethoxy silane as a silane coupling agent, and 2%;
silica particle size XFF31-2,3%.
Uniformly mixing the weighed polylactic acid, epoxy silicone oil and silane coupling agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 20 ℃, the rotating speed is 400rpm, and the mixing time is 8min to obtain a PLA mixture;
premixing the PLA mixture and the silicon dioxide by a high-speed mixer, wherein the premixing temperature is 10 ℃, the rotating speed is 300rpm, and the mixing time is 3min; extruding by a double-screw extruder, and granulating to obtain the modified polylactic acid material. Wherein the screw temperature was set at 60 ℃, 185 ℃, 180 ℃, 175 ℃, 170 ℃ from the feed inlet to the head section at a rotational speed of 200rpm.
Example 4
The raw materials with the total mass of 100kg are prepared according to the following weight percentages:
PLA FY401，94.2％；
molecular weight 2000,0.5% of epoxy-terminated silicone oil;
silane coupling agent 3-isocyanatopropyl triethoxysilane, 0.3%;
200% of silicon dioxide A and 5%.
Uniformly mixing the weighed polylactic acid, epoxy silicone oil and silane coupling agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 30 ℃, the rotating speed is 100rpm, and the mixing time is 3min to obtain a PLA mixture;
premixing the PLA mixture and the silicon dioxide by a high-speed mixer, wherein the premixing temperature is 30 ℃, the rotating speed is 400rpm, and the mixing time is 6min; extruding by a double-screw extruder, and granulating to obtain the modified polylactic acid material. Wherein, the liquid crystal display device comprises a liquid crystal display device, the screw temperature was set to 60 ℃, 185 ℃, 180 ℃, 175 ℃, 170 ℃ from the feed inlet to the head section, the rotation speed was 400rpm.
Example 5
The raw materials with the total mass of 100kg are prepared according to the following weight percentages:
PLA L105，98％；
the molecular weight of the epoxy-terminated silicone oil is 1000,1%;
silane coupling agent 3-isocyanatopropyl triethoxysilane, 0.1%;
silica a380,0.5%.
Uniformly mixing the weighed polylactic acid, epoxy silicone oil and silane coupling agent in a high-speed mixer, wherein the operation temperature of the high-speed mixer is 25 ℃, the rotating speed is 200rpm, and the mixing time is 4min to obtain a PLA mixture;
premixing the PLA mixture and the silicon dioxide by a high-speed mixer, wherein the premixing temperature is 20 ℃, the rotating speed is 100rpm, and the mixing time is 2min; extruding by a double-screw extruder, and granulating to obtain the modified polylactic acid material. Wherein the screw temperature was set at 60 ℃, 185 ℃, 180 ℃, 175 ℃, 170 ℃ from the feed inlet to the head section at a rotational speed of 500rpm.
Comparative example 1
Modified polylactic acid material was prepared in substantially the same manner as in example 1, except that epoxy-terminated silicone oil and a silane coupling agent were not added during the preparation, i.e., the raw materials included only PLA and silica of the same mass as in example.
Comparative example 2
Modified polylactic acid material was prepared in substantially the same manner as in example 1, except that no silica was added during the preparation, i.e., the raw materials included only PLA, epoxy-terminated silicone oil, and silane coupling agent of the same mass as in example.
Comparative example 3
Modified polylactic acid material was prepared in substantially the same manner as in example 1, except that no silane coupling agent was added during the preparation, i.e., the raw materials included only PLA, silica, and epoxy-terminated silicone oil of the same mass as in example.
Comparative example 4
Modified polylactic acid material was prepared in substantially the same manner as in example 1, except that epoxy-terminated silicone oil was not added during the preparation, i.e., the raw materials included only PLA, silica and silane coupling agent of the same mass as in example.
Comparative example 5
A modified polylactic acid material was prepared in substantially the same manner as in example 1, except that the epoxy-terminated silicone oil was replaced with a butadiene/butyl acrylate block copolymer (formula I) of the same mass.
Each performance test in 2 was performed on the modified polylactic acid materials prepared in examples 1 to 5 and comparative examples 1 to 5, respectively, and the test results were as follows:
TABLE 2 results of product Performance test
As can be seen from the test results of the properties in Table 2, the modified polylactic acid material prepared by the invention has the characteristics of high temperature resistance, high strength, good impact resistance, good fluidity and good degradability.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (15)
1. The modified polylactic acid material with high temperature resistance, impact resistance and high strength is characterized by comprising the following raw material components in percentage by weight:
88-98% of polylactic acid material;
0.5 to 5 percent of epoxy silicone oil;
silane coupling agent, 0.1-3%;
0.5 to 5 percent of filler;
the filler is silicon dioxide;
the silane coupling agent is one or more of 3-isocyanatopropyl triethoxysilane and 3-isocyanatopropyl trimethoxysilane.
2. The high-temperature-resistant impact-resistant high-strength modified polylactic acid material according to claim 1, which is characterized by comprising the following raw material components in percentage by weight:
92-97% of polylactic acid material;
1 to 4 percent of epoxy silicone oil;
silane coupling agent, 0.3-2%;
1 to 4 percent of filler.
3. The modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 1, wherein the melt index of the polylactic acid material is 3-30 g/10min at 190 ℃ under 2.16 kg.
4. The modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 3, wherein the melt index of the polylactic acid material is 5-25 g/10min at 190 ℃ under 2.16 kg.
5. The modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 1, wherein the molecular weight of the epoxy silicone oil is 1000-12000.
6. The modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 5, wherein the molecular weight of the epoxy silicone oil is 2000-10000.
7. The modified polylactic acid material having high temperature resistance, impact resistance and high strength according to any one of claims 1 to 6, wherein the filler has a particle size of 5nm to 2. Mu.m.
8. The modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 7, wherein the particle size of the filler is 10 nm-1 μm.
9. A method for preparing the modified polylactic acid material with high temperature resistance, impact resistance and high strength according to any one of claims 1 to 8, comprising the following steps:
1) Uniformly mixing polylactic acid, epoxy silicone oil and a silane coupling agent in a high-speed mixer;
2) Premixing the mixture obtained in the step 1) and the filler by a high-speed mixer, and extruding and granulating by a double-screw extruder to obtain the modified polylactic acid material.
10. The method for preparing the modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 9, wherein the mixing condition of the high-speed mixer in the step 1) is as follows: the temperature is 10-50 ℃, the rotating speed is 100-500 rpm, and the mixing time is 3-10 min.
11. The method for preparing the modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 9, wherein the mixing condition of the high-speed mixer in the step 1) is as follows: the temperature is 10-50 ℃, the rotating speed is 200-400 rpm, and the mixing time is 4-8 min.
12. The method for preparing a modified polylactic acid material with high temperature resistance, impact resistance and high strength according to any one of claims 9 to 11, wherein in step 2), the mixing conditions of the high-speed mixer are as follows: the temperature is 10-50 ℃, the rotating speed is 100-500 rpm, and the mixing time is 2-8 min.
13. The method for preparing a modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 12, wherein in the step 2), the mixing condition of the high-speed mixer is as follows: the temperature is 10-50 ℃, the rotating speed is 200-400 rpm, and the mixing time is 3-6 min.
14. The method for preparing a modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 12, wherein in the step 2), the operation conditions of the twin screw extruder are as follows: the temperature of the screw is 170-200 ℃ and the rotating speed is 150-500 rpm.
15. The method for preparing a modified polylactic acid material with high temperature resistance, impact resistance and high strength according to claim 14, wherein in the step 2), the operation conditions of the twin screw extruder are as follows: the temperature of the screw is 175-195 ℃ and the rotating speed is 200-400 rpm.
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