CN114230957A - High-toughness PLA/rice hull composite material and preparation method thereof - Google Patents
High-toughness PLA/rice hull composite material and preparation method thereof Download PDFInfo
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- CN114230957A CN114230957A CN202111557694.5A CN202111557694A CN114230957A CN 114230957 A CN114230957 A CN 114230957A CN 202111557694 A CN202111557694 A CN 202111557694A CN 114230957 A CN114230957 A CN 114230957A
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- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 240
- 235000009566 rice Nutrition 0.000 title claims abstract description 240
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 240000007594 Oryza sativa Species 0.000 title 1
- 241000209094 Oryza Species 0.000 claims abstract description 239
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 71
- 238000001035 drying Methods 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000004140 cleaning Methods 0.000 claims description 38
- 238000002791 soaking Methods 0.000 claims description 38
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract 4
- 229920000742 Cotton Polymers 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 abstract 1
- 239000002537 cosmetic Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 235000011888 snacks Nutrition 0.000 abstract 1
- 210000002268 wool Anatomy 0.000 abstract 1
- 239000004626 polylactic acid Substances 0.000 description 103
- 229920000747 poly(lactic acid) Polymers 0.000 description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 238000005406 washing Methods 0.000 description 32
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 230000000704 physical effect Effects 0.000 description 17
- 229910001868 water Inorganic materials 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- 239000010903 husk Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a high-toughness PLA/rice hull composite material and a preparation method thereof, wherein the high-toughness PLA/rice hull composite material comprises the following components in percentage by weight: 35-67% of modified PLA, 50-5% of modified rice hull and 15-29% of PBAT, wherein the PLA is subjected to GMA modification treatment. The rice hull is treated by alkali liquor and silane coupling agent together. The PLA/rice hull composite material has the advantages of high toughness, low cost, good biodegradability and good processability. The composite material can be widely used in the fields of clothing industry (the clothes blended with the wool and cotton can be prevented from wrinkling and keep the shape), packaging industry (packaging bags, packaging boxes, disposable snack boxes and other film products and cosmetic bottles, medicine bottles and other packaging containers), automobile industry (interior plastic, exterior plastic and chassis plastic), biomedical industry (bone materials, surgical sutures, ophthalmic materials) and the like. The preparation method of the PLA/rice hull composite material prepared by the invention is simple, the production process is easy to implement, and the PLA/rice hull composite material is green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-toughness PLA/rice hull composite material and a preparation method thereof.
Background
With the progress of society and the development of science and technology, plastic products are more and more widely applied in human life, but most of the raw materials of high polymer materials are derived from petrochemical resources and are non-renewable, which causes energy crisis in the past, and most of the high polymer materials are difficult to degrade in natural environment due to stable structure and are easy to cause environmental pollution. Therefore, the development of biodegradable polymer materials is one of the main ways to solve this dilemma.
The polylactic acid (PLA) is obtained by polymerizing lactic acid which is a fermentation product of renewable resources (crops such as corn, sugarcane and the like) as a raw material, has good degradability, and CO is a final product of degradation of waste PLA products2And H2O, can participate in the circulation of nature. However, the application field of polylactic acid is limited by the defects of poor toughness, low crystallinity, poor high temperature resistance, high production cost and the like, so that the polylactic acid has important practical value in toughening and modifying the polylactic acid. The rice hull is a natural polymer material, and has the advantages of large length-diameter ratio, low density, high specific strength, biodegradability and the like. Thousands of tons of rice hull wastes are generated in China every year, and the rice hull wastes are comprehensively utilized as biomass raw materials, so that the reasonable use of agricultural and forestry wastes can be promoted, the energy and environmental problems can be relieved, and huge economic benefits are generated. The PLA/rice hull composite material provided by the invention is prepared from PLA, PBAT and agricultural solid waste rice hulls serving as raw materials by a physical and chemical modification method and a melt blending technology, and has the advantages of excellent comprehensive performance, low cost and wide application prospect
Disclosure of Invention
The invention aims to provide a PLA/rice hull composite material and a preparation method thereof, and the composite material has the advantages of high toughness, environmental friendliness, low cost and simple processing technology. In order to achieve the above purpose, the invention provides the following technical scheme:
the invention firstly provides a PLA/rice hull composite material, which comprises the following components in percentage by weight: 35-67% of modified PLA, 50-5% of modified rice hull and 15-29% of PBAT;
wherein the modified PLA comprises the following components in percentage by weight: 84-92% PLA and 16-8% GMA;
wherein the modified rice hull comprises the following components in percentage by weight: 95-99% of rice hull and 5-1% of silane coupling agent;
preferably, the preparation method of the modified PLA comprises the following steps:
placing PLA and GMA into a system for full mixing, then adding DCP, and carrying out reaction blending for 7-9min at 170 ℃ to obtain modified PLA;
preferably, the preparation method of the modified rice hull comprises the following steps:
crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, soaking the dried rice hulls in prepared alkali liquor, cleaning the rice hulls after soaking, and drying the rice hulls for 12 hours at 80 ℃. Then putting the pretreated rice hulls into a silane coupling agent ethanol solution, soaking and stirring, and cleaning and drying for 12 hours at 80 ℃ after modification;
preferably, the silane coupling agent is selected from one or more of KH550, KH560, KH570, KH580, VTES, VTS and the like;
preferably, the concentration of the self-made alkali liquor is 3-7%, the proportion of the rice hulls to the alkali liquor is 1 (4-12), and the rice hulls are soaked in the alkali liquor for 4 hours;
preferably, the ratio of the rice husk to the silane coupling agent ethanol solution is 1: (4-12); soaking in an ethanol solution of a silane coupling agent for 4 hours;
the invention also provides a preparation method of the PLA/rice hull composite material, which comprises the following steps: and carrying out melt blending on the modified PLA, the modified rice hull and the PBAT to obtain the PLA/rice hull composite material.
Preferably, the melt blending temperature is 170 ℃ and the melt blending time is 8 min.
The invention has the advantages of
The invention firstly provides a PLA/rice hull composite material, which comprises the following components in percentage by weight: 35-67% of modified PLA, 50-5% of modified rice hull and 15-29% of PBAT; wherein the modified PLA comprises the following components in percentage by weight: 84-92% PLA and 16-8% GMA; wherein the modified rice hull comprises the following components in percentage by weight: 95-99% of rice husk and 5-1% of silane coupling agent. Compared with the prior art, the rice hulls are added into the modified PLA, so that the problem of recycling of agricultural wastes is solved, and the obtained PLA/rice hull composite material is low in cost, high in toughness and easy to degrade. The experimental results show that: the impact strength of the composite material can reach 218J/m, and the modulus can reach 2256 MPa.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The invention firstly provides a PLA/rice hull composite material, which comprises the following components in percentage by weight: 35-67% modified PLA resin, preferably 56-63%, more preferably 60-63%; 50-5% of modified rice husk, preferably 20-10%, more preferably 15-10%; 15-29% PBAT, preferably 24-27%, more preferably 26-27%.
Wherein the modified PLA comprises the following components in percentage by weight: 84-92% PLA, preferably 86-90%, more preferably 88%; 16-8% GMA, preferably 14-10%, more preferably 12%.
Wherein the modified rice hull comprises the following components in percentage by weight: 95-99% rice hulls, preferably 96-98%, more preferably 97%; 5-1% of a silane coupling agent, preferably 4-2%, more preferably 3%.
The PLA resin according to the present invention is a commercially available product which is commonly used by those skilled in the art.
The preparation method of the modified PLA according to the present invention preferably comprises:
placing PLA and GMA into a system for full mixing, then adding DCP, and carrying out reaction blending for 8min at 170 ℃ to obtain modified PLA;
the method of producing modified rice hulls according to the invention preferably includes:
crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, soaking the dried rice hulls in prepared alkali liquor, cleaning the rice hulls after soaking, and drying the rice hulls for 12 hours at 80 ℃. Then putting the pretreated rice hulls into a silane coupling agent ethanol solution, soaking and stirring, and cleaning and drying for 12 hours at 80 ℃ after modification;
according to the invention, the silane coupling agent is preferably one or more of gamma-aminopropyltriethoxysilane (KH 550), gamma-glycidoxypropyltrimethoxysilane (KH 560), gamma-methacryloxypropylsilane (KH 570), gamma-mercaptopropyltriethoxysilane (KH 580), Vinyltriethoxysilane (VTES), Vinyltrimethoxysilane (VTS) and the like;
according to the invention, the concentration of the self-made alkali liquor is preferably 3-7%, more preferably 4-6%, and more preferably 5%; the proportion of the rice hulls to the alkali liquor is preferably 1: (4-12), more preferably 1: (6-10), more preferably 1: 8; the soaking time in the alkali liquor is 2-7h, more preferably 3-6h, and more preferably 4 h;
according to the invention, the ratio of the rice husk to the silane coupling agent ethanol solution is preferably 1: (4-12), more preferably 1: (6-10), more preferably 1: 8; the soaking time in the silane coupling agent ethanol solution is 2-7h, more preferably 3-6h, and even more preferably 4 h.
The invention also provides a preparation method of the PLA/rice hull composite material, which comprises the following steps: and carrying out melt blending on the modified PLA resin, the modified rice hull and the PBAT to obtain the PLA/rice hull composite material. The melt blending temperature is preferably 170 ℃, and the melt blending time is preferably 8 min.
The present invention will be further illustrated in detail by the following examples, but it should be noted that these examples should not be construed as limiting the scope of the present invention in any way.
Example 1
Preparing modified PLA:
firstly, putting 60g of PLA and 9g of GMA into a system for full mixing, then adding 0.48g of DCP, and carrying out reaction blending for 8min at 170 ℃ to obtain modified PLA;
preparing modified rice hulls:
firstly, crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, and then putting the dried rice hulls into alkali liquor (with the concentration of 5%) for soaking treatment, wherein the weight ratio of the rice hulls to the alkali liquor is 1: 8. soaking for 4 hours, then cleaning the rice hulls, firstly washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning, setting the drying temperature to be 80 ℃, and drying for 12 hours. And then putting the pretreated rice hulls into a KH560 ethanol solution (with the concentration of 3%) for soaking modification treatment, wherein the weight ratio of the rice hulls to the KH560 ethanol solution is 1: 8. and simultaneously stirring for 4 hours, cleaning the modified rice hulls, washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning is finished, setting the drying temperature to 80 ℃, and drying for 12 hours.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 2
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
same as in example 1.
Preparing a PLA/rice hull composite material:
weighing 39.9g of modified PLA resin, 3g of modified rice hull and 17.1g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 3
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
same as in example 1.
Preparing a PLA/rice hull composite material:
weighing 35.7g of modified PLA resin, 9g of modified rice hull and 15.3g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 4
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
same as in example 1.
Preparing a PLA/rice hull composite material:
weighing 33.6g of modified PLA resin, 12g of modified rice hull and 14.4g of PBATT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 5
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
same as in example 1.
Preparing a PLA/rice hull composite material:
weighing 29.4g of modified PLA resin, 18g of modified rice hull and 12.6g of PBATT for melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, thus obtaining the PLA/rice hull composite material. The physical properties of the composite material are shown in Table 1. Example 6
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
same as in example 1.
Preparing a PLA/rice hull composite material:
weighing 25.2g of modified PLA resin, 24g of modified rice hull and 10.8g of PBATT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 7
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
same as in example 1.
Preparing a PLA/rice hull composite material:
21g of modified PLA resin, 30g of modified rice hull and PBAT9g are weighed and melted and blended, the mixing temperature is fixed at 170 ℃, the mixing time is 8min, and the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 8
Preparing modified PLA:
firstly, putting 58g of PLA and 11g of GMA into a system for full mixing, then adding 0.48g of DCP, and carrying out reaction blending for 8min at 170 ℃ to obtain modified PLA;
preparing modified rice hulls:
firstly, crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, and then putting the dried rice hulls into alkali liquor (with the concentration of 5%) for soaking treatment, wherein the weight ratio of the rice hulls to the alkali liquor is 1: 8. soaking for 4 hours, then cleaning the rice hulls, firstly washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning, setting the drying temperature to be 80 ℃, and drying for 12 hours. And then putting the pretreated rice hulls into a KH560 ethanol solution (with the concentration of 3%) for soaking modification treatment, wherein the weight ratio of the rice hulls to the KH560 ethanol solution is 1: 8. and simultaneously stirring for 4 hours, cleaning the modified rice hulls, washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning is finished, setting the drying temperature to 80 ℃, and drying for 12 hours.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 9
Preparing modified PLA:
firstly, 63.5g of PLA and 5.5g of GMA are put into a system to be fully mixed, then 0.48g of DCP is added, and the mixture is reacted and blended for 8min at the temperature of 170 ℃ to obtain modified PLA;
preparing modified rice hulls:
firstly, crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, and then putting the dried rice hulls into alkali liquor (with the concentration of 5%) for soaking treatment, wherein the weight ratio of the rice hulls to the alkali liquor is 1: 8. soaking for 4 hours, then cleaning the rice hulls, firstly washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning, setting the drying temperature to be 80 ℃, and drying for 12 hours. And then putting the pretreated rice hulls into a KH560 ethanol solution (with the concentration of 3%) for soaking modification treatment, wherein the weight ratio of the rice hulls to the KH560 ethanol solution is 1: 8. and simultaneously stirring for 4 hours, cleaning the modified rice hulls, washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning is finished, setting the drying temperature to 80 ℃, and drying for 12 hours.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 10
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
firstly, crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, and then putting the dried rice hulls into alkali liquor (with the concentration of 7%) for soaking treatment, wherein the weight ratio of the rice hulls to the alkali liquor is 1: 8. soaking for 4 hours, then cleaning the rice hulls, firstly washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning, setting the drying temperature to be 80 ℃, and drying for 12 hours. And then putting the pretreated rice hulls into a KH560 ethanol solution (with the concentration of 1%) for soaking modification treatment, wherein the weight ratio of the rice hulls to the KH560 ethanol solution is 1: 8. and simultaneously stirring for 4 hours, cleaning the modified rice hulls, washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning is finished, setting the drying temperature to 80 ℃, and drying for 12 hours.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 11
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
firstly, crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, and then putting the dried rice hulls into alkali liquor (with the concentration of 7%) for soaking treatment, wherein the weight ratio of the rice hulls to the alkali liquor is 1: 8. soaking for 4 hours, then cleaning the rice hulls, firstly washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning, setting the drying temperature to be 80 ℃, and drying for 12 hours. And then putting the pretreated rice hulls into a KH560 ethanol solution (with the concentration of 5%) for soaking modification treatment, wherein the weight ratio of the rice hulls to the KH560 ethanol solution is 1: 8. and simultaneously stirring for 4 hours, cleaning the modified rice hulls, washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning is finished, setting the drying temperature to 80 ℃, and drying for 12 hours.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 12
Preparing modified PLA:
firstly, putting 60g of PLA and 9g of GMA into a system for full mixing, then adding 0.28g of DCP, and carrying out reaction blending for 8min at 170 ℃ to obtain modified PLA;
preparing modified rice hulls:
same as in example 1.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 13
Preparing modified PLA:
firstly, putting 60g of PLA and 9g of GMA into a system for full mixing, then adding 0.69g of DCP, and carrying out reaction blending for 8min at 170 ℃ to obtain modified PLA;
preparing modified rice hulls:
same as in example 1.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 14
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
firstly, crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, and then putting the dried rice hulls into an alkali liquor (with the concentration of 3%) for soaking treatment, wherein the weight ratio of the rice hulls to the alkali liquor is 1: 8. soaking for 4 hours, then cleaning the rice hulls, firstly washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning, setting the drying temperature to be 80 ℃, and drying for 12 hours. And then putting the pretreated rice hulls into a KH560 ethanol solution (with the concentration of 3%) for soaking modification treatment, wherein the weight ratio of the rice hulls to the KH560 ethanol solution is 1: 8. and simultaneously stirring for 4 hours, cleaning the modified rice hulls, washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning is finished, setting the drying temperature to 80 ℃, and drying for 12 hours.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
Example 15
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
firstly, crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, and then putting the dried rice hulls into alkali liquor (with the concentration of 7%) for soaking treatment, wherein the weight ratio of the rice hulls to the alkali liquor is 1: 8. soaking for 4 hours, then cleaning the rice hulls, firstly washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning, setting the drying temperature to be 80 ℃, and drying for 12 hours. And then putting the pretreated rice hulls into a KH560 ethanol solution (with the concentration of 3%) for soaking modification treatment, wherein the weight ratio of the rice hulls to the KH560 ethanol solution is 1: 8. and simultaneously stirring for 4 hours, cleaning the modified rice hulls, washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning is finished, setting the drying temperature to 80 ℃, and drying for 12 hours.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1. Example 16
Preparing modified PLA:
same as in example 1.
Preparing modified rice hulls:
firstly, crushing rice hulls into 100-mesh particles, drying the crushed rice hulls, and then putting the dried rice hulls into alkali liquor (with the concentration of 7%) for soaking treatment, wherein the weight ratio of the rice hulls to the alkali liquor is 1: 8. soaking for 4 hours, then cleaning the rice hulls, firstly washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning, setting the drying temperature to be 80 ℃, and drying for 12 hours. And then putting the pretreated rice hulls into a KH570 ethanol solution (with the concentration of 3%) for soaking modification treatment, wherein the weight ratio of the rice hulls to the KH570 ethanol solution is 1: 8. and simultaneously stirring for 4 hours, cleaning the modified rice hulls, washing for 5-6 times by using clean water to ensure that the surfaces of the rice hulls are clean, finally washing for one time by using deionized water, putting the rice hulls into drying equipment after cleaning is finished, setting the drying temperature to 80 ℃, and drying for 12 hours.
Preparing a PLA/rice hull composite material:
weighing 37.8g of modified PLA resin, 6g of modified rice hull and 16.2g of PBAT, and carrying out melt blending, wherein the mixing temperature is fixed at 170 ℃, and the mixing time is 8min, so that the PLA/rice hull composite material can be obtained. The physical properties of the composite material are shown in Table 1.
TABLE 1 physical Properties of composites made in examples 1-16
| Serial number | PLA/PBAT/CH(wt/wt/wt) | Impact Strength (J/m) | Tensile Strength (MPa) | Modulus (MPa) |
| Example 1 | 66.5/28.5/10 | 163 | 31 | 1207 |
| Example 2 | 63/27/5 | 218 | 33 | 1495 |
| Example 3 | 59.5/25.5/15 | 111 | 31 | 1713 |
| Example 4 | 56/24/20 | 68 | 29 | 1552 |
| Example 5 | 49/21/30 | 56 | 21 | 1744 |
| Example 6 | 42/18/40 | 43 | 10 | 2256 |
| Example 7 | 35/15/50 | 37 | 7 | 1828 |
| Example 8 | 66.5/28.5/10 | 160 | 30 | 1155 |
| Example 9 | 66.5/28.5/10 | 158 | 30 | 1168 |
| Example 10 | 66.5/28.5/10 | 159 | 29 | 1134 |
| Example 11 | 66.5/28.5/10 | 161 | 30 | 1193 |
| Example 12 | 66.5/28.5/10 | 157 | 29 | 1101 |
| Example 13 | 66.5/28.5/10 | 155 | 31 | 1165 |
| Example 14 | 66.5/28.5/10 | 160 | 28 | 1096 |
| Example 15 | 66.5/28.5/10 | 161 | 30 | 1123 |
| Example 16 | 66.5/28.5/10 | 153 | 28 | 1136 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and modifications and variations thereof within the spirit and scope of the invention will be apparent to those skilled in the art.
Claims (9)
1. A high-toughness PLA/rice hull composite material and a preparation method thereof are characterized by comprising the following components in percentage by weight: 35-67% of modified PLA, 50-5% of modified rice hull and 15-29% of PBAT;
the modified PLA comprises the following components in percentage by weight: 84-92% PLA and 16-8% GMA;
the modified rice hull comprises the following components in percentage by weight: 95-99% of rice hull and 5-1% of silane coupling agent;
the preparation method of the modified PLA comprises the following steps: placing PLA and GMA into a system for full mixing, then adding DCP, and carrying out reaction blending at 170 ℃ to obtain modified PLA;
the preparation method of the modified rice hull comprises the following steps:
a1, crushing granular rice hulls by using a small crusher, sieving the crushed materials, and drying to obtain powder rice hulls;
a2, soaking the rice hulls treated in the A1 in prepared alkali liquor, cleaning and drying after soaking;
a3, putting the rice hulls treated in the A2 into a silane coupling agent ethanol solution, soaking and stirring, and cleaning and drying after modification;
the preparation method of the PLA/rice hull composite material comprises the following steps: and carrying out melt blending on the modified PLA, the PBAT and the modified rice hulls to obtain the PLA/rice hull composite material.
2. The PLA/rice hull composite material and the preparation method thereof as claimed in claim 1, wherein the amount of DCP used in the preparation method of the modified PLA is 0.4-1.0% of the modified PLA.
3. The PLA/rice hull composite material and the preparation method thereof as claimed in claim 1, wherein the concentration of the homemade lye is 3-7%, and the ratio of the rice hulls to the lye is 1: (4-12), and the soaking time is 2-7 hours.
4. The method for preparing PLA/rice hull composite material according to claim 1, wherein the rice hull treated with alkali solution is dried at 80 ℃ for 12 hours.
5. The method for preparing PLA/rice hull composite material according to claim 1, wherein the ratio of the rice hull to the silane coupling agent ethanol solution is 1: (4-12), and the soaking time is 2-7 hours.
6. The method for preparing PLA/rice hull composite material according to claim 1, wherein the silane coupling agent is one or more selected from gamma-aminopropyltriethoxysilane (KH 550), gamma-glycidoxypropyltrimethoxysilane (KH 560), gamma-methacryloxypropylsilane (KH 570), gamma-mercaptopropyltriethoxysilane (KH 580), Vinyltriethoxysilane (VTES), Vinyltrimethoxysilane (VTS), etc.
7. The method for preparing a PLA/rice hull composite according to claim 1, wherein the rice hull particles are 100 mesh in size.
8. The process for preparing a PLA/rice hull composite according to claim 1, characterized in that the modified rice hull is dried at 80 ℃ for 12 hours.
9. The preparation method of the PLA/rice hull composite material according to claim 1, wherein the melt blending temperature is 170 ℃ and the melt blending time is 6-12 min.
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