CN115873388A - Hydrophobic high-bamboo-powder-filled biodegradable composite material and preparation method thereof - Google Patents
Hydrophobic high-bamboo-powder-filled biodegradable composite material and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 84
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- 239000011425 bamboo Substances 0.000 claims abstract description 84
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims 1
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
A hydrophobic high bamboo powder filled biodegradable composite material and a preparation method thereof, wherein the composite material comprises the following raw materials: 20 to 70 parts of PLA; 1.0 to 20 parts of PLA-g-MAH; 10 to 30 parts of modified bamboo powder; 0.2 to 1 part of antioxidant; 0.1 to 2 parts of a lubricant; 0.1 to 8 parts of a compatilizer; 0.1 to 3 parts of a coupling agent; 0.1 to 5 portions of end group silane modified polyether. According to the invention, the surface of the material is modified by carrying out surface modification treatment on the bamboo powder, the surface polarity of the material is reduced, the reduction of the number of surface hydroxyl groups promotes the bamboo powder to be fully dispersed in a PLA matrix, the mechanical property of the material is maintained, then the compatibility of the bamboo powder and a resin matrix is improved by carrying out hydrophobic compatibilization modification on a PLA/bamboo powder system, the use period is prolonged by improving the hydrophobicity of the composite material by adding silane modified polyether, and meanwhile, the cost can be obviously reduced by filling high-component bamboo powder.
Description
Technical Field
The invention relates to a biodegradable composite material, in particular to a hydrophobic high bamboo powder filled biodegradable composite material and a preparation method thereof.
Background
With the rapid development of society, the traditional petroleum-based plastics are spread throughout our daily life, petroleum-based materials are over-developed as non-renewable resources, and the global energy crisis situation is more severe. The global countries attach increasing importance to the ecological environment, and the biodegradable material is beginning to receive wide attention as a novel environment-friendly material.
Polylactic acid (PLA) is a pure natural biological base material, is a high polymer material obtained by fermenting, purifying, polymerizing and other steps of crops rich in starch, and similarly, bamboo powder fiber is one of the high polymer materials with the most abundant storage capacity in the nature.
Polylactic acid (PLA) materials have the advantages of high hardness, easy processing, good biocompatibility and the like, but the current PLA materials are still higher in price compared with the traditional plastics. The bamboo powder has the characteristics of wide source, low cost and the like, and is the only natural high polymer material in the filler. If PLA and bamboo powder are subjected to composite modification, the material cost is greatly reduced while the PLA characteristic is maintained, the main component of the bamboo powder is cellulose, a large amount of polar hydroxyl groups are contained in a cellulose structural unit, so that the water absorption of the material is stronger, and meanwhile, the problem that the bamboo powder is poor in compatibility with a resin matrix exists in the processing process is solved.
CN112920573A discloses a preparation method of a polylactic acid transparent straw, which comprises the steps of mixing wollastonite powder, talcum powder, limestone and methyl cellulose, impregnating and alkalizing, oxidizing, polymerizing at high temperature, cooling, cleaning, sintering, weighing bamboo fibers, crop straws and an aluminum-titanium coupling agent after the plasticizer particles are cooled, soaking in deionized water, filtering and drying to obtain modified fibers, adding a mixture of polylactic acid and polyethylene into an open mill, mixing the prepared plasticizer particles, modified fibers, a proper amount of a transparent agent and an antibacterial agent, adding the mixture into the open mill, and extruding the obtained blended material through an extruder to obtain a material which has higher toughness and strength, is convenient to carry and is safe and convenient to use, but the problem of migration and precipitation of the components of the plasticizer exists subsequently in the invention.
CN114031911A discloses a degradable bio-based film material and a preparation method thereof, wherein the bio-based film material is prepared from the following raw materials in parts by weight: polylactic acid, dextran, straw fiber, modified amylopectin, silk fibroin, ammonium dihydrogen phosphate, sodium alginate, polyethylene glycol, ethyl vanillin, a coupling agent, a plasticizer, an antibacterial agent and other materials are blended and extruded to obtain modified particles. The composite bio-based material disclosed by the invention is easy to obtain raw materials, environment-friendly and good in degradability, but the component system is complex and not beneficial to industrial production, and meanwhile, the starch filling water absorption is strong, and the risk of too fast performance attenuation caused by water absorption exists in the later stage.
CN111808406B discloses a heat-resistant plant fiber PLA compound which can be processed at low temperature and keep the original color of the fiber with simple operation and a preparation method thereof. The preparation method comprises the steps of preparing PLA, PBS, a plasticizer, plant fibers, a coupling agent-ethanol solution, an antioxidant and a lubricant, wherein the coupling agent-ethanol solution is obtained by compounding the coupling agent and the ethanol solution according to a mass ratio of 1. The heat-resistant plant fiber PLA compound has the effect of keeping the original color of the fiber after low-temperature processing, but has the advantages of low filling and high cost, and is not beneficial to popularization and use.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide a hydrophobic high-bamboo-powder-filled biodegradable composite material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a hydrophobic high bamboo powder filled biodegradable composite material comprises the following raw materials in percentage by mass:
20-70 parts of PLA;
1.0-20 parts of PLA-g-MAH;
10-30 parts of modified bamboo powder;
0.2-1 part of antioxidant;
0.1-2 parts of a lubricant;
0.1-8 parts of a compatilizer;
0.1-3 parts of a coupling agent;
0.1-5 parts of end group silane modified polyether.
According to a further technical scheme, the raw materials preferably comprise the following components in percentage by mass:
35-65 parts of PLA;
10-20 parts of PLA-g-MAH;
20-30 parts of modified bamboo powder;
0.3-0.5 part of antioxidant;
0.5-1 part of lubricant;
5-8 parts of a compatilizer;
1-3 parts of a coupling agent;
1-3 parts of end silane modified polyether.
According to a further technical scheme, the PLA is PLA resin, and the melt index is less than or equal to 10g/10min (190 ℃,2.16 kg). Can be selected from: LX175 and LX575 of Dadall, 4032D and 3052D of Natural works, REVODE110 and REVODE190 of Zhejiang Haizang.
In a further technical scheme, the preparation method of the PLA-g-MAH comprises the following steps:
according to 100 parts of PLA, firstly dissolving 3 parts of Maleic Anhydride (MAH) and 0.3 part of dicumyl peroxide (DCP) in 20ml of ethanol, pouring the solution into polylactic acid after the dissolution is finished, uniformly mixing the solution and the polylactic acid until the ethanol is volatilized, adding the mixture into an internal mixer for banburying and blending, setting the temperature of the internal mixer to be 170 ℃, carrying out banburying for 5 minutes, carrying out extrusion granulation by a single-screw extruder after the banburying is finished, and setting the temperatures from one zone of the extruder to a machine head to be 130 ℃, 145 ℃, 165 ℃, 160 ℃ and 150 ℃ respectively; finally, the particles are placed in a vacuum oven to be dried for 24 hours at the temperature of 60 ℃ to obtain PLA-g-MAH.
According to a further technical scheme, the preparation method of the modified bamboo powder comprises the following steps:
firstly, weighing 500g of dried bamboo powder, wherein the mesh number of the bamboo powder is 40-200 meshes; and then adding the bamboo powder into a NaOH solution with the mass fraction of 12%, heating and stirring for 6 hours to fully react, carrying out suction filtration on the alkalized bamboo powder for 5 times by using a Buchner funnel, and finally putting the alkali-treated wood fiber into a vacuum drying oven to carry out vacuum drying for 12 hours at the temperature of 40 ℃ to obtain the alkali-treated modified bamboo powder.
According to a further technical scheme, the antioxidant is hindered phenol antioxidant or phosphite antioxidant, and is selected from one or more of antioxidant 1010, antioxidant 1010 and antioxidant 1076.
According to a further technical scheme, the lubricant is one or more of silicone, stearic acid, stearate, ethylene bis-stearamide and derivatives thereof.
According to a further technical scheme, the compatilizer is an epoxy compatilizer and is selected from one or more of ethylene butyl acrylate grafted glycidyl methacrylate (EBA-GMA), polyethylene oxide (PEO) and ethylene acrylic acid copolymer (EAA).
In a further technical scheme, the coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH 550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH 560) and gamma- (methacryloyloxy) propyltrimethoxysilane (KH 570).
According to a further technical scheme, the terminal silane modified polyether is silane coupling agent modified polyether, and the preparation method comprises the following steps:
carrying out hydrosilylation reaction on 0.01mol of terminal allyl polyoxypropylene ether and 0.05mol of methyl hydrogen dichlorosilane at 88-98 ℃ for 3-5 h under the catalysis of chloroplatinic acid, then reacting with methanol-cyclopropane solution at 35-55 ℃ for 3h, and then heating to 70 ℃ for reaction for 3h to obtain the terminal silane polyether.
Further, the invention also comprises a preparation method of the hydrophobic high bamboo powder filled biodegradable composite material, which comprises the following steps:
step one, weighing the components in parts by weight;
step two, adding the resin and the auxiliary agent into a high-speed mixer, uniformly mixing, and adding into a double-screw extruder for extrusion granulation; the melt extrusion temperature of the double-screw extruder is 150-180 ℃, and the screw rotating speed is 150-300 r/min;
and step three, water-cooling and granulating to obtain the hydrophobic bamboo powder filling composite modified material.
The working principle and the advantages of the invention are as follows:
1. according to the invention, PLA (polylactic acid) is grafted by adding Maleic Anhydride (MAH), dicumyl peroxide (DCP) is used as an initiator, alkoxy radicals take a hydrogen abstraction reaction, active radicals on a main chain of polylactic acid can become grafting points of the maleic anhydride, and the grafting points of the maleic anhydride and substances with functional groups such as amino groups, hydroxyl groups and the like can act together, so that a grafting reaction is carried out, and the compatibility and the interface bonding capability can be improved by adding PLA grafted Maleic Anhydride (MAH) grafts.
2. According to the invention, the bamboo powder is subjected to alkali treatment, the impurities such as pectin in the bamboo powder fiber can be dissolved by the NaOH solution, a large amount of impurities are removed, the polarity of the wood fiber surface can be reduced by consuming a large amount of hydroxyl on the surface of the bamboo powder, and the compatibility of the bamboo powder matrix and PLA can be improved.
3. According to the bamboo powder composite material modified by PLA and alkali treatment, the compatilizer is added, so that the dispersibility of the bamboo powder in the resin matrix is further improved, the two-phase bonding force of the bamboo powder and the PLA is enhanced, the ratio of the bamboo powder in a composite system is further increased, and the cost is reduced.
4. In order to further improve the hydrophobicity of a PLA/bamboo powder system, the silane coupling agent and the silane modified polyether are added, the silane coupling agent is firstly hydrolyzed with residual moisture in the terminal silane, hydrolytic crosslinking is avoided, the structural stability is ensured, the silane coupling agent and the terminal silane on the main chain of the resin are hydrolyzed with moisture in the air to generate corresponding silanol groups and then are continuously condensed, and the coupling agent provides more crosslinking points to enable the main chain to form a more three-dimensional network structure, so that the crosslinking degree is improved. And some silane coupling agents can also improve the bonding force of the resin and the bamboo powder, because the siloxane of the silane coupling agent is hydrolyzed or the silicon hydroxyl groups after the hydrolysis and the hydroxyl groups on the surface are condensed, and the hydrophobicity of the PLA/bamboo powder composite material is further improved.
In conclusion, because the pure PLA/bamboo powder composite material has poor compatibility and is easy to absorb water, the bamboo powder is subjected to surface modification treatment, the surface polarity of the material is reduced, the reduction of the number of surface hydroxyl groups promotes the bamboo powder to be fully dispersed in a PLA matrix, the mechanical property of the material is maintained, then the PLA/bamboo powder system is subjected to hydrophobic compatibilization modification, the compatibility of the bamboo powder and a resin matrix is improved, the hydrophobicity of the composite material is improved by adding silane modified polyether, the service cycle is prolonged, and meanwhile, the cost can be obviously reduced by filling high-component bamboo powder.
Drawings
FIG. 1 is a schematic diagram of the preparation route of silane-terminated polyethers;
FIG. 2 is a diagram of the mechanism of hydrolysis of the terminal silane polyether.
Detailed Description
The invention is further described below with reference to the following figures and examples:
the present disclosure will be described in detail and with reference to the drawings, and it is to be understood that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The singular forms "a", "an", "the" and "the", as used herein, also include the plural forms. As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
See figures 1 and 2.
Example 1:
the raw materials were prepared according to the composition of example 1 shown in Table 1. Uniformly mixing PLA, PLA-g-MAH, alkali-treated bamboo powder, an antioxidant, a lubricant, a compatilizer, a coupling agent and silane modified polyether by a high-speed mixer, adding the mixed raw materials into a hopper of a double-screw extrusion device, melting and extruding by double screws, setting the extrusion temperature of the double-screw extrusion device to be 170 ℃, and obtaining the PLA/bamboo powder modified particles after bracing, traction, cooling and grain cutting.
Example 2:
the raw materials were prepared according to the composition of example 2 shown in Table 1. Uniformly mixing PLA, PLA-g-MAH, alkali-treated bamboo powder, an antioxidant, a lubricant, a compatilizer, a coupling agent and silane modified polyether by a high-speed mixer, adding the mixed raw materials into a hopper of a double-screw extrusion device, melting and extruding the raw materials by double screws, setting the extrusion temperature of the double-screw extrusion device to be 170 ℃, and obtaining the PLA/bamboo powder modified particles by bracing, traction, cooling and granulating the raw materials.
Example 3:
the raw materials were prepared according to the composition of example 3 shown in Table 1. Uniformly mixing PLA, PLA-g-MAH, alkali-treated bamboo powder, an antioxidant, a lubricant, a compatilizer, a coupling agent and silane modified polyether by a high-speed mixer, adding the mixed raw materials into a hopper of a double-screw extrusion device, melting and extruding by double screws, setting the extrusion temperature of the double-screw extrusion device to be 170 ℃, and obtaining the PLA/bamboo powder modified particles after bracing, traction, cooling and grain cutting.
Example 4:
the raw materials were formulated in accordance with the compositions of example 4 shown in Table 1. Uniformly mixing PLA, PLA-g-MAH, alkali-treated bamboo powder, an antioxidant, a lubricant, a compatilizer, a coupling agent and silane modified polyether by a high-speed mixer, adding the mixed raw materials into a hopper of a double-screw extrusion device, melting and extruding by double screws, setting the extrusion temperature of the double-screw extrusion device to be 170 ℃, and obtaining the PLA/bamboo powder modified particles after bracing, traction, cooling and grain cutting.
Example 5:
the raw materials were prepared according to the composition of example 5 shown in Table 1. Uniformly mixing PLA, alkali-treated bamboo powder, an antioxidant, a lubricant, a compatilizer, a coupling agent and silane modified polyether by a high-speed mixer, adding the mixed raw materials into a hopper of a double-screw extrusion device, melting and extruding by double screws, setting the extrusion temperature of the double-screw extrusion device to be 170 ℃, and bracing, drawing, cooling and dicing to obtain the PLA/bamboo powder modified particles.
Comparative example 1:
the raw materials were prepared in accordance with the components of comparative example 1 shown in Table 1. Uniformly mixing PLA, PLA-g-MAH, alkali-treated bamboo powder, an antioxidant, a lubricant, a compatilizer and a coupling agent by a high-speed mixer, adding the mixed raw materials into a hopper of a double-screw extrusion device, melting and extruding by double screws, setting the extrusion temperature of the double-screw extrusion device to be 170 ℃, and drawing, cooling and dicing to obtain the PLA/bamboo powder modified particles.
Comparative example 2:
the raw materials were prepared in accordance with the components of comparative example 2 shown in Table 1. Uniformly mixing PLA, alkali-treated bamboo powder, an antioxidant, a lubricant, a compatilizer, a coupling agent and silane modified polyether by a high-speed mixer, adding the mixed raw materials into a hopper of a double-screw extrusion device, melting and extruding by double screws, setting the extrusion temperature of the double-screw extrusion device to be 170 ℃, and bracing, drawing, cooling and dicing to obtain the PLA/bamboo powder modified particles.
Comparative example 3:
the raw materials were prepared in accordance with the composition of comparative example 3 shown in Table 1. Uniformly mixing PLA, alkali-treated bamboo powder, an antioxidant, a lubricant, a compatilizer, a coupling agent and silane modified polyether by a high-speed mixer, adding the mixed raw materials into a hopper of a double-screw extrusion device, melting and extruding by double screws, setting the extrusion temperature of the double-screw extrusion device to be 170 ℃, and bracing, drawing, cooling and dicing to obtain the PLA/bamboo powder modified particles.
Table 1: dosage of the formula of the examples and the comparative examples
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| PLA LX175 | 61.2 | 61.2 | 61.2 | 41.7 | 36.7 | - | 57.2 | 50.7 |
| PLA 4032D | - | - | - | - | - | 60.2 | - | - |
| PLA-g-MAH | 10 | 10 | 10 | 15 | 20 | - | 5 | 10 |
| Alkali treated bamboo powder | 20 | 20 | 20 | 30 | 30 | 30 | 30 | 30 |
| Antioxidant 1010 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Antioxidant 168 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant agent | 0.5 | 0.5 | 0.5 | 1 | 1 | 0.5 | 0.5 | 1 |
| Compatilizer EBA-GMA | 5 | - | - | 8 | - | - | 5 | - |
| Compatibilizer PEO | - | 5 | - | - | 8 | 8 | - | - |
| Compatibilizer EAA | - | - | 5 | - | - | - | - | 5 |
| Coupling agent KH550 | 1 | - | - | 1 | 1 | 1 | ||
| Coupling agent KH560 | - | 1 | - | - | 1 | 1 | ||
| Coupling agent KH570 | - | 1 | - | |||||
| Silane modified polyether | 1 | 1 | 1 | 3 | 3 | - | 1 | 2 |
Table 2: results of performance testing of examples and comparative examples
As can be seen from tables 1 and 2:
1. in the embodiment of the invention, the PLA which is grafted and modified by MA is added, the linear structure of the original PLA is adopted, and the MA monomer is introduced into the main chain of the polylactic acid, so that the molecular space resistance of the polylactic acid is increased, and the polylactic acid becomes a three-dimensional network structure, thereby preventing the water molecules from attacking the main chain of the polylactic acid, improving the hydrophobicity of the material, simultaneously, the active free radicals can become grafting points of maleic anhydride, and can act with substances with functional groups such as amino groups, hydroxyl groups and the like, thereby generating grafting reaction, and improving the compatibility and the interface bonding capability.
2. The bamboo powder treated by the alkaline NaOH solution is added in the embodiment of the invention, so that the surface polarity of the bamboo powder is reduced, and the bamboo powder has better interface compatibility with a resin matrix under the condition of high bamboo powder filling.
3. In the embodiment of the invention, the compatible modification auxiliary agents such as PTW, PEO, EAA and the like are added, so that the compatibility of the modified bamboo powder and PLA is improved, the compactness of the structure of the composite material is improved, and the hydrophobicity of the composite material is improved.
4. According to the embodiment of the invention, the silane coupling agent and the silane modified polyether are added, so that a more three-dimensional net structure is formed on the main chain, the crosslinking degree is improved, and the hydrophobicity of the PLA/bamboo powder composite material is further improved.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. A hydrophobic high bamboo powder filled biodegradable composite material is characterized in that: the raw materials comprise the following components in percentage by mass:
20 to 70 parts of PLA;
1.0 to 20 parts of PLA-g-MAH;
10 to 30 parts of modified bamboo powder;
0.2 to 1 part of antioxidant;
0.1 to 2 parts of a lubricant;
0.1 to 8 portions of compatilizer;
0.1 to 3 parts of a coupling agent;
0.1 to 5 parts of end silane modified polyether.
2. The hydrophobic high bamboo powder filled biodegradable composite material as claimed in claim 1, wherein: the PLA is PLA resin, and the melt index is less than or equal to 10g/10min (190 ℃,2.16 kg).
3. The hydrophobic high bamboo powder filled biodegradable composite material as claimed in claim 1, wherein: the preparation method of the PLA-g-MAH comprises the following steps:
according to 100 parts of PLA, firstly dissolving 3 parts of maleic anhydride and 0.3 part of dicumyl peroxide in 30ml of ethanol, pouring the solution into polylactic acid after the dissolution is finished, uniformly mixing the solution and the polylactic acid until the ethanol is volatilized, adding the mixture into an internal mixer for banburying and blending, setting the temperature of the internal mixer to be 170 ℃, setting the banburying time to be 5 minutes, and extruding and granulating the mixture by a single-screw extruder after the banburying is finished, wherein the temperatures from one zone of the extruder to a machine head are respectively set to be 130 ℃, 145 ℃, 165 ℃, 160 ℃ and 150 ℃; and finally, placing the particles in a vacuum oven to dry for 24 hours at the temperature of 60 ℃ to obtain PLA-g-MAH.
4. The hydrophobic high bamboo powder filled biodegradable composite material as claimed in claim 1, wherein: the preparation method of the modified bamboo powder comprises the following steps:
firstly, weighing 500g of dried bamboo powder, wherein the mesh number of the bamboo powder is 40-200 meshes; and then adding the bamboo powder into a NaOH solution with the mass fraction of 12%, heating and stirring for 6 hours to fully react, carrying out suction filtration on the alkalized bamboo powder for 5 times by using a Buchner funnel, and finally putting the alkali-treated wood fiber into a vacuum drying oven to carry out vacuum drying for 12 hours at the temperature of 40 ℃ to obtain the alkali-treated modified bamboo powder.
5. The hydrophobic high bamboo powder filled biodegradable composite material as claimed in claim 1, wherein: the antioxidant is hindered phenol antioxidant and phosphite antioxidant, and is selected from one or more of antioxidant 1010, antioxidant 1010 and antioxidant 1076.
6. The hydrophobic high bamboo powder filled biodegradable composite material as claimed in claim 1, wherein: the lubricant is one or more of silicone, stearic acid, stearate, ethylene bis stearamide and derivatives thereof.
7. The hydrophobic high bamboo powder filled biodegradable composite material as claimed in claim 1, wherein: the compatilizer is an epoxy compatilizer and is selected from one or more of ethylene butyl acrylate grafted glycidyl methacrylate, polyethylene oxide and ethylene acrylic acid copolymer.
8. The hydrophobic high bamboo powder filled biodegradable composite material as claimed in claim 1, wherein: the coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
9. The hydrophobic high bamboo powder filled biodegradable composite material as claimed in claim 1, wherein: the terminal silane modified polyether is silane coupling agent modified polyether, and the preparation method comprises the following steps:
carrying out hydrosilation reaction on 0.01mol of terminal allyl polyoxypropylene ether and 0.05mol of methylhydrogen dichlorosilane at 88-98 ℃ for 3-5 h under the catalysis of chloroplatinic acid, then reacting with a methanol-cyclopropane solution at 35-55 ℃ for 3h, and then heating to 70 ℃ for 3h to obtain the terminal silane polyether.
10. A preparation method of a hydrophobic high bamboo powder filled biodegradable composite material is characterized by comprising the following steps: the preparation method of the hydrophobic high bamboo powder filled biodegradable composite material according to any one of claims 1 to 9, wherein the preparation method comprises the following steps:
step one, weighing the components in parts by weight;
step two, adding the resin and the auxiliary agent into a high-speed mixer, uniformly mixing, and adding into a double-screw extruder for extrusion granulation; the melt extrusion temperature of the double-screw extruder is 150 to 180 ℃, and the screw rotating speed is 150 to 300 revolutions per minute;
and step three, water-cooling and granulating to obtain the hydrophobic bamboo powder filled composite modified material.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225947A (en) * | 2011-04-29 | 2011-10-26 | 南通德益化工有限公司 | Preparation method of polyether modified siloxane |
| CN105199110A (en) * | 2015-10-19 | 2015-12-30 | 苏州思德新材料科技有限公司 | Surfactant used in preparation of slow rebound polyurethane foam and preparation technology of surfactant |
| CN105237977A (en) * | 2015-11-06 | 2016-01-13 | 福州市福塑科学技术研究所有限公司 | Bamboo fiber reinforced degradable PLA material and preparation method thereof |
| CN108047452A (en) * | 2017-12-20 | 2018-05-18 | 山东东岳有机硅材料股份有限公司 | A kind of levelling agent super high molecular weight Siloxane-Oxyalkylene Copolymers and preparation method and application |
| CN111909450A (en) * | 2020-08-11 | 2020-11-10 | 上海第二工业大学 | Preparation method of modified bamboo powder material |
| CN113861406A (en) * | 2021-11-01 | 2021-12-31 | 江西晨光新材料股份有限公司 | Method for preparing silane modified polyether by using dichlorosilane |
-
2022
- 2022-12-30 CN CN202211723361.XA patent/CN115873388A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225947A (en) * | 2011-04-29 | 2011-10-26 | 南通德益化工有限公司 | Preparation method of polyether modified siloxane |
| CN105199110A (en) * | 2015-10-19 | 2015-12-30 | 苏州思德新材料科技有限公司 | Surfactant used in preparation of slow rebound polyurethane foam and preparation technology of surfactant |
| CN105237977A (en) * | 2015-11-06 | 2016-01-13 | 福州市福塑科学技术研究所有限公司 | Bamboo fiber reinforced degradable PLA material and preparation method thereof |
| CN108047452A (en) * | 2017-12-20 | 2018-05-18 | 山东东岳有机硅材料股份有限公司 | A kind of levelling agent super high molecular weight Siloxane-Oxyalkylene Copolymers and preparation method and application |
| CN111909450A (en) * | 2020-08-11 | 2020-11-10 | 上海第二工业大学 | Preparation method of modified bamboo powder material |
| CN113861406A (en) * | 2021-11-01 | 2021-12-31 | 江西晨光新材料股份有限公司 | Method for preparing silane modified polyether by using dichlorosilane |
Non-Patent Citations (2)
| Title |
|---|
| 左迎峰;李萍;刘文杰;李新功;江萍;吴义强;: "碱处理对竹纤维/聚乳酸可降解复合材料性能影响研究", 功能材料, no. 02, 28 February 2018 (2018-02-28), pages 02006 - 02012 * |
| 黄文润: "《硅烷偶联剂及硅树脂》", vol. 1, 31 August 2010, 四川出版集团·四川科学技术出版社, pages: 27 * |
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