CN113754952A - Preparation process of modified cellulose nano-fibril/polymer composite material - Google Patents
Preparation process of modified cellulose nano-fibril/polymer composite material Download PDFInfo
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- CN113754952A CN113754952A CN202010497358.5A CN202010497358A CN113754952A CN 113754952 A CN113754952 A CN 113754952A CN 202010497358 A CN202010497358 A CN 202010497358A CN 113754952 A CN113754952 A CN 113754952A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a preparation process of a modified cellulose nano-fibril/polymer composite material, belonging to the technical field of plant-based nano-fibril composite materials. The raw materials comprise polymer, compatibilizer, paper pulp fiber, concentrated sulfuric acid, glacial acetic acid and acetic anhydride. The invention has the beneficial effects that: the hydrogen bond binding force among fibrils is reduced by modifying and pretreating the plant fiber, the dissociation of the fibrils and the synchronous preparation of the modified cellulose nano-fibril/polymer composite material are realized by means of the high shear and high temperature of a double-screw extruder, the production energy consumption is greatly reduced, the production process of the composite material is simplified, and the method is a composite material production technology with an industrial application prospect; in addition, the modified CNF has good compatibility with a polymer matrix, improves the mechanical property of the composite material, reduces the dependence on and use of petroleum resources, and has the advantages of low carbon, environmental protection and excellent performance.
Description
Technical Field
The invention relates to a preparation process of a modified cellulose nano-fibril/polymer composite material, belonging to the technical field of plant-based nano-fibril composite materials.
Technical Field
The Cellulose Nanofibrils (CNF) have the characteristics of high strength, high length-diameter ratio, low thermal expansion coefficient, degradability and the like, and have great application potential in the field of polymer green reinforced fillers. Compared with Cellulose Nanocrystalline (CNC), the interwoven three-dimensional network structure can better transmit and disperse load, endows the material with certain toughness, can limit the violent movement of polymer molecules to a certain extent, improves the thermodynamic property, and is a nano reinforced material with great development potential. In recent years, the extraction of CNF from biomass resources and the preparation of polymer composites using its performance advantages different from CNC have become a research hotspot in the field of nanocellulose enhancement.
Because the compatibility of the CNF with strong hydrophilicity and the nonpolar or low-polar high polymer is poor, the high-performance composite material cannot be prepared, the current research work mainly aims to improve the hydrophobicity of the CNF through various modification treatments, so as to achieve the purpose of improving the dispersibility and the interface compatibility of the CNF in the high polymer matrix, and obtain certain results.
At present, the preparation methods of the CNF/polymer composite material mainly comprise a solution pouring method, a melt blending method, a layer-by-layer self-assembly method, an impregnation method and the like. The melt blending method is widely applied to the field of composite material preparation as a nano composite material preparation process with great industrial application prospect. Tingaut and the like compound acetylated and modified microfibrillated cellulose (MFC) and PLA to obtain a PLA/MFC nano composite material, and the dispersion of the MFC in the composite material is better along with the improvement of acetylation degree; when the addition amount of MFC is 10%, the thermal stability and the mechanical property of the composite material are improved. Sato et al prepared Cellulose Nanofibers (CNF) with different hydrophobicity by surface modification of cellulose nanofibers with Alkenyl Succinic Anhydride (ASA); and (3) melting and mixing the modified CNF and High Density Polyethylene (HDPE) by a double-screw extruder, and performing injection molding to prepare the CNF/HDPE nanocomposite. In any case, the method usually needs to go through the processes of CNF preparation-modification-compounding and the like, and has the disadvantages of complex process, low production efficiency and higher cost. Exploring an efficient mass production process for CNF reinforced composites remains the biggest challenge in achieving cost-effective composite fabrication.
Disclosure of Invention
Aiming at the problems of poor compatibility of hydrophilic CNF and a polymer matrix, complex composite process and the like, the invention provides a preparation process of a modified cellulose nano fibril/polymer composite material, which carries out modification pretreatment on fibers, reduces the hydrogen bond bonding force between fibrils, realizes the dissociation of fibrils and the synchronous preparation of the modified CNF/polymer composite material by means of the high shear and high temperature of a double-screw extruder, greatly reduces the production energy consumption and cost, and simplifies the production process of the composite material; in addition, the modified CNF has good compatibility with a polymer matrix, improves the mechanical property of the composite material, reduces the dependence on and use of petroleum resources, and has the advantages of low carbon, environmental protection and excellent performance.
According to the invention, pulp fibers are used as a raw material, and acetic anhydride is used as an acylation reagent to perform acetylation modification on the pulp fibers, so that the surface polarity of the modified fibers is reduced, and the dispersibility of the modified fibers in a weak polar/nonpolar polymer matrix and the interfacial compatibility of two phases are enhanced; on the other hand, the part-OH on the cellulose chain is replaced by CH3And C-O substitution weakens the hydrogen bond interaction between filaments and is beneficial to the dissociation of the filaments in the subsequent melt mixing process.
Through the pretreatment of the method, the dissociation of the fibril and the preparation of the composite material are synchronously realized by the high shearing force of the double-screw extruder in the process of melting and blending the modified fiber and the polymer matrix, the production efficiency is improved, and the production energy consumption is reduced, so that the preparation method of the composite material has a good market application prospect.
In order to achieve the aim, the modified cellulose nanofibril/polymer composite material is prepared from the following raw materials in percentage by mass:
90-99 parts of polymer resin, 1-10 parts of modified cellulose nano-fibril and 0-3 parts of compatibilizer;
the specific preparation method comprises the following steps:
1. weighing paper pulp fiber raw materials, soaking in deionized water for 4h, pulping and defibering according to QB/T3703-1999 method with watt force, and drying for later use;
2. weighing the dry paper pulp fibers obtained in the step (1), placing the dry paper pulp fibers in a round-bottom flask provided with a condensing reflux device, adding glacial acetic acid to adjust the concentration of the pulp to be 1% -8%, then adding 0.02-0.05 g/g of concentrated sulfuric acid catalyst of absolute dry pulp and acetic anhydride esterification reagent vinegar, wherein the molar ratio of the acetic anhydride to the paper pulp fibers is 0.5-2.5, reacting at 40-50 ℃ for 0.5-3 h, and after the reaction is finished, repeatedly centrifuging and washing at 5000r/min until the supernatant is neutral to prepare the modified fibers;
3. crushing the polymer and the compatibilizer particles, and sieving the crushed particles with a 60-300-mesh sieve to obtain polymer and compatibilizer powder;
4. adjusting the concentration of the modified fiber obtained in the step (2) to 1% -3%, adding the polymer and the compatibilizer powder obtained in the step (3), magnetically stirring for 30min, and then carrying out vacuum filtration. Then drying the filter cake in a 60 ℃ oven, and crushing to obtain granules;
5. and (4) adding the particles in the step (4) into a Haake torque rheometer, setting the torque to be 30rpm, and melting and mixing for 10min at 160-190 ℃. And after cooling and granulation, adding the granules into a haake rheometer again for mixing, and repeating the process for 1-3 times to obtain the modified cellulose nanofibril/polymer composite material for subsequent processing.
The pulp fiber in the step (1) can be plant fiber raw materials such as dissolving pulp fiber, softwood fiber or hardwood fiber and the like; the polymer in the step (3) is polypropylene PP, polyethylene PE or polyamide PA, and the compatibilizer is maleic anhydride grafted polypropylene MAPP, maleic anhydride grafted polyethylene MAPE or silane coupling agent KH 550.
The invention has the following effects:
1. the invention realizes the dissociation of the fibrils and the synchronous preparation of the modified cellulose nano fibrils/polymer composite material by means of the high shear and high temperature of the double-screw extruder, reduces the production energy consumption and cost, simplifies the production process of the composite material, and opens up a new way for the efficient large-scale preparation of the nano fiber reinforced composite material.
2. The dissociated modified CNF is obtained in the process of melt blending of the modified fiber and the polymer matrix, the two phases of the dissociated modified CNF are uniformly distributed in the polymer matrix and have good interface compatibility, the enhancement effect brought by the nanometer size effect of the CNF can be fully exerted, the three-dimensional network structures interwoven with each other can also better transmit and absorb external stress, and the mechanical property of the prepared composite material is greatly improved compared with that of a pure polymer.
3. The invention reduces the dependence on and use of petroleum resources, and has the advantages of low carbon, environmental protection and excellent performance.
Detailed Description
The present invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the present application.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
Example 1
The modified CNF/PP composite material is prepared by the following steps:
1. acetylation hydrophobic modification of dissolving pulp
Weighing 200g of dissolving pulp board, shredding, soaking in deionized water for 4h, pulping and defibering according to QB/T3703-1999W force, and drying at room temperature for later use;
accurately weighing 10g of dissolving pulp in the step I, placing the dissolving pulp in a round-bottom flask provided with a condensation reflux device, adding 100ml of glacial acetic acid, 0.5g of concentrated sulfuric acid and 9.5g of acetic anhydride, and uniformly mixing;
placing the mixture obtained in the step II in a water bath kettle at 50 ℃ for reaction for 1 h; after the reaction is finished, repeatedly centrifuging and washing at 5000r/min until the supernatant is neutral;
fourthly, measuring the water content of the product in the third step and storing the product in a refrigerator at 5 ℃ for later use;
2. wet primary mixing of acetylated modified dissolving pulp/PP composite material
Crushing polypropylene PP and maleic anhydride grafted polypropylene MAPP, and sieving with a 100-mesh sieve to obtain PP and MAPP powder;
accurately weighing 1.2g of acetylated hydrophobically modified dissolving pulp, adjusting the pulp concentration to be 2%, then adding 40g of polypropylene powder and 1.2g of maleic anhydride grafted polypropylene powder in the step I, magnetically stirring for 30min, and then carrying out vacuum filtration;
thirdly, drying the filter cake obtained in the second step in a drying oven at 60 ℃ and crushing for later use;
3. preparation of modified CNF/PP composite material
Firstly, adding the preliminarily mixed hydrophobic modified dissolving pulp/PP granules into a Haake torque rheometer to be melted and mixed for 10min, wherein the rotating speed of a screw is 30rpm, and the mixing temperature is 170 ℃;
secondly, after the composite material is cooled and granulated, adding the granules into the Haake rheometer again for mixing, and repeating the process for 2 times;
and thirdly, uniformly spreading the granules mixed in the second step in a standard die, preheating for 3min at 170 ℃ and 0MPa, hot-pressing for 10min at 170 ℃ and 10MPa, and cold-pressing for 5min at room temperature and 10MPa to obtain the acetylated CNF/PP composite board with the thickness of 1mm and 4 mm.
Example 2
The modified CNF/HDPE composite material is prepared by the following steps:
1. NBKP acetylation modification
10g of defibered bleached softwood kraft pulp (NBKP) dried at room temperature to a constant weight were weighed out accurately, placed in a round-bottomed flask equipped with a condensing reflux apparatus, and 100ml of glacial acetic acid, 0.5g of concentrated sulfuric acid and 9.5g of acetic anhydride were added and reacted at 50 ℃ for 1 hour. After the reaction is finished, repeatedly centrifuging and washing at 5000r/min until the supernatant is neutral. The moisture content of the product was measured and stored in a refrigerator at 5 ℃ for further use.
2. Wet primary mixing of acetylated modified NBKP/HDPE composite material
Accurately weighing 1.5g of acetylation modified NBKP in the step (1), adjusting the concentration of the slurry to 2%, then adding 40g of high-density polyethylene powder and 1.2g of maleic anhydride grafted polyethylene powder, magnetically stirring for 30min, then carrying out vacuum filtration, and drying in an oven at 60 ℃;
3. preparation of modified CNF/HDPE composite material
And (3) adding the NBKP/PE granules preliminarily mixed in the step (2) into a Haake torque rheometer to melt and mix for 10min, wherein the screw rotation speed is 30rpm, and the mixing temperature is 165 ℃. After cooling granulation, the granules were again added to the haake rheometer for mixing, and the process was repeated 2 times. After mixing, uniformly spreading the crushed granules in a standard die, preheating at 165 ℃ and 0MPa for 3min, hot-pressing at 165 ℃ and 10MPa for 10min, and cold-pressing at room temperature and 10MPa for 5min to obtain the acetylated CNF/HDPE composite board with the thickness of 1mm and 4 mm.
Example 3
The modified CNF/PA6 composite material was prepared according to the following procedure:
1. acetylation modification of dissolving pulp
10g of the digested slurry, dried to constant weight at room temperature, was weighed out accurately and placed in a round-bottomed flask equipped with a reflux condenser, 100ml of glacial acetic acid, 0.5g of concentrated sulfuric acid and 9.5g of acetic anhydride were added and reacted at 50 ℃ for 1 hour. After the reaction is finished, repeatedly centrifuging and washing at 5000r/min until the supernatant is neutral. The moisture content of the product was measured and stored in a refrigerator at 5 ℃ for further use.
2. Wet primary mixing of acetylated modified dissolving pulp/PA composite material
Accurately weighing 1.5g of acetylation modified dissolving pulp in the step (1), adjusting the concentration of the pulp to 1.5%, then adding 40g of nylon 6 and 0.8g of silane coupling agent KH560, magnetically stirring for 30min, then carrying out vacuum filtration, and drying in an oven at 60 ℃;
3. preparation of modified CNF/P6A composite material
And (3) adding the dissolved pulp/PE granules preliminarily mixed in the step (2) into a Haake torque rheometer to be melted and mixed for 10min, wherein the rotating speed of a screw is 30rpm, and the mixing temperature is 170 ℃. After cooling granulation, the granules were again added to the haake rheometer for mixing, and the process was repeated 2 times. After mixing, uniformly spreading the crushed granules in a standard die, preheating at 170 ℃ and 0MPa for 3min, hot-pressing at 170 ℃ and 10MPa for 10min, and cold-pressing at room temperature and 10MPa for 5min to obtain the acetylated CNF/PA6 composite board with the thickness of 1mm and 4 mm.
The modified CNF/polymer composite materials prepared in examples 1, 2, and 3 were subjected to quality tests of tensile strength, flexural strength, and impact strength, and the test results are shown in table 1.
TABLE 1 comparison of examples 1-3 with Polymer Material Properties
The tensile strength, young's modulus, flexural strength, flexural modulus and impact strength of the modified CNF/polymer composites prepared in examples 1, 2 and 3 were all superior to those of the polymer monomer before compounding.
The traditional polymer material preparation method comprises the following steps: and directly adding the polymer powder into a double-screw extruder for melt extrusion granulation, and carrying out preheating, hot pressing and cold pressing to obtain the polymer plate with the standard thickness.
Claims (2)
1. A preparation process of a modified cellulose nanofibril/polymer composite material is characterized by comprising the following steps:
preparation of modified fiber: weighing paper pulp fiber raw materials, defibering and drying the paper pulp fiber raw materials, placing the paper pulp fiber raw materials into a round-bottom flask provided with a condensation reflux device, adding glacial acetic acid to adjust the concentration of the pulp to be 1% -8%, then adding 0.02-0.05 g/g of concentrated sulfuric acid catalyst of absolute dry pulp and an acetic anhydride esterification reagent, reacting for 0.5-3 h at 40-50 ℃, repeatedly centrifuging and washing at 5000r/min until the supernatant is neutral after the reaction is finished, and preparing the obtained acetylation modified fiber pulp;
wet mixing of modified fiber and polymer: crushing the polymer and the compatibilizer particles, and sieving the crushed particles with a 60-300-mesh sieve to obtain polymer and compatibilizer powder; adjusting the concentration of the acetylated modified fiber slurry in the step I to 1% -3%, adding a powdery polymer and a compatibilizer, wherein the mixture contains 90-99 parts of the polymer, 1-10 parts of the modified fiber and 0-3 parts of the compatibilizer by mass, and performing vacuum filtration after magnetic stirring for 30 min; then drying the filter cake in a 60 ℃ oven, and crushing to obtain granules;
preparing the modified cellulose nano fibril/polymer composite material: and (4) adding the granules in the step two into a Haake torque rheometer, setting the torque to be 30rpm, melting and mixing for 10min at 160-190 ℃, cooling and granulating, adding the granules into the Haake rheometer again for mixing, and repeating the process for 1-3 times to obtain the cellulose nanofibril/polymer composite material for subsequent processing.
2. The novel process for preparing a modified cellulose nanofibril/polymer composite according to claim 1, wherein: the polymer is polypropylene PP, polyethylene PE and polyamide PA; the compatibilizer is maleic anhydride grafted polypropylene MAPP, maleic anhydride grafted polyethylene MAPE and a silane coupling agent KH 550.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117545A (en) * | 1995-09-29 | 2000-09-12 | Rhodia Chimie | Surface-modified cellulose microfibrils, method for making the same, and use thereof as a filler in composite materials |
| CN107429071A (en) * | 2015-03-19 | 2017-12-01 | 国立大学法人京都大学 | Containing chemical modification is cellulose nano-fibrous and the fiber-reinforced resin composition of thermoplastic resin |
| CN109608844A (en) * | 2018-12-21 | 2019-04-12 | 张富森 | The preparation method of the full Preen nono composite material of acetic acid esterified nano-cellulose-polylactic acid |
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2020
- 2020-06-04 CN CN202010497358.5A patent/CN113754952A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6117545A (en) * | 1995-09-29 | 2000-09-12 | Rhodia Chimie | Surface-modified cellulose microfibrils, method for making the same, and use thereof as a filler in composite materials |
| CN107429071A (en) * | 2015-03-19 | 2017-12-01 | 国立大学法人京都大学 | Containing chemical modification is cellulose nano-fibrous and the fiber-reinforced resin composition of thermoplastic resin |
| CN109608844A (en) * | 2018-12-21 | 2019-04-12 | 张富森 | The preparation method of the full Preen nono composite material of acetic acid esterified nano-cellulose-polylactic acid |
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