CN110054838B - Cellulose hybrid filler reinforced polymer composite material and preparation method thereof - Google Patents
Cellulose hybrid filler reinforced polymer composite material and preparation method thereof Download PDFInfo
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- CN110054838B CN110054838B CN201910343478.7A CN201910343478A CN110054838B CN 110054838 B CN110054838 B CN 110054838B CN 201910343478 A CN201910343478 A CN 201910343478A CN 110054838 B CN110054838 B CN 110054838B
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
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Abstract
The invention discloses a cellulose hybrid filler reinforced polymer composite material and a preparation method thereof, wherein the cellulose hybrid filler reinforced polymer composite material comprises the following raw materials: 100 parts of a polymer matrix; 5 parts of a compatilizer; 1-40 parts of granite waste/agricultural and forestry waste hybrid filler. The preparation method comprises the following steps: (1) mixing the granite waste and the agricultural and forestry waste, and adding water to prepare an aqueous dispersion; (2) milling the aqueous dispersion to obtain a micro-nano hybrid filler dispersion; (3) carrying out suction filtration on the micro-nano hybrid filler solution, drying and mechanically crushing to prepare micro-nano hybrid filler powder; (4) blending the micro-nano hybrid filler powder with a polymer and a compatilizer, and stirring; (5) and extruding and granulating the mixture by a machine, and performing injection molding by an injection molding machine to obtain a corresponding product. The invention has the advantages that: reasonably and effectively realizes high-value utilization of the cellulose, avoids the problem of environmental pollution, effectively solves the problem that cellulose is easy to agglomerate in a nonpolar polymer, and endows the polymer composite material with excellent mechanical properties.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to an artificial granite calcium carbonate waste residue/agricultural and forestry waste hybrid filler reinforced polymer composite material and a preparation method thereof.
Background
The artificial granite is stone material produced with polymer, inorganic gelatinizer or their mixture as adhesive material, crushed natural stone material, aluminum hydroxide powder, etc. as main material, and through mixing, coagulation, solidification and other steps. The resin-based artificial granite is an artificial stone which is prepared by using crushed aggregates and powder of marble, limestone and the like as main raw materials and using resin as a bonding material. A large amount of waste residues are generated in the processing process of the artificial granite, the main components of the waste residues are calcium carbonate and unsaturated polyester, the waste residues are difficult to degrade and cannot be processed for the second time, and the environment can be polluted due to improper treatment.
The agricultural and forestry wastes refer to organic substances discarded in the whole agricultural production process, such as crop straws, bagasse, rice husks, barks and the like. The agricultural and forestry wastes contain a large amount of natural cellulose and are important biomass resources, China is a big agricultural country, the agricultural and forestry wastes are continuously accumulated to occupy a large amount of cultivated land, farmers mostly solve the problem by adopting an incineration mode, and serious pollution can be caused to the environment in the past. The conversion and utilization of agricultural and forestry waste energy is one of the research hotspots in the field of renewable energy.
Agricultural and forestry wastes such as straws, bagasse and other materials are rich in cellulose, and the cellulose contains rich hydrogen bonds, so that intramolecular hydrogen bonds are easily formed and are difficult to peel, and micro-nano fibrosis is realized, so that when the cellulose is used for reinforcing a nonpolar polymer, the cellulose is not ideal in dispersion condition in a nonpolar polymer matrix and is easy to mutually aggregate, an agglomeration phenomenon is caused, and the mechanical property of the composite material cannot be improved. Therefore, the improvement of the interface interaction between the cellulose and the polymer matrix has important significance for the application of the cellulose reinforced composite material. At present, solvent replacement, surfactant addition, in-situ polymerization or direct surface modification of cellulose are mostly adopted to improve the interfacial interaction between the cellulose and a polymer matrix, but the improvement effect is not ideal, and the use of an organic solvent not only causes environmental pollution, but also increases the cost, and is difficult to be used in actual production. Therefore, the development of a preparation method of the cellulose reinforced polymer with low cost, no toxicity and environmental friendliness has very important practical significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a cellulose hybrid filler reinforced polymer composite material and a preparation method thereof, which can effectively solve the problems in the prior art.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a cellulose hybrid filler reinforced polymer composite material comprises the following raw materials:
the raw materials are in parts by weight except for special specifications.
100 parts of a polymer matrix;
5 parts of a compatilizer;
1-40 parts of granite waste/agricultural and forestry waste hybrid filler.
The mass ratio of the granite waste to the agricultural and forestry waste hybrid filler in the granite waste/agricultural and forestry waste hybrid filler is 1: 1-2: 1.
Further, the granite waste is artificial granite calcium carbonate waste residue; the agricultural and forestry waste is straw residue or bagasse; the polymer matrix is nonpolar polymer such as polypropylene.
Furthermore, the mesh number of the granite waste/agricultural and forestry waste hybrid filler is 200-500 meshes.
Further, the polymer composite material comprises the following raw materials: 100 parts of polypropylene, 5 parts of a compatilizer, 10 parts of a granite waste/agricultural and forestry waste hybrid filler, wherein the mass ratio of the granite waste to the agricultural and forestry waste hybrid filler is 3: 2.
the invention also discloses a preparation method of the filler reinforced polymer composite material, which comprises the following steps:
(1) mixing the artificial granite calcium carbonate waste residue powder with agricultural and forestry wastes such as straws and bagasse according to a certain proportion, and adding water to prepare an aqueous dispersion with the mass percent concentration of 0.5-2%;
(2) grinding the aqueous dispersion obtained in the step (1) for multiple times in a mechanical grinding mode to realize micro-nano fiberization of agricultural and forestry waste such as straws and bagasse and prepare micro-nano hybrid filler dispersion;
(3) carrying out suction filtration on the micro-nano hybrid filler solution obtained in the step (2), drying for 2-3 hours at 100-120 ℃, and further mechanically crushing by using a high-speed crusher to obtain micro-nano hybrid filler powder;
(4) blending the micro-nano hybrid filler powder obtained in the step (3) with a polymer and a compatilizer according to a certain proportion, and stirring for 10-20 min by a high-speed stirrer;
(5) and (4) extruding and granulating the mixture obtained in the step (4) through a double-screw extruder, and performing injection molding through an injection molding machine to obtain a corresponding product.
Compared with the prior art, the invention has the advantages that:
(1) the invention adopts artificial granite waste and agricultural and forestry waste, and reasonably and effectively realizes high-value utilization of the polymer composite material by using the artificial granite waste and the agricultural and forestry waste to reinforce the polymer composite material, thereby avoiding the problem of environmental pollution.
(2) According to the invention, the micro-nano fiberization of agricultural and forestry wastes such as straws and bagasse is realized by adopting a multi-stage shearing machine for milling, meanwhile, the calcium carbonate waste residues are introduced to assist the stripping of cellulose, and the micro-nano hybrid filler is prepared by utilizing the hydrogen bond interaction between oxygen-containing groups in the calcium carbonate waste residues and hydroxyl groups on natural cellulose such as straws and bagasse. The large amount of unsaturated polyester contained in the artificial granite waste residue can increase the interfacial interaction between the cellulose and the non-polar polymer substrate, improve the dispersion condition of the cellulose in the polymer matrix, effectively solve the problem that the cellulose is easy to agglomerate in the non-polar polymer, and endow the polymer composite material with excellent mechanical properties.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail by the following embodiments.
Example 1:
weighing 100 parts of polypropylene, 5 parts of a compatilizer, 3:2 mass ratio of the artificial granite calcium carbonate waste residues to the agricultural and forestry waste such as straw and bagasse, and 5 parts of granite waste/agricultural and forestry waste hybrid filler.
Firstly, mixing the artificial granite calcium carbonate waste residue powder with agricultural and forestry wastes such as straws and bagasse according to the proportion of 1:2 to prepare an aqueous solution with the mass percentage concentration of 5%. Grinding by a multistage shearing machine to realize micro-nano fibrosis of agricultural and forestry wastes such as straws and bagasse, preparing micro-nano hybrid filler dispersion liquid, performing suction filtration on the micro-nano hybrid filler solution, placing the micro-nano hybrid filler solution in an oven, drying for 3 hours at 120 ℃, crushing by a high-speed crusher to prepare micro-nano hybrid filler powder, wherein the powder mesh is 300 meshes, blending polypropylene and the micro-nano hybrid filler powder in proportion, adding the mixture into a high-speed stirrer, stirring for 10min, extruding and granulating by a double-screw extruder, and setting the temperature of an extruder screw to be: 170/180/185/190/190/180 ℃ and screw speed of 100rpm, and then injection molded by an injection molding machine at 190 ℃ to form dumbbell-type standard tensile test specimens.
Example 2:
weighing 100 parts of polypropylene, 5 parts of a compatilizer, 3:2 parts of artificial granite calcium carbonate waste residues, straw, bagasse and other agricultural and forestry waste in a mass ratio, and 10 parts of granite waste/agricultural and forestry waste hybrid filler. The procedure was as in example 1.
Example 3:
100 parts of polypropylene, 5 parts of a compatilizer, 3:2 mass ratio of artificial granite calcium carbonate waste residues to agricultural and forestry waste such as straw and bagasse, and 20 parts of granite waste/agricultural and forestry waste hybrid filler are weighed according to the mass ratio. The procedure was as in example 1.
Comparative example 1:
100 parts of polypropylene was weighed by mass, and the preparation process was the same as in example 1.
TABLE 1 test results
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Tensile Strength (MPa) | 35.8 | 41.6 | 39.3 | 31.4 |
| Elongation at Break (%) | 48 | 32 | 18 | 76 |
| Young's modulus (MPa) | 1067.8 | 1176.8 | 1668.6 | 1270.2 |
| Impact Strength (kJ/m)2) | 10.8 | 11.4 | 14.8 | 9.3 |
As can be seen from Table 1, the artificial granite calcium carbonate waste residue/agricultural and forestry waste hybrid filler reinforced polymer composite material prepared by the invention has more excellent mechanical properties.
It will be appreciated by those of ordinary skill in the art that the examples described herein are intended to assist the reader in understanding the manner in which the invention is practiced, and it is to be understood that the scope of the invention is not limited to such specifically recited statements and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (5)
1. A cellulose hybrid filler reinforced polymer composite characterized by: the polymer composite material comprises the following raw materials:
the parts of the raw materials are parts by weight except for special specifications;
100 parts of a polymer matrix;
5 parts of a compatilizer;
1-40 parts of granite waste/agricultural and forestry waste hybrid filler;
the mass ratio of the granite waste to the agricultural and forestry waste hybrid filler in the granite waste/agricultural and forestry waste hybrid filler is 1: 1-2: 1.
2. A cellulose hybrid filler reinforced polymer composite according to claim 1, characterized in that: the granite waste is artificial granite calcium carbonate waste residue; the agricultural and forestry waste is straw residue or bagasse; the polymer matrix is a polypropylene non-polar polymer.
3. A cellulose hybrid filler reinforced polymer composite according to claim 2, characterized in that: the mesh number of the granite waste/agricultural and forestry waste hybrid filler is 200-500 meshes.
4. A cellulose hybrid filler reinforced polymer composite according to claim 1, characterized in that: the polymer composite material comprises the following raw materials: 100 parts of polypropylene, 5 parts of a compatilizer, 10 parts of a granite waste/agricultural and forestry waste hybrid filler, wherein the mass ratio of the granite waste to the agricultural and forestry waste hybrid filler is 3: 2.
5. the method of claim 1, wherein the method comprises the steps of: the method comprises the following steps:
(1) mixing the artificial granite calcium carbonate waste residue powder with straws and bagasse agricultural and forestry wastes according to a certain proportion, and adding water to prepare an aqueous dispersion with the mass percent concentration of 0.5-2%;
(2) grinding the aqueous dispersion obtained in the step (1) for multiple times in a mechanical grinding mode to realize micro-nano fibrosis of straws and bagasse forestry and agricultural residues and prepare a micro-nano hybrid filler dispersion;
(3) carrying out suction filtration on the micro-nano hybrid filler solution obtained in the step (2), drying for 2-3 hours at 100-120 ℃, and further mechanically crushing by using a high-speed crusher to obtain micro-nano hybrid filler powder;
(4) blending the micro-nano hybrid filler powder obtained in the step (3) with a polymer and a compatilizer according to a certain proportion, and stirring for 10-20 min by a high-speed stirrer;
(5) and (4) extruding and granulating the mixture obtained in the step (4) through a double-screw extruder, and performing injection molding through an injection molding machine to obtain a corresponding product.
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| CN111362789A (en) * | 2020-04-23 | 2020-07-03 | 贺州学院 | Method for synthesizing calcium formate from waste residue of artificial granite |
| CN112724512A (en) * | 2020-12-23 | 2021-04-30 | 北京理工大学 | Preparation method of nano-cellulose polypropylene master batch |
| CN115745524A (en) * | 2022-12-06 | 2023-03-07 | 四川大学 | Artificial organic stone waste residue-micro-nano cellulose hybrid reinforced material and preparation method thereof |
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