CN116574390B - Inorganic hybridization reinforced straw-based biomass composite material and preparation method thereof - Google Patents
Inorganic hybridization reinforced straw-based biomass composite material and preparation method thereof Download PDFInfo
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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
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
The invention relates to an inorganic hybridization reinforced straw-based biomass composite material and a preparation method thereof. The invention aims to solve the problems of high cost, complex production process, easy generation of waste water during straw modification and high energy consumption of the existing biodegradable straw-based composite material. The straw-based biomass composite material is prepared from straw powder, wood powder, oil extraction soybean meal, ore powder with layered silicate components and aqueous solution of polyamide polyamine-epichlorohydrin resin; the preparation method comprises the following steps: 1. weighing; 2. preparing a powder mixture; 3. spraying aqueous solution of polyamide polyamine-epichlorohydrin resin into the powder mixture; 4. and (5) hot press molding.
Description
Technical Field
The invention relates to a straw-based biomass composite material and a preparation method thereof.
Background
China has rich straw resources, but the high-efficiency high-value utilization of the rich biomass resources of the straw becomes a global problem due to the problems of complex components, low fiber quality, high ash content, seasonal supply and the like. The straw resources in China are still mainly utilized by energy and feed, about 1/3 of the straw resources are burnt or abandoned on site, the resources are wasted, and the environment is seriously polluted. Aiming at the problems, domestic and foreign scholars develop extensive researches on clean pulping, composite forming, artificial board manufacturing and other industrial raw material utilization of the straws, and prove that the straws and the polymer are compounded, the straws are used for replacing plastics and the straws are used for replacing wood, so that the straw-based composite material which can be used in fields of furniture, packaging, building materials, automobile interior trim and the like can be prepared, the efficient utilization of the straws can be realized, the utilization added value of the straws can be improved, and the application field of the straw-based composite material can be expanded.
The conventional straw-based composite material is mainly prepared by compounding straw or modified straw with non-degradable synthetic plastics such as polyethylene, polypropylene, polystyrene and the like. Because polyethylene, polypropylene and other plastics are difficult to degrade, the use of the polyolefin synthetic plastics still has adverse effects on the environment, and the polyolefin synthetic plastics have weak polarity and are difficult to generate good interface gluing with straw, so that the straw needs to be modified. For example, the straw plastic composite materials reported in patent application numbers 202211441679.9, 201810692562.5, 202211696983.8 and the like all need to modify the straw, so that the production process is complex, a large amount of wastewater is easy to generate when the straw is cleaned, a large amount of energy consumption is generated when the modified straw is dried, and the environment-friendly energy-saving environment-friendly development concept is not met. Therefore, students and enterprises adopt expensive degradable plastics such as polylactic acid, polyhydroxyalkanoate and the like to replace polyethylene, polypropylene and other difficult-to-degrade plastics to prepare novel biodegradable straw plastic composite materials, for example, the application numbers 201710706600.3, 202111527021.5, 202010529164.9, 201810493331.1, 201710781946.X, 202111386371.4 and other invention patents, which all solve the problem that the straw plastic composite materials have difficult-to-degrade components, but all adopt NaHCO 3 composite solution, paraffin emulsion, silane coupling agent KH560 solution, 2, 4-diamino-6-methyl-1, 3, 5-triazine grafted polyvinyl acetate, 2-ureido-4-hydroxy-6-methylpyrimidine functionalized isoleucine and the like to modify the straws to prepare ideal composite materials, so that the problems of complicated manufacturing process and high raw material cost exist. In order to meet the large-scale industrial application requirements of the straw-based composite material, the production and application problems of high raw material cost, complex preparation process, easy generation of a large amount of wastewater, high energy consumption and the like are required to be effectively solved.
Disclosure of Invention
The invention aims to solve the problems of high cost, complex production process, easiness in generating waste water by straw modification and high energy consumption of the existing biodegradable straw-based composite material, and provides an inorganic hybridization reinforced straw-based biomass composite material and a preparation method thereof.
The inorganic hybrid reinforced straw-based biomass composite material is prepared from 100 parts by weight of straw powder, 60-90 parts by weight of wood powder, 15-40 parts by weight of oil-pressed soybean meal powder, 10-20 parts by weight of ore powder with layered silicate components and 65-240 parts by weight of aqueous solution of polyamide polyamine-epichlorohydrin resin; the mass percentage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 8-15%.
The preparation method of the inorganic hybridization reinforced straw-based biomass composite material is completed according to the following steps:
1. Weighing 100 parts of straw powder, 60-90 parts of wood powder, 15-40 parts of oil-pressed soybean meal powder, 10-20 parts of ore powder with layered silicate components and 65-240 parts of polyamide polyamine-epichlorohydrin resin aqueous solution according to parts by mass; the mass percentage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 8-15%;
2. uniformly mixing 100 parts of weighed straw powder, 60-90 parts of wood powder, 15-40 parts of oil-pressed soybean meal powder and 10-20 parts of ore powder with layered silicate components to obtain a powder mixture;
3. Spraying 65-240 parts of aqueous solution of polyamide polyamine-epichlorohydrin resin into the powder mixture under the stirring condition, and continuously stirring until the mixture is uniformly dispersed after spraying to obtain the powder mixture containing the polyamide polyamine-epichlorohydrin resin;
4. And (3) performing hot press molding on a powder mixture containing polyamide polyamine-epichlorohydrin resin to obtain the inorganic hybrid reinforced straw-based biomass composite material.
The beneficial effects of the invention are as follows:
1) The preparation method has the advantages that expensive degradable plastic base materials are not required to be added, and the prepared biodegradable straw-based biomass-based composite material has the characteristics of low cost and green and environment-friendly product;
2) The organic-inorganic hybridization of straw powder, oil extraction soybean meal and wood powder (shown in figure 4) is enhanced based on the effective chemical crosslinking effect of polyamide polyamine-epichlorohydrin resin solution on the straw powder, the oil extraction soybean meal and the wood powder, so that a crosslinked network structure is formed among the straw powder, the soybean powder, the wood powder, the polyamide polyamine-epichlorohydrin resin and the ore powder, and excellent mechanical property and water resistance are endowed on the basis of keeping the biodegradability of the straw-wood powder-oil extraction soybean meal composite material;
3) By means of the crosslinking effect of the low-cost aqueous environment-friendly polyamide polyamine-epichlorohydrin resin solution (1800-2600 yuan/ton), the easily-obtained, low-cost, renewable and biodegradable straw powder, wood powder and oil-pressed bean pulp powder are directly utilized as main raw materials, modification pretreatment such as activation, plasticization or grafting is not needed for the straw powder, the wood powder, the oil-pressed bean pulp powder and the ore powder, and the low-cost straw-based biomass composite material which is biodegradable, has excellent mechanical property and water resistance and is suitable for base materials in various industrial fields can be prepared by one-step hot press molding, has the tensile strength of more than 20MPa, the static bending strength of more than 29MPa and the impact strength of more than 2.9kJ/m 2, is resistant to boiling in 4 hours, keeps good tensile property, has a simple production process, and provides a new method for efficient industrial raw material utilization of crop straws.
Drawings
Fig. 1 is a physical diagram of an inorganic hybrid reinforced straw-based biomass composite material, a is an embodiment four, b is an embodiment five, c is an embodiment seven, and d is an embodiment six;
FIG. 2 is an XRD plot of an inorganic hybrid enhanced straw-based biomass composite material prepared in example three;
FIG. 3 shows the boiling water insolubility, A is montmorillonite ore powder, B is wood powder reinforced straw-based biomass composite board prepared in comparative experiment four, and C is inorganic hybrid reinforced straw-based biomass composite material prepared in example three;
FIG. 4 is a graph showing the crosslinking reaction of the polyamide polyamine-epichlorohydrin resin of the invention on straw, wood flour and pressed soybean meal.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
The first embodiment is as follows: the inorganic hybridization reinforced straw-based biomass composite material is prepared from 100 parts by weight of straw powder, 60-90 parts by weight of wood powder, 15-40 parts by weight of pressed oil bean pulp powder, 10-20 parts by weight of ore powder with layered silicate components and 65-240 parts by weight of polyamide polyamine-epichlorohydrin resin aqueous solution; the mass percentage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 8-15%.
The smaller the granularity of the oil-extracted soybean meal powder is, the better the composite effect is, and the higher the mechanical property and the water resistance are, but the production cost and the composite effect are both considered, and the oil-extracted soybean meal powder passing through a 120-mesh to 200-mesh screen is the most suitable. The mechanical property and the water resistance can be improved by properly increasing the consumption of the oil-pressed soybean meal, but after the consumption is more than 16 percent of the total mass of the straw powder and the wood powder, the improvement of the mechanical property and the water resistance is not obvious, and the cost is increased. Therefore, the production cost and the composite material performance are both considered, and the use amount of the oil-extracted soybean meal powder is 10-16% of the total mass of the straw powder and the wood powder.
The ore powder in the specific embodiment is ore with layered silicate components such as kaolin, bentonite, montmorillonite and the like, and is obtained by physical crushing and sieving with a sieve with the mesh number not less than 800, or can be directly used as the ore powder in the market. The layered silicate component contained in the ore powder is easily intercalated by water-soluble polyamide polyamine-epichlorohydrin resin with a cationic structure under the hot-pressing condition, and then has good adsorption effect with hydrophilic components or chain segments such as straw, bean powder, wood powder and the like to form a compact organic-inorganic hybridization system, so that a good hybridization reinforcing effect is generated on the composite material of the ore powder. And after the ore powder is added, the boiling water insoluble matter is improved, and a compound effect appears. The smaller the granularity of the ore powder (for example, obtained after passing through a 4000-mesh screen), the better the hybridization enhancement effect on straw, wood powder, pressed oil powder and aqueous polyamide polyamine-epichlorohydrin resin is, the higher the mechanical property is, but the larger the production cost and the energy consumption of the ore powder with smaller granularity are, and the production cost and the composite effect are both the most suitable for the ore powder passing through a 1250-2000-mesh screen.
The specific embodiment increases the concentration of the polyamide polyamine-epichlorohydrin resin, which is equivalent to increasing the dosage of the resin, can improve the mechanical property of the material, but can increase the cost; the concentration of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is reduced, the water content is increased, the hot press molding time is increased, and the method is favorable for uniformly dispersing the polyamide polyamine-epichlorohydrin resin in a powder mixture and prepressing and molding a blank of a special-shaped product; therefore, the mass percentage concentration of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is preferably 9 to 12 percent.
The beneficial effects of this concrete implementation are:
1) The preparation method has the advantages that expensive degradable plastic base materials are not required to be added, and the prepared biodegradable straw-based biomass-based composite material has the characteristics of low cost and green and environment-friendly product;
2) The organic-inorganic hybridization of straw powder, oil extraction soybean meal and wood powder (shown in figure 4) is enhanced based on the effective chemical crosslinking effect of polyamide polyamine-epichlorohydrin resin solution on the straw powder, the oil extraction soybean meal and the wood powder, so that a crosslinked network structure is formed among the straw powder, the soybean powder, the wood powder, the polyamide polyamine-epichlorohydrin resin and the ore powder, and excellent mechanical property and water resistance are endowed on the basis of keeping the biodegradability of the straw-wood powder-oil extraction soybean meal composite material;
3) By means of the crosslinking effect of the low-cost aqueous environment-friendly polyamide polyamine-epichlorohydrin resin solution (1800-2600 yuan/ton), the easily-obtained, low-cost, renewable and biodegradable straw powder, wood powder and oil-pressed bean pulp powder are directly utilized as main raw materials, modification pretreatment such as activation, plasticization or grafting is not needed for the straw powder, the wood powder, the oil-pressed bean pulp powder and the ore powder, and the low-cost straw-based biomass composite material which is biodegradable, has excellent mechanical property and water resistance and is suitable for base materials in various industrial fields can be prepared by one-step hot press molding, has the tensile strength of more than 20MPa, the static bending strength of more than 29MPa and the impact strength of more than 2.9kJ/m 2, is resistant to boiling in 4 hours, keeps good tensile property, has a simple production process, and provides a new method for efficient industrial raw material utilization of crop straws.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the mass percentage of the polyamide polyamine-epichlorohydrin resin aqueous solution is 9-12%. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the straw powder is wheat straw, rice straw, beanstalk or reed straw, and is obtained by physical crushing and passing through a screen with the mesh number not less than 12; the water content of the straw powder is lower than 10%. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the wood powder is one or a mixture of a plurality of raw wood, a wood board, wood processing residues and waste wood, and is obtained after physical crushing processing and passing through a screen with the mesh number not less than 12; the water content of the wood powder is lower than 12%. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the oil-pressed soybean meal powder is one or a mixture of two of low-temperature soybean meal and high-temperature soybean meal obtained by preparing oil from soybeans, and is obtained by physical crushing and passing through a screen with the mesh number not less than 120; the water content of the oil-pressed soybean meal powder is below 10%. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the ore powder with the layered silicate component is kaolin, bentonite or montmorillonite, and is obtained by physical crushing and passing through a screen with the mesh number not less than 800. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: the preparation method of the inorganic hybridization reinforced straw-based biomass composite material is completed according to the following steps:
1. Weighing 100 parts of straw powder, 60-90 parts of wood powder, 15-40 parts of oil-pressed soybean meal powder, 10-20 parts of ore powder with layered silicate components and 65-240 parts of polyamide polyamine-epichlorohydrin resin aqueous solution according to parts by mass; the mass percentage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 8-15%;
2. uniformly mixing 100 parts of weighed straw powder, 60-90 parts of wood powder, 15-40 parts of oil-pressed soybean meal powder and 10-20 parts of ore powder with layered silicate components to obtain a powder mixture;
3. Spraying 65-240 parts of aqueous solution of polyamide polyamine-epichlorohydrin resin into the powder mixture under the stirring condition, and continuously stirring until the mixture is uniformly dispersed after spraying to obtain the powder mixture containing the polyamide polyamine-epichlorohydrin resin;
4. And (3) performing hot press molding on a powder mixture containing polyamide polyamine-epichlorohydrin resin to obtain the inorganic hybrid reinforced straw-based biomass composite material.
The hot press forming in the step four of this embodiment is achieved by maintaining the necessary forming time t= (0.8 Th-1.2 Th) min (Th is the thickness of the inorganic hybrid reinforced straw-based biomass composite material, the unit is mm, the accuracy is 0.1mm, and if the unit is a special-shaped product, the area with the largest thickness is the standard), at the forming temperature of 110-160 ℃ and the forming pressure of 2-3.5 MPa, the purpose is to ensure sufficient crosslinking to form the composite material, and the composite material plate is obtained by hot press forming.
The inorganic hybrid reinforced straw-based biomass composite material has excellent mechanical properties (tensile strength is more than 20MPa, static bending strength is more than 29MPa, impact strength is more than 2.9kJ/m 2) and ideal water resistance (tolerance to 4h boiling water and good tensile property is reserved); the thickness of the composite material and the water content of the mixed material/blank have important influence on the hot press forming time, and increasing the thickness of the composite material can slow down the heating of the core layer of the mixed material/blank, so that the forming time is properly prolonged to ensure the core layer to be fully solidified; the water content of the mixed material/blank is improved, and the arrangement time of the composite material in hot press molding can be prolonged.
Eighth embodiment: the present embodiment is different from the seventh embodiment in that: and thirdly, spraying 65-240 parts of aqueous solution of polyamide polyamine-epichlorohydrin resin into the powder mixture under the condition that the stirring speed is 100-200 r/min. The other is the same as in the seventh embodiment.
Detailed description nine: this embodiment differs from the seventh or eighth embodiment in that: placing a powder mixture containing polyamide polyamine-epichlorohydrin resin into a die, and preserving heat and pressure at 110-160 ℃ and 2-3.5 MPa for t to obtain an inorganic hybridization reinforced straw-based biomass composite material;
Let the thickness of the inorganic hybridization reinforced straw-based biomass composite material be Th, and the unit is mm, t= (0.8 Th-1.2 Th) min. The others are the same as in the seventh or eighth embodiment.
The specific embodiment can be used for hot press molding of regular products such as flat plates, sheets and the like.
Detailed description ten: this embodiment differs from one of the seventh to ninth embodiments in that: step four, placing a powder mixture containing polyamide polyamine-epichlorohydrin resin into a mould, prepressing for 1-2 min under the condition of the pressure of 1-2.0 MPa to obtain a blank, then placing the blank into the mould with the temperature of 110-160 ℃, and preserving heat and pressure under the conditions of the temperature of 110-160 ℃ and the pressure of 2-3.5 MPa for t to obtain the inorganic hybridization reinforced straw-based biomass composite material;
let the thickness of the inorganic hybridization reinforced straw-based biomass composite material be Th, and the unit is mm, t= (0.8 Th-1.2 Th) min. The others are the same as in one of the seventh to ninth embodiments.
The special embodiment can be used for hot press molding of special-shaped products such as trays, bowls, boxes and the like so as to ensure the quality and the yield of the composite profile.
The following examples are used to verify the benefits of the present invention:
embodiment one:
The inorganic hybridization reinforced straw-based biomass composite material is prepared from 100 parts by weight of straw powder, 80 parts by weight of wood powder, 25 parts by weight of oil-pressed soybean meal powder, 10 parts by weight of ore powder with layered silicate components and 120 parts by weight of aqueous solution of polyamide polyamine-epichlorohydrin resin; the mass percentage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 12%;
The straw powder is obtained by physically crushing beanstalk and sieving the beanstalk with a 16-mesh sieve; the water content of the straw powder is 6-8%;
the wood powder is obtained by physically crushing poplar boards and sieving the poplar boards with a 16-mesh sieve; the water content of the wood powder is 6% -8%;
The oil-pressed soybean meal powder is a compound obtained by mixing low-temperature soybean meal and high-temperature soybean meal with the mass ratio of 1:1 and is obtained by physical crushing and sieving with a 200-mesh sieve; the water content of the oil-pressed soybean meal powder is 9% -10%;
the ore powder with the layered silicate component is kaolin, and is obtained after physical crushing processing and passing through a 1250-mesh screen.
The preparation method of the inorganic hybridization reinforced straw-based biomass composite material is completed according to the following steps:
1. Weighing 100 parts of straw powder, 80 parts of wood powder, 25 parts of oil-pressed soybean meal, 10 parts of ore powder with layered silicate components and 120 parts of polyamide polyamine-epichlorohydrin resin aqueous solution according to parts by mass; the mass percentage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 12%;
2. Uniformly mixing 100 parts of weighed straw powder, 80 parts of wood powder, 25 parts of pressed oil bean pulp powder and 10 parts of ore powder with layered silicate components to obtain a powder mixture;
3. spraying 120 parts of aqueous solution of polyamide polyamine-epichlorohydrin resin into the powder mixture at the stirring speed of 150r/min, and continuously stirring until the mixture is uniformly dispersed after spraying to obtain the powder mixture containing the polyamide polyamine-epichlorohydrin resin;
4. Placing a powder mixture containing polyamide polyamine-epichlorohydrin resin into a die, and carrying out heat preservation and pressure maintaining for 6min under the conditions of 135 ℃ and 3MPa of temperature by a flat press forming method to obtain an inorganic hybridization reinforced straw-based biomass composite board; the thickness Th of the inorganic hybridization reinforced straw-based biomass composite board is 5.5mm.
Embodiment two: the first difference between this embodiment and the first embodiment is that: the ore powder with the layered silicate component is prepared by crushing, grinding and sieving bentonite. The other is the same as in the first embodiment.
Embodiment III: the first difference between this embodiment and the first embodiment is that: the ore powder with the layered silicate component is obtained by crushing, grinding and sieving montmorillonite. The other is the same as in the first embodiment.
Embodiment four:
The inorganic hybridization reinforced straw-based biomass composite material is prepared from 100 parts by weight of straw powder, 80 parts by weight of wood powder, 25 parts by weight of oil-pressed soybean meal powder, 10 parts by weight of ore powder with layered silicate components and 155 parts by weight of aqueous solution of polyamide polyamine-epichlorohydrin resin; the mass percentage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 10%;
the straw powder is obtained by physically crushing reed stems and passing through a 16-mesh screen; the water content of the straw powder is 6-8%;
the wood powder is obtained by physically crushing poplar boards and sieving the poplar boards with a 16-mesh sieve; the water content of the wood powder is 6% -8%;
The oil-pressed soybean meal powder is a compound obtained by mixing low-temperature soybean meal and high-temperature soybean meal with the mass ratio of 1:1 and is obtained by physical crushing and sieving with a 200-mesh sieve; the water content of the oil-pressed soybean meal powder is 9% -10%;
the ore powder with the layered silicate component is kaolin, and is obtained after physical crushing processing and passing through a 1250-mesh screen.
The preparation method of the inorganic hybridization reinforced straw-based biomass composite material is completed according to the following steps:
1. Weighing 100 parts of straw powder, 80 parts of wood powder, 25 parts of oil-pressed soybean meal, 10 parts of ore powder with layered silicate components and 155 parts of polyamide polyamine-epichlorohydrin resin aqueous solution according to parts by mass; the mass percentage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 10%;
2. Uniformly mixing 100 parts of weighed straw powder, 80 parts of wood powder, 25 parts of pressed oil bean pulp powder and 10 parts of ore powder with layered silicate components to obtain a powder mixture;
3. Spraying 155 parts of aqueous solution of polyamide polyamine-epichlorohydrin resin into the powder mixture at the stirring speed of 150r/min, and continuously stirring until the mixture is uniformly dispersed after spraying to obtain the powder mixture containing the polyamide polyamine-epichlorohydrin resin;
4. Placing a powder mixture containing polyamide polyamine-epichlorohydrin resin into a die, and preserving heat and pressure for 3min under the conditions of 145 ℃ and 3MPa of temperature and pressure by a flat press forming method to obtain an inorganic hybridization reinforced straw-based biomass composite board; the thickness Th of the inorganic hybridization reinforced straw-based biomass composite board is 4.2mm.
Fifth embodiment: the first difference between this embodiment and the first embodiment is that: the straw powder is obtained by physically crushing beanstalk and passing through a 16-mesh screen. The other is the same as in the first embodiment.
Example six: the first difference between this embodiment and the first embodiment is that: the straw powder is obtained by physically crushing wheat straw and sieving the wheat straw with a 16-mesh sieve. The other is the same as in the first embodiment.
Embodiment seven: the first difference between this embodiment and the first embodiment is that: the straw powder is obtained by physically crushing rice straw and sieving the crushed rice straw with a 16-mesh sieve. The other is the same as in the first embodiment.
Comparative experiment one: the first difference between this embodiment and the first embodiment is that: omitting the addition of wood flour and ore flour having a layered silicate component; the straw powder is obtained by physically crushing reed stems and passing through a 16-mesh screen; the dosage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 65 parts; and obtaining the straw-based composite board without wood powder and ore powder reinforcement. The other is the same as in the first embodiment.
Comparison experiment II: the first difference between this embodiment and the first embodiment is that: omitting the addition of wood flour and ore flour having a layered silicate component; the dosage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 65 parts; and obtaining the straw-based composite board without wood powder and ore powder reinforcement. The other is the same as in the first embodiment.
Comparison experiment three: the first difference between this embodiment and the first embodiment is that: omitting the addition of the ore fines having the layered silicate component; the wood flour is 40 parts; the dosage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 90 parts; obtaining the wood powder reinforced straw-based biomass composite board. The other is the same as in the first embodiment.
Comparison experiment four: the first difference between this embodiment and the first embodiment is that: omitting the addition of the ore fines having the layered silicate component; the wood flour is 80 parts; the dosage of the aqueous solution of the polyamide polyamine-epichlorohydrin resin is 110 parts; obtaining the wood powder reinforced straw-based biomass composite board. The other is the same as in the first embodiment.
Fig. 1 is a physical diagram of an inorganic hybrid reinforced straw-based biomass composite material, a is an embodiment four, b is an embodiment five, c is an embodiment seven, and d is an embodiment six.
Fig. 2 is an XRD graph of an inorganic hybrid enhanced straw-based biomass composite material prepared in example three. As can be seen from the graph, the X-ray diffraction (XRD) curves of the montmorillonite have typical montmorillonite diffraction peaks at 24.8 degrees, 20.8 degrees and 6.3 degrees, and the inorganic hybridization reinforced straw-based biomass composite material prepared in the third embodiment has the diffraction peaks at 6.3 degrees disappeared and the diffraction peaks at 24.8 degrees and 20.8 degrees obviously weakened, so that the organic-inorganic hybridization effect is formed by montmorillonite ore powder and a polyamide polyamine-epichlorohydrin resin, straw, bean powder and wood powder composite system.
Grinding the sample and passing through a 100-mesh screen to obtain sample powder, adding 1g of sample powder into 100g of water, keeping the mixture for 2 hours under the boiling condition of the water, cooling, measuring the solid content of insoluble matters, and calculating the percentage of the solid content of insoluble matters in the original sample powder to obtain the boiling water insoluble rate. Fig. 3 shows boiling water insolubility, a is montmorillonite ore powder, B is wood powder reinforced straw-based biomass composite board prepared in comparative experiment four, and C is inorganic hybrid reinforced straw-based biomass composite material prepared in example three. The inorganic hybridization reinforced straw-based biomass composite material has 84.8 percent of boiling water insoluble matters, has a higher composite effect than the wood powder reinforced straw-based biomass composite board (B: 82.3 percent) without montmorillonite ore powder and the simple montmorillonite ore (A: 76.9 percent), and further proves the hybridization reinforcing effect of the montmorillonite ore powder on the straw-based composite system.
The wood powder-free and ore powder-reinforced straw-based composite boards prepared in the first and second tests are labeled A1 and A2, the wood powder-reinforced straw-based biomass composite boards prepared in the third and fourth tests are labeled B1 and B2, the inorganic hybrid-reinforced straw-based biomass composite boards prepared in the first and third tests are labeled C1-C3 in sequence, and the inorganic hybrid-reinforced straw-based biomass composite boards prepared in the fourth and seventh tests are labeled D1-D4 in sequence.
The wood flour and ore flour reinforced straw-based composite board obtained by the comparative experiments one to two, the wood flour reinforced straw-based biomass composite board obtained by the comparative experiments three and four, and the inorganic hybrid reinforced straw-based biomass composite board obtained by the examples one to seven were subjected to tests of absolute dry density and static bending strength according to the national standard GB/T4897-2015, were subjected to tests of dry tensile strength and dry boiling tensile strength according to the ASTM D638-03 standard (test piece was boiled in boiling water for 4 hours and then baked in an oven at 63 ℃ for 4 hours), were subjected to an impact strength test according to the ASTM D256-04 standard, and the biodegradability was evaluated by using the mass loss rate of the composite material after 8 weeks of soil burial.
The results of the comparison experiments are shown as A1 and A2 samples in Table 1, when no wood powder and inorganic filler are reinforced, based on the crosslinking effect and the interfacial gluing effect of polyamide polyamine-epichlorohydrin resin on the oil-pressed soybean meal powder and the straw powder, the straw powder and the oil-pressed soybean meal powder form a straw-based biomass composite material with certain mechanical property and boiling water resistance under the hot press molding effect, the density is 0.78g/cm 3～0.81g/cm3, the static bending strength is 13.01-29.04 MPa, the impact strength is 1.33kJ/m 2～3.59kJ/m2, the dry tensile strength is 7.76-18.17 MPa, the boiling water resistance and the boiling dry tensile strength are 5.29-10.56 MPa, the mass loss rate after the reed rod is buried in outdoor soil for 8 weeks is 32.4-36.9%, the mechanical property and the water resistance of the reed rod-based biomass composite material are obviously superior to those of the bean straw-based biomass composite material because of fiber toughness, but the biodegradability of the reed rod-based biomass composite material is slightly weaker than that of the bean-based biomass composite material.
The results of the third and fourth comparison tests are shown as the samples B1 and B2 in the table 1, and compared with the A2 plate without the wood powder, the mechanical property and the water resistance of the biomass-based composite plate with the wood powder are obviously improved. When wood powder accounting for 40% of the mass of the straw powder is added, the density (0.79 g/cm 3) of the wood powder is basically equivalent to that of A2, but the static bending strength of the wood powder is improved by 40.4%, the impact strength is improved by 42.1%, the dry tensile strength is improved by 86.9%, the boiling dry tensile strength is improved by 147.1%, and the mass loss rate of the wood powder after 8 weeks of outdoor soil burial is reduced (-6.8%); when the mass of the added wood powder reaches 80% of the mass of the straw powder, the density (0.75 g/cm 3) is basically equivalent to that of A2, but the static bending strength is improved by 116.1%, the impact strength is improved by 97.7%, the dry tensile strength is improved by 129.4%, the boiling dry tensile strength is improved by 204.3%, and the mass loss rate after the outdoor soil is buried for 8 weeks is reduced by 11.1%. As the wood fiber is used as perennial woody plant fiber, the strength and toughness of the wood fiber are superior to those of beanstalk fiber of annual herbaceous plants, so that the mechanical property and the water resistance of the wood fiber can be effectively improved by increasing the consumption of the wood powder, but the wood fiber is unfavorable for more fully utilizing the straw.
Examples one to three results are shown in C1-C3 samples of Table 1, and the addition of ore powder with a layered silicate component as a reinforcing component can further improve both the mechanical properties and the water resistance of the straw-based biomass composite board as compared with the B2 board reinforced without the ore powder. If the kaolin is used for reinforcement, the density (0.78 g/cm 3) is basically equivalent to that of B2, but the static bending strength is improved by 25.6%, the impact strength is improved by 19.0%, the dry tensile strength is improved by 28.8%, the kaolin can resist boiling water and the boiling dry tensile strength is improved by 18.8%, and the mass loss rate after the outdoor soil is buried for 8 weeks is reduced by 3.4%; if bentonite is used for reinforcement, the density (0.76 g/cm 3) is basically equivalent to that of B2, but the static bending strength is improved by 17.9%, the impact strength is improved by 24.3%, the dry tensile strength is improved by 24.4%, the boiling dry tensile strength is improved by 3.5%, and the mass loss rate after outdoor soil is buried for 8 weeks is kept equivalent (32.2%). It can be seen that although all three ore powders have a better reinforcing effect, the reinforcing effect of kaolin is generally better than that of bentonite and montmorillonite.
The results of the fourth to seventh examples are shown in the D1-D4 samples in Table 1, based on the enhancement of wood powder and ore powder, the combination of the crosslinking of polyamide polyamine-epichlorohydrin resin can realize the preparation of biomass-based composite materials with good mechanical properties, water resistance and biodegradability by using different types of straws, the density is about 0.80g/cm 3, the static bending strength is higher than 29MPa, the impact strength is higher than 2.9kJ/m 2, the dry tensile strength is higher than 20MPa, the boiling water boiling resistance and the boiling dry tensile strength are both higher than 11MPa, the mass loss rate after the outdoor soil is buried for 8 weeks is higher than 30%, and the application requirements of the fields of general packaging materials, automobile interior trim materials, non-bearing interior trim materials, furniture materials and the like can be met. However, the performances of the straw-based biomass composite materials prepared under the same conditions have certain differences due to the differences of the wood fiber content, the wood fiber morphology, the weak interface substance (siliceous and waxy components) content and the like of different types of straws, wherein the performances of reed stems and beanstalk are relatively good.
TABLE 1
Claims (3)
1. The inorganic hybridization reinforced straw-based biomass composite material is characterized by being prepared from 100 parts by weight of straw powder, 80-90 parts by weight of wood powder, 25-40 parts by weight of oil-pressed soybean meal, 10 parts by weight of ore powder with layered silicate components and 65-155 parts by weight of aqueous solution of polyamide polyamine-epichlorohydrin resin; the mass percentage of the polyamide polyamine-epichlorohydrin resin aqueous solution is 8% -10%;
The straw powder is reed stems, and is obtained by physical crushing and passing through a screen with the mesh number not less than 12; the water content of the straw powder is lower than 10%;
the ore powder with the layered silicate component is kaolin, and is obtained after physical crushing processing and passing through a screen with the mesh number not less than 800 meshes;
The wood powder is obtained by physical crushing and passing through a screen with the mesh number not less than 12; the water content of the wood powder is lower than 12%;
the oil-pressed soybean meal powder is a mixture of low-temperature soybean meal and high-temperature soybean meal obtained by preparing oil from soybeans, and is obtained by physical crushing and passing through a screen with the mesh number not less than 120 meshes; the water content of the oil-pressed soybean meal powder is below 10%;
The preparation method of the composite material comprises the following steps:
1. Weighing 100 parts of straw powder, 80 parts to 90 parts of wood powder, 25 parts to 40 parts of oil-pressed soybean meal powder, 10 parts of ore powder with layered silicate components and 65 parts to 155 parts of polyamide polyamine-epichlorohydrin resin aqueous solution according to parts by mass; the mass percentage of the polyamide polyamine-epichlorohydrin resin aqueous solution is 8% -10%;
2. uniformly mixing 100 parts of weighed straw powder, 80-90 parts of wood powder, 25-40 parts of oil-pressed soybean meal powder and 10 parts of ore powder with layered silicate components to obtain a powder mixture;
3. spraying 65-155 parts of aqueous solution of polyamide polyamine-epichlorohydrin resin into the powder mixture under the stirring condition, and continuously stirring until the mixture is uniformly dispersed after spraying to obtain the powder mixture containing the polyamide polyamine-epichlorohydrin resin;
4. Carrying out hot press molding on a powder mixture containing polyamide polyamine-epichlorohydrin resin to obtain an inorganic hybridization reinforced straw-based biomass composite material;
the specific operation of the fourth step is as follows:
placing a powder mixture containing polyamide polyamine-epichlorohydrin resin into a mold, and preserving heat and pressure at 110-135 ℃ and under the pressure of 2-3.5 MPa for t to obtain an inorganic hybridization reinforced straw-based biomass composite material; and (3) assuming that the thickness of the inorganic hybridization reinforced straw-based biomass composite material is Th and the unit is mm, t= (0.8 Th-1.2 Th) min.
2. The inorganic hybrid reinforced straw-based biomass composite material according to claim 1, wherein the wood flour is one or a mixture of a plurality of raw wood, a wood board, a wood processing residue and waste wood.
3. The inorganic hybrid reinforced straw-based biomass composite material according to claim 1, wherein in the third step, 65-155 parts of aqueous solution of polyamide polyamine-epichlorohydrin resin is sprayed into the powder mixture under the condition that the stirring speed is 100-200 r/min.
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