CN112480357A - Flame-retardant polyurethane nano-cellulose reinforced material and preparation method thereof - Google Patents
Flame-retardant polyurethane nano-cellulose reinforced material and preparation method thereof Download PDFInfo
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- CN112480357A CN112480357A CN202011406039.5A CN202011406039A CN112480357A CN 112480357 A CN112480357 A CN 112480357A CN 202011406039 A CN202011406039 A CN 202011406039A CN 112480357 A CN112480357 A CN 112480357A
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Abstract
The invention discloses a flame-retardant polyurethane nano-cellulose reinforced material and a preparation method thereof, wherein the flame-retardant polyurethane nano-cellulose reinforced material comprises the following raw materials in parts by weight: 60-80 parts of an oligomer polyol raw material: 80-120 parts of foaming agent: 20-35 parts of a foam stabilizer: 2-3 parts of initiator: 3-5 parts of a chain extender: 2-4 parts of a cross-linking agent: 1-3 parts of plant raw materials: 10-15 parts of epoxy resin, 5-10 parts of epoxy resin, 8-13 parts of inorganic flame retardant, 25-30 parts of flame-retardant filler and 5-6 parts of compounding agent. According to the invention, the plant raw materials and the epoxy resin are added in the formula, the plant raw materials can be used for preparing the nano-cellulose, the nano-cellulose has excellent carbon forming capability and reinforcing effect, the flame retardant effect of the polyurethane foam board can be improved, the mechanical property is excellent, the epoxy resin has excellent adhesive property, high modulus, high strength and thermal stability, and the epoxy resin can play a role in forced mutual solubility and synergistic effect with the nano-cellulose, so that the stability is improved, and the performance complementation is realized.
Description
Technical Field
The invention relates to a flame-retardant material and a preparation method thereof, in particular to a flame-retardant polyurethane nano-cellulose reinforced material and a preparation method thereof, belonging to the technical field of flame-retardant materials.
Background
Polyurethane is commonly used in aviation, railway, building, sports and other aspects, polyurethane rigid foam is a high molecular polymer which is prepared by mixing isocyanate and polyether as main raw materials through special equipment under the action of various auxiliary agents such as a foaming agent, a catalyst, a flame retardant and the like and foaming on site through high-pressure spraying, and polyurethane has two types of soft foam and hard foam, wherein the polyurethane rigid foam is a novel synthetic material with heat preservation and waterproof functions, and is mainly applied to the heat preservation of building outer walls, the integration of roof waterproof and heat preservation, the heat preservation and insulation of refrigeration houses, pipeline heat preservation materials, building boards, refrigerated trucks, refrigeration house heat insulation materials and the like, but the existing polyurethane foam has many problems or defects:
the existing polyurethane foam has poor high temperature resistance and is easy to deform under a high-temperature state for a long time, so that the heat insulation effect is reduced; the existing polyurethane foam can be burnt and decomposed when encountering fire, and can generate a large amount of toxic smoke, thereby greatly harming the property and life safety of people; although the existing polyurethane foam has certain strength, the toughness is poor, the requirement on engineering can not be completely met in some occasions, and the polyurethane foam is easy to break when in use.
Disclosure of Invention
The invention aims to solve the problems and provide a flame-retardant polyurethane nano-cellulose reinforced material and a preparation method thereof.
The invention achieves the aim through the following technical scheme, and the flame-retardant polyurethane nano-cellulose reinforced material comprises the following raw materials in parts by weight: 60-80 parts of an oligomer polyol raw material: 80-120 parts of foaming agent: 20-35 parts of a foam stabilizer: 2-3 parts of initiator: 3-5 parts of a chain extender: 2-4 parts of a cross-linking agent: 1-3 parts of plant raw materials: 10-15 parts of epoxy resin, 5-10 parts of epoxy resin, 8-13 parts of inorganic flame retardant, 25-30 parts of flame-retardant filler and 5-6 parts of compounding agent.
Preferably, the isocyanate raw material is a mixture of toluene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate, and the mass ratio of the toluene diisocyanate to the diphenylmethane diisocyanate to the dicyclohexylmethane diisocyanate is 2.5: 3: 1.5.
preferably, the oligomer polyol raw material is a mixture of polyester polyol and polyether polyol, and the mass ratio of the polyester polyol to the polyether polyol is 1: 2.
preferably, the foaming agent is one or two of calcium carbonate, magnesium carbonate and sodium bicarbonate, and the foam stabilizer is polyether modified organopolysiloxane.
Preferably, the initiator is an inorganic peroxide initiator, the inorganic peroxide initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate, and the chain extender is one of an amine chain extender and an alcohol chain extender.
Preferably, the plant raw materials are wood, cotton linter, wheat straw, reed, hemp, mulberry bark, paper mulberry bark, bagasse and the like.
Preferably, the epoxy resin is a polycondensation product of epichlorohydrin and bisphenol a or a polyol.
Preferably, the inorganic flame retardant is one of aluminum hydroxide, magnesium hydroxide and red phosphorus, and the flame-retardant filler is one of talcum powder, mica powder and wollastonite powder.
Preferably, the compounding agent is one or more of an antioxidant, an ultraviolet absorber, a colorant, a plasticizer and a catalyst.
A preparation method of a flame-retardant polyurethane nano-cellulose reinforced material comprises the following steps:
the method comprises the steps of firstly, preparing a cellulose raw material, pouring weighed plant raw materials into a sulfite solution for cooking, removing lignin in the plant raw materials to obtain sulfite pulp, bleaching the sulfite pulp, further removing hemicellulose, filtering to obtain the fiber plant raw materials, mixing the fiber plant raw materials with inorganic acid, smashing into pulp to prepare a cellulose coarse material, performing partial depolymerization on the cellulose coarse material, removing a non-crystalline part, and purifying to obtain the cellulose raw material.
And secondly, preparing nano-cellulose, namely adding hydrochloric acid, sulfuric acid and cellulose raw materials into a reaction kettle, controlling the temperature of the reaction kettle to be between 55 and 65 ℃, stirring for 50 to 55 minutes, and centrifuging for multiple times to obtain a nano-cellulose suspension solution.
And thirdly, preparing a mixed material, namely putting an oligomer polyol raw material into a preparation cylinder, sequentially adding a foaming agent, a foam homogenizing agent, an initiator, a chain extender, a nano-cellulose suspension solution and a proper amount of water into the preparation cylinder, controlling the temperature of the preparation cylinder to be between 120 and 135 ℃, continuously stirring, adding a cross-linking agent and epoxy resin into the preparation cylinder when stirring for 35 to 40 minutes, and fully stirring for 20 to 30 minutes to obtain the mixed material.
And fourthly, foaming, namely adding the isocyanate raw material into the mixed material, controlling the temperature of the preparation cylinder to be between 100 and 110 ℃, stirring, adding the accessory ingredient into the preparation cylinder in the stirring process, standing the mixed material after stirring until a steam pocket is generated, and controlling the standing time to be between 65 and 70 hours.
And fifthly, curing and shaping, namely conveying the mold into an oven, adjusting the temperature of the oven to 15-20 ℃, pouring the foamed mixed material into the mold for curing for 40-65 minutes, adjusting the temperature of the oven to 70-95 ℃, and curing the foamed mixed material at high temperature for 3-3.5 hours to obtain the plate.
And sixthly, performing flame retardant treatment, namely coating a film on the surface of the shaped board, then mixing the inorganic flame retardant and the flame retardant filler to obtain a mixed coating, then uniformly coating the mixed coating on the board, placing the board to be aired for 1.5 to 3 hours at normal temperature after coating is finished, and finally performing secondary film coating on the board to obtain a finished product.
The invention has the beneficial effects that:
1. according to the invention, the plant raw materials and the epoxy resin are added in the formula, the plant raw materials can be used for preparing the nano-cellulose, the nano-cellulose has excellent char forming capability and reinforcing effect, the flame retardant effect of the polyurethane foam board can be improved, the mechanical property is excellent, the epoxy resin has excellent bonding property, high modulus, high strength and thermal stability, the characteristics of compactness, water resistance, good leakage resistance, high strength, strong adhesive force and the like, the price is moderate, and the functions of forced mutual dissolution and synergistic effect with the nano-cellulose can be realized, so that the stability is improved, and the performance complementation is realized;
2. according to the invention, the inorganic flame retardant and the flame-retardant filler are added in the formula, and are mixed and then coated on the polyurethane foam board, so that the combustion-supporting capacity of the polyurethane foam board can be improved, the inorganic flame retardant has good environmental protection property, does not release smoke, does not generate harmful and controversial gas, and has low cost, and the flame-retardant filler can dilute, store heat, conduct heat, cool, realize surface effect and the like on high polymers;
3. the invention can carry out different flame-retardant treatments on the polyurethane foam board in the preparation process, and when the common flame-retardant board is manufactured, the mixed coating is directly coated on the surface of the board without film coating treatment, thereby reducing the manufacturing cost.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the flame-retardant polyurethane nano-cellulose reinforced material comprises the following raw materials in parts by weight: 60-80 parts of an oligomer polyol raw material: 80-120 parts of foaming agent: 20-35 parts of a foam stabilizer: 2-3 parts of initiator: 3-5 parts of a chain extender: 2-4 parts of a cross-linking agent: 1-3 parts of plant raw materials: 10-15 parts of epoxy resin, 5-10 parts of epoxy resin, 8-13 parts of inorganic flame retardant, 25-30 parts of flame-retardant filler and 5-6 parts of compounding agent.
Specifically, the isocyanate raw material is a mixture of toluene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate, and the mass ratio of the toluene diisocyanate to the diphenylmethane diisocyanate to the dicyclohexylmethane diisocyanate is 2.5: 3: 1.5.
specifically, the oligomer polyol raw material is a mixture of polyester polyol and polyether polyol, and the mass ratio of the polyester polyol to the polyether polyol is 1: 2.
specifically, the foaming agent is one or two of calcium carbonate, magnesium carbonate and sodium bicarbonate, and the foam stabilizer is polyether modified organopolysiloxane.
Specifically, the initiator is an inorganic peroxide initiator, the inorganic peroxide initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate, and the chain extender is one of an amine chain extender and an alcohol chain extender.
Specifically, the plant raw materials comprise wood, cotton linter, wheat straw, reed, hemp, mulberry bark, paper mulberry bark, bagasse and the like.
Specifically, the epoxy resin is a polycondensation product of epichlorohydrin and bisphenol A or polyol.
Specifically, the inorganic flame retardant is one of aluminum hydroxide, magnesium hydroxide and red phosphorus, and the flame-retardant filler is one of talcum powder, mica powder and wollastonite powder.
Specifically, the compounding agent is one or more of an antioxidant, an ultraviolet absorber, a coloring agent, a plasticizer and a catalyst.
A preparation method of a flame-retardant polyurethane nano-cellulose reinforced material comprises the following steps:
the method comprises the steps of firstly, preparing a cellulose raw material, pouring weighed plant raw materials into a sulfite solution for cooking, removing lignin in the plant raw materials to obtain sulfite pulp, bleaching the sulfite pulp, further removing hemicellulose, filtering to obtain the fiber plant raw materials, mixing the fiber plant raw materials with inorganic acid, smashing into pulp to prepare a cellulose coarse material, performing partial depolymerization on the cellulose coarse material, removing a non-crystalline part, and purifying to obtain the cellulose raw material.
And secondly, preparing nano-cellulose, namely adding hydrochloric acid, sulfuric acid and cellulose raw materials into a reaction kettle, controlling the temperature of the reaction kettle to be between 55 and 65 ℃, stirring for 50 to 55 minutes, and centrifuging for multiple times to obtain a nano-cellulose suspension solution.
And thirdly, preparing a mixed material, namely putting an oligomer polyol raw material into a preparation cylinder, sequentially adding a foaming agent, a foam homogenizing agent, an initiator, a chain extender, a nano-cellulose suspension solution and a proper amount of water into the preparation cylinder, controlling the temperature of the preparation cylinder to be between 120 and 135 ℃, continuously stirring, adding a cross-linking agent and epoxy resin into the preparation cylinder when stirring for 35 to 40 minutes, and fully stirring for 20 to 30 minutes to obtain the mixed material.
And fourthly, foaming, namely adding the isocyanate raw material into the mixed material, controlling the temperature of the preparation cylinder to be between 100 and 110 ℃, stirring, adding the accessory ingredient into the preparation cylinder in the stirring process, standing the mixed material after stirring until a steam pocket is generated, and controlling the standing time to be between 65 and 70 hours.
And fifthly, curing and shaping, namely conveying the mold into an oven, adjusting the temperature of the oven to 15-20 ℃, pouring the foamed mixed material into the mold for curing for 40-65 minutes, adjusting the temperature of the oven to 70-95 ℃, and curing the foamed mixed material at high temperature for 3-3.5 hours to obtain the plate.
And sixthly, performing flame retardant treatment, namely mixing the inorganic flame retardant and the flame retardant filler to obtain a mixed coating, uniformly coating the mixed coating on the board, and airing the board at normal temperature for 1.5 to 2 hours after finishing coating to obtain a finished product.
The preparation method is suitable for manufacturing common flame-retardant plates.
Example two:
the flame-retardant polyurethane nano-cellulose reinforced material comprises the following raw materials in parts by weight: 60-80 parts of an oligomer polyol raw material: 80-120 parts of foaming agent: 20-35 parts of a foam stabilizer: 2-3 parts of initiator: 3-5 parts of a chain extender: 2-4 parts of a cross-linking agent: 1-3 parts of plant raw materials: 10-15 parts of epoxy resin, 5-10 parts of epoxy resin, 8-13 parts of inorganic flame retardant, 25-30 parts of flame-retardant filler and 5-6 parts of compounding agent.
Specifically, the isocyanate raw material is a mixture of toluene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate, and the mass ratio of the toluene diisocyanate to the diphenylmethane diisocyanate to the dicyclohexylmethane diisocyanate is 2.5: 3: 1.5.
specifically, the oligomer polyol raw material is a mixture of polyester polyol and polyether polyol, and the mass ratio of the polyester polyol to the polyether polyol is 1: 2.
specifically, the foaming agent is one or two of calcium carbonate, magnesium carbonate and sodium bicarbonate, and the foam stabilizer is polyether modified organopolysiloxane.
Specifically, the initiator is an inorganic peroxide initiator, the inorganic peroxide initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate, and the chain extender is one of an amine chain extender and an alcohol chain extender.
Specifically, the plant raw materials comprise wood, cotton linter, wheat straw, reed, hemp, mulberry bark, paper mulberry bark, bagasse and the like.
Specifically, the epoxy resin is a polycondensation product of epichlorohydrin and bisphenol A or polyol.
Specifically, the inorganic flame retardant is one of aluminum hydroxide, magnesium hydroxide and red phosphorus, and the flame-retardant filler is one of talcum powder, mica powder and wollastonite powder.
Specifically, the compounding agent is one or more of an antioxidant, an ultraviolet absorber, a coloring agent, a plasticizer and a catalyst.
A preparation method of a flame-retardant polyurethane nano-cellulose reinforced material comprises the following steps:
the method comprises the steps of firstly, preparing a cellulose raw material, pouring weighed plant raw materials into a sulfite solution for cooking, removing lignin in the plant raw materials to obtain sulfite pulp, bleaching the sulfite pulp, further removing hemicellulose, filtering to obtain the fiber plant raw materials, mixing the fiber plant raw materials with inorganic acid, smashing into pulp to prepare a cellulose coarse material, performing partial depolymerization on the cellulose coarse material, removing a non-crystalline part, and purifying to obtain the cellulose raw material.
And secondly, preparing nano-cellulose, namely adding hydrochloric acid, sulfuric acid and cellulose raw materials into a reaction kettle, controlling the temperature of the reaction kettle to be between 55 and 65 ℃, stirring for 50 to 55 minutes, and centrifuging for multiple times to obtain a nano-cellulose suspension solution.
And thirdly, preparing a mixed material, namely putting an oligomer polyol raw material into a preparation cylinder, sequentially adding a foaming agent, a foam homogenizing agent, an initiator, a chain extender, a nano-cellulose suspension solution and a proper amount of water into the preparation cylinder, controlling the temperature of the preparation cylinder to be between 120 and 135 ℃, continuously stirring, adding a cross-linking agent and epoxy resin into the preparation cylinder when stirring for 35 to 40 minutes, and fully stirring for 20 to 30 minutes to obtain the mixed material.
And fourthly, foaming, namely adding the isocyanate raw material into the mixed material, controlling the temperature of the preparation cylinder to be between 100 and 110 ℃, stirring, adding the accessory ingredient into the preparation cylinder in the stirring process, standing the mixed material after stirring until a steam pocket is generated, and controlling the standing time to be between 65 and 70 hours.
And fifthly, curing and shaping, namely conveying the mold into an oven, adjusting the temperature of the oven to 15-20 ℃, pouring the foamed mixed material into the mold for curing for 40-65 minutes, adjusting the temperature of the oven to 70-95 ℃, and curing the foamed mixed material at high temperature for 3-3.5 hours to obtain the plate.
And sixthly, performing flame retardant treatment, namely coating a film on the surface of the shaped plate, then mixing the inorganic flame retardant and the flame retardant filler to obtain a mixed coating, then uniformly coating the mixed coating on the plate, placing the plate to be aired for 2 to 3 hours at normal temperature after coating is finished, and finally performing secondary film coating on the plate to obtain a finished product.
The preparation method is suitable for manufacturing high-grade flame-retardant plates.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A flame-retardant polyurethane nano-cellulose reinforced material is characterized in that: the formula comprises the following raw materials in parts by weight: 60-80 parts of an oligomer polyol raw material: 80-120 parts of foaming agent: 20-35 parts of a foam stabilizer: 2-3 parts of initiator: 3-5 parts of a chain extender: 2-4 parts of a cross-linking agent: 1-3 parts of plant raw materials: 10-15 parts of epoxy resin, 5-10 parts of epoxy resin, 8-13 parts of inorganic flame retardant, 25-30 parts of flame-retardant filler and 5-6 parts of compounding agent.
2. The flame retardant polyurethane nanocellulose reinforcement material of claim 1, wherein: the isocyanate raw material is a mixture of toluene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate, and the mass ratio of the toluene diisocyanate to the diphenylmethane diisocyanate to the dicyclohexylmethane diisocyanate is 2.5: 3: 1.5.
3. the flame retardant polyurethane nanocellulose reinforcement material of claim 1, wherein: the oligomer polyol raw material is a mixture of polyester polyol and polyether polyol, and the mass ratio of the polyester polyol to the polyether polyol is 1: 2.
4. the flame retardant polyurethane nanocellulose reinforcement material of claim 1, wherein: the foaming agent is one or two of calcium carbonate, magnesium carbonate and sodium bicarbonate, and the foam homogenizing agent is polyether modified organopolysiloxane.
5. The flame retardant polyurethane nanocellulose reinforcement material of claim 1, wherein: the initiator is an inorganic peroxide initiator, the inorganic peroxide initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate, and the chain extender is one of an amine chain extender and an alcohol chain extender.
6. The flame retardant polyurethane nanocellulose reinforcement material of claim 1, wherein: the plant raw materials are wood, cotton linter, wheat straw, reed, hemp, mulberry bark, paper mulberry bark, bagasse and the like.
7. The flame retardant polyurethane nanocellulose reinforcement material of claim 1, wherein: the epoxy resin is a polycondensation product of epichlorohydrin and bisphenol A or polyhydric alcohol.
8. The flame retardant polyurethane nanocellulose reinforcement material of claim 1, wherein: the inorganic flame retardant is one of aluminum hydroxide, magnesium hydroxide and red phosphorus, and the flame-retardant filler is one of talcum powder, mica powder and wollastonite powder.
9. The flame retardant polyurethane nanocellulose reinforcement material of claim 1, wherein: the compounding agent is one or more of an antioxidant, an ultraviolet absorbent, a coloring agent, a plasticizer and a catalyst.
10. The method for preparing a flame retardant polyurethane nanocellulose reinforcing material from the flame retardant polyurethane nanocellulose reinforcing material according to any one of claims 1 to 9, characterized by: the preparation method comprises the following steps:
firstly, preparing a cellulose raw material, pouring weighed plant raw materials into a sulfite solution for cooking, removing lignin in the plant raw materials to obtain sulfite slurry, bleaching the sulfite slurry, further removing hemicellulose, filtering to obtain the fiber plant raw materials, mixing the fiber plant raw materials with inorganic acid, smashing into slurry to prepare a cellulose coarse material, partially depolymerizing the cellulose coarse material, removing a non-crystalline part, and purifying to obtain the cellulose raw material;
secondly, preparing nano-cellulose, namely adding hydrochloric acid, sulfuric acid and cellulose raw materials into a reaction kettle, controlling the temperature of the reaction kettle to be between 55 and 65 ℃, stirring for 50 to 55 minutes, and centrifuging for multiple times to obtain a nano-cellulose suspension solution;
thirdly, preparing a mixed material, namely putting an oligomer polyol raw material into a preparation cylinder, sequentially adding a foaming agent, a foam homogenizing agent, an initiator, a chain extender, a nano-cellulose suspension solution and a proper amount of water into the preparation cylinder, controlling the temperature of the preparation cylinder to be between 120 and 135 ℃, continuously stirring, adding a cross-linking agent and epoxy resin into the preparation cylinder when stirring for 35 to 40 minutes, and fully stirring for 20 to 30 minutes to obtain the mixed material;
step four, foaming, namely adding the isocyanate raw material into the mixed material, controlling the temperature of a preparation cylinder to be between 100 and 110 ℃, stirring, adding the accessory ingredient into the preparation cylinder in the stirring process, standing the mixed material after stirring until a steam pocket is generated, and controlling the standing time to be between 65 and 70 hours;
fifthly, curing and shaping, namely conveying the mold into an oven, adjusting the temperature of the oven to 15-20 ℃, pouring the foamed mixed material into the mold for curing for 40-65 minutes, adjusting the temperature of the oven to 70-95 ℃, and curing the foamed mixed material at high temperature for 3-3.5 hours to obtain a plate;
and sixthly, performing flame retardant treatment, namely coating a film on the surface of the shaped board, then mixing the inorganic flame retardant and the flame retardant filler to obtain a mixed coating, then uniformly coating the mixed coating on the board, placing the board to be aired for 1.5 to 3 hours at normal temperature after coating is finished, and finally performing secondary film coating on the board to obtain a finished product.
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