CN113307939B - Environment-friendly polyurethane foam and preparation method thereof - Google Patents
Environment-friendly polyurethane foam and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly polyurethane foam and a preparation method thereof. Firstly, uniformly mixing silkworm excrement powder with polyethylene glycol and micromolecular alcohol, adding concentrated sulfuric acid, and reacting at the temperature of 130-160 ℃ for 2-4h to prepare liquefied silkworm excrement polyether polyol; dissolving rutin in formyldimethylamine, cooling to-5-5 ℃, slowly adding sodium borohydride, stirring at room temperature for 2-4h, and preparing modified rutin; putting nano graphene oxide into deionized water, adding ammonia water to adjust the pH value, stirring, introducing nitrogen, adding modified rutin and lanthanum chloride, heating to 90-110 ℃, and preserving heat for 12-16 hours to obtain modified graphene; uniformly mixing liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water, adding modified graphene, uniformly stirring, adding isocyanate, uniformly stirring, pouring into a mould, foaming and curing to obtain the environment-friendly polyurethane foam. The environment-friendly polyurethane foam has antibacterial property and flame resistance, and can be used as a medical equipment material.
Description
Technical Field
The invention relates to the field of polyurethane foam, in particular to environment-friendly polyurethane foam and a preparation method thereof.
Background
The polyurethane foam is generally synthesized by polymerizing polyisocyanate, polyol and various auxiliaries, and has the mechanical properties of low density, heat preservation, sound absorption, noise prevention, shock absorption and buffering, so that the polyurethane foam is widely applied to furniture, buildings, refrigeration and transportation. Polyurethane is divided into soft foam and hard foam, the soft foam is used for sofa furniture, toys and the like, and the hard foam is used for building outer wall heat insulation, pipeline heat insulation materials, heat insulation plates and the like.
The rigid polyurethane foam is a flammable thermal insulation material, when the rigid polyurethane foam is used for heat insulation plates and building materials, the improvement of the flame retardant property of the rigid polyurethane foam is very important, and the improvement of the flame retardant property of the rigid polyurethane foam is very limited due to the common flame retardant of elements such as chlorine, bromine, phosphorus and the like. When rigid polyurethane foams are used in medical applications, it is often desirable that the materials have antimicrobial properties, but rigid polyurethane foams are now less studied in this regard. The traditional polyurethane foam synthesized by polymerization of polyisocyanate and polyol is difficult to degrade and pollutes the environment, while the polyurethane foam prepared by adopting natural products as polyol is degradable and has lower cost.
Disclosure of Invention
The invention aims to provide environment-friendly polyurethane foam and a preparation method thereof, and aims to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of environment-friendly polyurethane foam comprises the following steps:
(1) mixing faeces Bombycis powder with polyethylene glycol and small molecular alcohol, adding concentrated sulfuric acid as catalyst, reacting at 160 deg.C for 2-4h, adjusting solution to neutrality, and filtering to obtain liquefied faeces Bombycis polyether polyol.
Silkworm excrement is silkworm excrement and contains rich coarse fiber, coarse fat, lignin and other polyhydroxy biomass, and the liquefied silkworm excrement polyether polyol prepared through liquefaction can be used for preparing polyurethane foam. Silkworm excrement has wide source, and the polyurethane foam prepared by the bio-based method is degradable and environment-friendly.
(2) Dissolving rutin in formyldimethylamine to form a reaction solution, cooling the reaction solution to-5-5 ℃, slowly adding sodium borohydride for multiple times, heating the reaction solution to room temperature after the sodium borohydride is added, stirring for reaction for 2-4h, concentrating to remove the formyldimethylamine after the reaction is finished, and extracting ethyl acetate for three times to obtain the modified rutin.
Rutin, as a natural flavonoid glycoside, has anti-inflammatory, antibacterial and antioxidant properties, but is poor in water solubility, almost insoluble in chloroform, ether and benzene, slightly soluble in ethanol and ethyl acetate, and capable of enhancing the compatibility with isocyanate by reducing the ketone group part of rutin into alcoholic hydroxyl through sodium borohydride, and is beneficial to uniform dispersion of rutin in polyurethane foam.
(3) Putting nano graphene oxide into deionized water, adding ammonia water to adjust the pH value to 11.5-12.5, stirring, introducing nitrogen, adding modified rutin and lanthanum chloride, heating to 90-110 ℃, keeping the temperature for 12-16h, and dialyzing and separating to obtain the modified graphene.
The phenolic hydroxyl group of the modified rutin has strong reducibility, and the reduced graphene oxide can be prepared from the graphene oxide, so that the graphene oxide can be uniformly distributed in the polyurethane foam. And the strong coordination oxygen atom in the unreduced carbonyl group in the modified rutin can generate a complex with the rare earth lanthanum ion.
(4) Uniformly mixing liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water, adding modified graphene, uniformly stirring, adding isocyanate, uniformly stirring, pouring into a mould, heating to 50-70 ℃, foaming, curing for 1-2 hours, and thus obtaining the environment-friendly polyurethane foam.
The liquefied silkworm excrement polyether polyol contains rich hydroxyl, the liquefied silkworm excrement polyether polyol is used as polyol, the modified graphene is doped, and the polyurethane foam is prepared by reacting with isocyanate.
Because the graphene oxide is reduced by the modified rutin and simultaneously absorbs the rare earth lanthanum element, the sheet layer of the graphene is thickened, the thermal stability of the sheet layer is enhanced, and the reduced graphene oxide with better thermal stability can form a protective carbon layer on the surface of the environment-friendly polyurethane foam in the combustion process, so that the flame retardant property of the environment-friendly polyurethane foam is enhanced; and the rare earth lanthanum ions on the surface of the graphene and the strong coordination oxygen atoms in the modified rutin molecules generate a complex, so that the antibacterial property of the environment-friendly polyurethane foam is further enhanced.
In the step (1), the small molecular alcohol is ethylene glycol or glycerol.
In the step (4), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
The environment-friendly polyurethane foam comprises, by mass, 160 parts of liquefied silkworm excrement polyether polyol, 180 parts of isocyanate, 5-7 parts of modified graphene, 3-6 parts of a foaming agent, 2-4 parts of a catalyst, 5-7 parts of a foam stabilizer, 2-5 parts of an inorganic flame retardant and 7-10 parts of distilled water.
The raw materials of the modified graphene comprise, by mass, 5-7 parts of modified rutin, 1-2 parts of lanthanum chloride and 1-2 parts of nano graphene oxide.
The modified rutin comprises, by mass, 20-30 parts of rutin, 80-150 parts of formyldimethylamine and 2-4 parts of sodium borohydride.
The raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 8-10 parts of silkworm excrement powder, 2-4 parts of polyethylene glycol, 1-2 parts of small molecular alcohol and 0.5-2 parts of concentrated sulfuric acid.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the liquefied silkworm excrement polyether polyol is used as polyol, the modified graphene is doped, and the polyurethane foam is prepared by reacting with isocyanate, the degradable characteristic of the polyurethane foam improves the environmental protection property of the polyurethane foam, and the rutin component in the modified graphene is doped, so that the polyurethane foam has antibacterial property and oxidation resistance and can absorb ultraviolet rays. The reduced graphene oxide with good thermal stability enhances the flame retardant property of the environment-friendly polyurethane foam; and the rare earth lanthanum element on the surface of the graphene and the strong coordination oxygen atom in the modified rutin molecule form a complex, so that the antibacterial property of the environment-friendly polyurethane foam is further enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
(1) Mixing faeces Bombycis powder with polyethylene glycol and ethylene glycol, adding concentrated sulfuric acid as catalyst, reacting at 130 deg.C for 4 hr, adjusting solution to neutrality, and filtering to obtain liquefied faeces Bombycis polyether polyol.
(2) Dissolving rutin in formyldimethylamine to form a reaction solution, cooling the reaction solution to-5 ℃, slowly adding sodium borohydride for multiple times, heating the reaction solution to room temperature after the sodium borohydride is added, stirring for reaction for 2 hours, concentrating to remove the formyldimethylamine after the reaction is finished, and extracting with ethyl acetate for three times to obtain the modified rutin.
(3) Putting nano graphene oxide into deionized water, adding ammonia water to adjust the pH value to 11.5, stirring, introducing nitrogen, adding modified rutin and lanthanum chloride, heating to 90 ℃, keeping the temperature for 16 hours, and dialyzing and separating to obtain the modified graphene.
(4) 100g of liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water are uniformly mixed, modified graphene is added and uniformly stirred, isocyanate is added, the mixture is uniformly stirred and poured into a mold, the mixture is heated to 50 ℃ for foaming, and curing is carried out for 2 hours, so that the environment-friendly polyurethane foam is prepared.
In the step (4), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
The environment-friendly polyurethane foam comprises the following raw materials, by mass, 120 parts of liquefied silkworm excrement polyether polyol, 120 parts of isocyanate, 5 parts of modified graphene, 3 parts of a foaming agent, 2 parts of a catalyst, 5 parts of a foam stabilizer, 2 parts of an inorganic flame retardant and 7 parts of distilled water.
The raw materials of the modified graphene comprise, by mass, 5 parts of modified rutin, 1 part of lanthanum chloride and 1 part of nano graphene oxide.
The modified rutin comprises the following raw materials, by mass, 20 parts of rutin, 80 parts of formyldimethylamine and 2 parts of sodium borohydride.
The raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 8 parts of silkworm excrement powder, 2 parts of polyethylene glycol, 1 part of ethylene glycol and 0.5 part of concentrated sulfuric acid.
Example 2
(1) Mixing faeces Bombycis powder with polyethylene glycol and ethylene glycol, adding concentrated sulfuric acid as catalyst, reacting at 145 deg.C for 3 hr, adjusting solution to neutrality, and filtering to obtain liquefied faeces Bombycis polyether polyol.
(2) Dissolving rutin in formyldimethylamine to form a reaction solution, cooling the reaction solution to 0 ℃, slowly adding sodium borohydride for multiple times, heating the reaction solution to room temperature after the sodium borohydride is added, stirring for reaction for 3 hours, concentrating to remove the formyldimethylamine after the reaction is finished, and extracting with ethyl acetate for three times to obtain the modified rutin.
(3) Putting nano graphene oxide into deionized water, adding ammonia water to adjust the pH value to 12, stirring, introducing nitrogen, adding modified rutin and lanthanum chloride, heating to 100 ℃, preserving heat for 14 hours, and dialyzing and separating to obtain the modified graphene.
(4) Uniformly mixing liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water, adding modified graphene, uniformly stirring, adding isocyanate, uniformly stirring, pouring into a mould, heating to 60 ℃ for foaming, and curing for 1.5 hours to obtain the environment-friendly polyurethane foam.
In the step (4), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
The environment-friendly polyurethane foam comprises the following raw materials, by mass, 140 parts of liquefied silkworm excrement polyether polyol, 150 parts of isocyanate, 6 parts of modified graphene, 5 parts of a foaming agent, 3 parts of a catalyst, 6 parts of a foam stabilizer, 3 parts of an inorganic flame retardant and 9 parts of distilled water.
The raw materials of the modified graphene comprise, by mass, 6 parts of modified rutin, 1.5 parts of lanthanum chloride and 1.5 parts of nano graphene oxide.
The modified rutin comprises the following raw materials, by mass, 25 parts of rutin, 120 parts of formyldimethylamine and 3 parts of sodium borohydride.
The raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 9 parts of silkworm excrement powder, 3 parts of polyethylene glycol, 1.5 parts of ethylene glycol and 1 part of concentrated sulfuric acid.
Example 3
(1) Mixing faeces Bombycis powder with polyethylene glycol and small molecular alcohol, adding concentrated sulfuric acid as catalyst, reacting at 160 deg.C for 4 hr, adjusting solution to neutrality, and filtering to obtain liquefied faeces Bombycis polyether polyol.
(2) Dissolving rutin in formyldimethylamine to form a reaction solution, cooling the reaction solution to 5 ℃, slowly adding sodium borohydride for multiple times, heating the reaction solution to room temperature after the sodium borohydride is added, stirring for reaction for 2 hours, concentrating to remove the formyldimethylamine after the reaction is finished, and extracting with ethyl acetate for three times to obtain the modified rutin.
(3) Putting nano graphene oxide into deionized water, adding ammonia water to adjust the pH value to 12, stirring, introducing nitrogen, adding modified rutin and lanthanum chloride, heating to 110 ℃, preserving heat for 16 hours, and dialyzing and separating to obtain the modified graphene.
(4) Uniformly mixing liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water, adding modified graphene, uniformly stirring, adding isocyanate, uniformly stirring, pouring into a mold, heating to 70 ℃, foaming, and curing for 2 hours to obtain the environment-friendly polyurethane foam.
In the step (4), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
The environment-friendly polyurethane foam comprises the following raw materials, by mass, 160 parts of liquefied silkworm excrement polyether polyol, 120 parts of isocyanate, 7 parts of modified graphene, 36 parts of a foaming agent, 4 parts of a catalyst, 5 parts of a foam stabilizer, 5 parts of an inorganic flame retardant and 7 parts of distilled water.
The raw materials of the modified graphene comprise, by mass, 5 parts of modified rutin, 2 parts of lanthanum chloride and 2 parts of nano graphene oxide.
The modified rutin comprises the following raw materials, by mass, 30 parts of rutin, 80 parts of formyldimethylamine and 4 parts of sodium borohydride.
The raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 10 parts of silkworm excrement powder, 2 parts of polyethylene glycol, 1 part of ethylene glycol and 1 part of concentrated sulfuric acid.
Example 4
(1) Mixing faeces Bombycis powder with polyethylene glycol and ethylene glycol, adding concentrated sulfuric acid as catalyst, reacting at 160 deg.C for 2 hr, adjusting solution to neutrality, and filtering to obtain liquefied faeces Bombycis polyether polyol.
(2) Dissolving rutin in formyldimethylamine to form a reaction solution, cooling the reaction solution to 5 ℃, slowly adding sodium borohydride for multiple times, heating the reaction solution to room temperature after the sodium borohydride is added, stirring for reaction for 4 hours, concentrating to remove the formyldimethylamine after the reaction is finished, and extracting with ethyl acetate for three times to obtain the modified rutin.
(3) Putting the nano graphene oxide into deionized water, adding ammonia water to adjust the pH value to 12.5, stirring, introducing nitrogen, adding modified rutin and lanthanum chloride, heating to 110 ℃, keeping the temperature for 12 hours, and dialyzing and separating to obtain the modified graphene.
(4) 100g of liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water are uniformly mixed, modified graphene is added and uniformly stirred, isocyanate is added, the mixture is uniformly stirred and poured into a mold, the mixture is heated to 70 ℃ for foaming, and curing is carried out for 1 hour, so as to obtain the environment-friendly polyurethane foam.
In the step (4), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
The environment-friendly polyurethane foam comprises the following raw materials, by mass, 160 parts of liquefied silkworm excrement polyether polyol, 180 parts of isocyanate, 7 parts of modified graphene, 6 parts of a foaming agent, 4 parts of a catalyst, 7 parts of a foam stabilizer, 5 parts of an inorganic flame retardant and 10 parts of distilled water.
The raw materials of the modified graphene comprise, by mass, 7 parts of modified rutin, 2 parts of lanthanum chloride and 2 parts of nano graphene oxide.
The modified rutin comprises the following raw materials, by mass, 30 parts of rutin, 150 parts of formyldimethylamine and 4 parts of sodium borohydride.
The raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 10 parts of silkworm excrement powder, 4 parts of polyethylene glycol, 2 parts of ethylene glycol and 2 parts of concentrated sulfuric acid.
Comparative example 1
Comparative example 1 is compared with example 2, comparative example 1 does not carry out reduction modification on rutin, and other conditions are consistent with example 2.
(1) Mixing faeces Bombycis powder with polyethylene glycol and ethylene glycol, adding concentrated sulfuric acid as catalyst, reacting at 145 deg.C for 3 hr, adjusting solution to neutrality, and filtering to obtain liquefied faeces Bombycis polyether polyol.
(2) Putting the nano graphene oxide into deionized water, adding ammonia water to adjust the pH value to 12, stirring, introducing nitrogen, adding rutin and lanthanum chloride, heating to 100 ℃, preserving heat for 14 hours, and dialyzing and separating to obtain the modified graphene.
(3) Uniformly mixing liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water, adding modified graphene, uniformly stirring, adding isocyanate, uniformly stirring, pouring into a mould, heating to 60 ℃ for foaming, and curing for 1.5 hours to obtain the environment-friendly polyurethane foam.
In the step (3), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
The environment-friendly polyurethane foam comprises the following raw materials, by mass, 140 parts of liquefied silkworm excrement polyether polyol, 150 parts of isocyanate, 6 parts of modified graphene, 5 parts of a foaming agent, 3 parts of a catalyst, 6 parts of a foam stabilizer, 3 parts of an inorganic flame retardant and 9 parts of distilled water.
The raw materials of the modified graphene comprise, by mass, 6 parts of rutin, 1.5 parts of lanthanum chloride and 1.5 parts of nano graphene oxide.
The raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 9 parts of silkworm excrement powder, 3 parts of polyethylene glycol, 1.5 parts of ethylene glycol and 1 part of concentrated sulfuric acid.
Comparative example 2
Comparative example 2 compares with example 2, and comparative example 2 does not add lanthanum chloride to the modified graphene, and the other conditions are consistent with example 2.
(1) Mixing faeces Bombycis powder with polyethylene glycol and ethylene glycol, adding concentrated sulfuric acid as catalyst, reacting at 145 deg.C for 3 hr, adjusting solution to neutrality, and filtering to obtain liquefied faeces Bombycis polyether polyol.
(2) Dissolving rutin in formyldimethylamine to form a reaction solution, cooling the reaction solution to 0 ℃, slowly adding sodium borohydride for multiple times, heating the reaction solution to room temperature after the sodium borohydride is added, stirring for reaction for 3 hours, concentrating to remove the formyldimethylamine after the reaction is finished, and extracting with ethyl acetate for three times to obtain the modified rutin.
(3) Putting the nano graphene oxide into deionized water, adding ammonia water to adjust the pH value to 12, stirring, introducing nitrogen, adding the modified rutin, heating to 100 ℃, keeping the temperature for 14 hours, and dialyzing and separating to obtain the modified graphene.
(4) Uniformly mixing liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water, adding modified graphene, uniformly stirring, adding isocyanate, uniformly stirring, pouring into a mould, heating to 60 ℃ for foaming, and curing for 1.5 hours to obtain the environment-friendly polyurethane foam.
In the step (4), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
The environment-friendly polyurethane foam comprises the following raw materials, by mass, 140 parts of liquefied silkworm excrement polyether polyol, 150 parts of isocyanate, 6 parts of modified graphene, 5 parts of a foaming agent, 3 parts of a catalyst, 6 parts of a foam stabilizer, 3 parts of an inorganic flame retardant and 9 parts of distilled water.
The raw materials of the modified graphene comprise, by mass, 6 parts of modified rutin and 1.5 parts of nano graphene oxide.
The modified rutin comprises the following raw materials, by mass, 25 parts of rutin, 120 parts of formyldimethylamine and 3 parts of sodium borohydride.
The raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 9 parts of silkworm excrement powder, 3 parts of polyethylene glycol, 1.5 parts of ethylene glycol and 1 part of concentrated sulfuric acid.
Comparative example 3
Comparative example 3 is compared with example 2, and comparative example 3 replaces the modified graphene with the lanthanum oxide-modified rutin, and the other conditions are the same as those in example 2.
(1) Mixing faeces Bombycis powder with polyethylene glycol and ethylene glycol, adding concentrated sulfuric acid as catalyst, reacting at 145 deg.C for 3 hr, adjusting solution to neutrality, and filtering to obtain liquefied faeces Bombycis polyether polyol.
(2) Dissolving rutin in formyldimethylamine to form a reaction solution, cooling the reaction solution to 0 ℃, slowly adding sodium borohydride for multiple times, heating the reaction solution to room temperature after the sodium borohydride is added, stirring for reaction for 3 hours, concentrating to remove the formyldimethylamine after the reaction is finished, and extracting with ethyl acetate for three times to obtain the modified rutin.
(3) And (2) putting the modified rutin into deionized water, adding ammonia water to adjust the pH value to 12, stirring, introducing nitrogen, adding lanthanum chloride, heating to 90 ℃, keeping the temperature for 16 hours, and dialyzing and separating to obtain the rare earth lanthanum-modified rutin.
(4) Uniformly mixing liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water, adding lanthanum oxide-modified rutin, uniformly stirring, adding isocyanate, uniformly stirring, pouring into a mold, heating to 60 ℃ for foaming, and curing for 1.5 hours to obtain the environment-friendly polyurethane foam.
In the step (4), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
The environment-friendly polyurethane foam comprises the following raw materials, by mass, 140 parts of liquefied silkworm excrement polyether polyol, 150 parts of isocyanate, 6 parts of modified graphene, 5 parts of a foaming agent, 3 parts of a catalyst, 6 parts of a foam stabilizer, 3 parts of an inorganic flame retardant and 9 parts of distilled water.
The raw materials of the modified graphene comprise, by mass, 6 parts of modified rutin and 1.5 parts of nano graphene oxide.
The modified rutin comprises the following raw materials, by mass, 25 parts of rutin, 120 parts of formyldimethylamine and 3 parts of sodium borohydride.
The raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 9 parts of silkworm excrement powder, 3 parts of polyethylene glycol, 1.5 parts of ethylene glycol and 1 part of concentrated sulfuric acid.
Experiment 1
The environmentally friendly polyurethane foams prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to a performance test, and (1) thermal conductivity was measured. The thermal conductivity of the environmentally friendly polyurethane foam was measured using a heat flow meter from Netzsch company, Selb Germany. (2) A limiting oxygen index. The limiting oxygen index was determined using a limiting oxygen index meter. (3) And (4) bacteriostasis rate. And testing the antibacterial rates of escherichia coli and staphylococcus aureus on the surface of the environment-friendly polyurethane foam by using a flat plate counting method.
The test results are shown in the following table:
TABLE 1
As can be seen from Table 1, in comparison with example 2, in comparative example 1, rutin is not reduced and modified in comparative example 1, and other conditions are consistent with example 2, and the antibacterial rates of Escherichia coli and Staphylococcus aureus in comparative example 1 and example 2 are respectively reduced by 2.4% and 1.9%, while the limiting oxygen index and the thermal conductivity are basically unchanged, which indicates that rutin is not reduced, so that the dispersibility in the environment-friendly polyurethane foam is poor, and the antibacterial activity is poor.
Compared with example 2, in comparative example 2, lanthanum chloride is not added into the modified graphene, and other conditions are consistent with example 2, and the heat conductivity coefficient of comparative example 2 is basically unchanged compared with example 2, but the limit oxygen is reduced, which indicates that the graphene oxide is not modified, the dispersion is not uniform, the flame resistance is not good, and the rare earth lanthanum is reduced in the system, so that the bacteriostatic property of the polyurethane foam is reduced.
Compared with the example 2, in the comparative example 3, the rare earth lanthanum-modified rutin is used for replacing the modified graphene, other conditions are consistent with those of the example 2, and the limiting oxygen index of the comparative example 3 is reduced, so that the resistance of the material can be enhanced by the graphene.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the environment-friendly polyurethane foam is characterized by comprising the following steps:
(1) uniformly mixing silkworm excrement powder with polyethylene glycol and micromolecular alcohol, adding concentrated sulfuric acid, reacting at the temperature of 130-160 ℃ for 2-4h, adjusting the solution to be neutral after the reaction is finished, and filtering and retaining the filtrate to obtain liquefied silkworm excrement polyether polyol;
(2) dissolving rutin in formyldimethylamine, cooling to-5-5 ℃, slowly adding sodium borohydride, stirring at room temperature for reaction for 2-4h, and concentrating to remove the formyldimethylamine after the reaction is finished to obtain modified rutin;
(3) putting nano graphene oxide into deionized water, adding ammonia water to adjust the pH value, stirring, introducing nitrogen, adding modified rutin and lanthanum chloride, heating to 90-110 ℃, preserving heat for 12-16h, and dialyzing and separating to obtain modified graphene;
(4) uniformly mixing liquefied silkworm excrement polyether polyol, a foaming agent, a catalyst, a foam stabilizer, an inorganic flame retardant and distilled water, adding modified graphene, uniformly stirring, adding isocyanate, uniformly stirring, pouring into a mould, foaming and curing to obtain the environment-friendly polyurethane foam.
2. The method for preparing an environmentally friendly polyurethane foam according to claim 1, wherein: in the step (1), the small molecular alcohol is ethylene glycol or glycerol.
3. The method for preparing an environmentally friendly polyurethane foam according to claim 1, wherein: in the step (3), the pH value of the solution is adjusted to 11.5-12.5.
4. The method for preparing an environmentally friendly polyurethane foam according to claim 1, wherein: in the step (4), the foaming temperature is 50-70 ℃, and the curing time is 1-2 h.
5. The method for preparing an environmentally friendly polyurethane foam according to claim 1, wherein: in the step (4), the isocyanate is diphenylmethane diisocyanate, the foaming agent is pentane, the catalyst is hydroxyethyl ethylenediamine, the foam stabilizer is silicone oil, and the inorganic flame retardant is monoammonium phosphate.
6. The method for preparing an environmentally friendly polyurethane foam according to claim 1, wherein: the environment-friendly polyurethane foam comprises, by mass, 160 parts of liquefied silkworm excrement polyether polyol, 180 parts of isocyanate, 5-7 parts of modified graphene, 3-6 parts of a foaming agent, 2-4 parts of a catalyst, 5-7 parts of a foam stabilizer, 2-5 parts of an inorganic flame retardant and 7-10 parts of distilled water.
7. The method for preparing an environmentally friendly polyurethane foam according to claim 6, wherein: the raw materials of the modified graphene comprise, by mass, 5-7 parts of modified rutin, 1-2 parts of lanthanum chloride and 1-2 parts of nano graphene oxide.
8. The method for preparing an environmentally friendly polyurethane foam according to claim 7, wherein: the modified rutin comprises, by mass, 20-30 parts of rutin, 80-150 parts of formyldimethylamine and 2-4 parts of sodium borohydride.
9. The method for preparing an environmentally friendly polyurethane foam according to claim 6, wherein: the raw materials of the liquefied silkworm excrement polyether polyol comprise, by mass, 8-10 parts of silkworm excrement powder, 2-4 parts of polyethylene glycol, 1-2 parts of small molecular alcohol and 0.5-2 parts of concentrated sulfuric acid.
10. An eco-friendly polyurethane foam prepared by the method of preparing an eco-friendly polyurethane foam according to any one of claims 1 to 9.
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