CN111518258A - Preparation method of composite vegetable oil-based polyurethane foam material - Google Patents
Preparation method of composite vegetable oil-based polyurethane foam material Download PDFInfo
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- C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention relates to a preparation method of a composite vegetable oil-based polyurethane foam material, belonging to the technical field of polyurethane foam materials. According to the invention, sesame oil and epoxidized soybean oil are used as raw materials to prepare vegetable oil polyol, and hydrogenated castor oil is added to prepare a composite vegetable oil-based polyurethane foam material, and meanwhile, diphenylmethane diisocyanate is added as a raw material, so that the reaction activity of the diphenylmethane diisocyanate is high, and the dosage of a catalyst can be reduced, thereby reducing the content of harmful volatile organic matters in the polyurethane foam, improving the safety of the polyurethane foam, and the diphenylmethane diisocyanate has low steam pressure and is convenient to store, transport and produce, the safety of the production process is improved, the risk coefficient of the polyurethane foam in the production process is reduced, and the polyurethane foam prepared by using the diphenylmethane diisocyanate as a raw material has the advantages of safe process technology and good environmental protection performance.
Description
Technical Field
The invention relates to a preparation method of a composite vegetable oil-based polyurethane foam material, belonging to the technical field of polyurethane foam materials.
Background
Polyurethanes (PU), known collectively as polyurethanes, are polymers having overlapping urethane groups on the polymer backbone, and are generally prepared by the polymerization of di-or polyisocyanates with di-or polyols. Because the number of functional groups of the two main raw materials can be adjusted, PU with different molecular structures can be obtained: when the isocyanate and the polyol are both difunctional, the prepared PU is a high polymer with a linear structure; when one or two of the raw materials, all or only part of the raw materials have more than two active functional groups, the PU prepared is a high polymer with a three-dimensional structure. The molecular structure of PU determines its performance, so PU is widely used in paint, plastic, adhesive, elastomer, etc. In recent years, the use of PU in these fields has been rapidly developed, and particularly, polyurethane foams, aqueous polyurethane coatings, and polyurethane elastomers have been rapidly developed.
Foam is one of the main products of PU materials. The polyurethane foam has the characteristics of porosity, low density, high strength and the like, so that the polyurethane foam has good physical and mechanical properties and low thermal conductivity, and is widely applied to heat-insulating and cold-insulating materials for buildings. The density and mechanical strength of the polyurethane foam material can be adjusted by changing the types of raw materials and reaction formulas so as to meet the requirements of the development of human society. In addition, because the polyurethane foam material is processed into a finished product by directly reacting the raw materials, a complex intermediate process is omitted, convenience is provided for the rapid development of the polyurethane foam material, and the polyurethane foam material becomes one of important supporting materials particularly in the industries of furniture, transportation, building heat preservation and cold insulation and the like. With the development of polyurethane foam materials, the polyurethane foam materials are gradually developed in the fields of agriculture, three-waste treatment, energy conservation, national defense and military and the like.
The polyol is one of two main raw materials for synthesizing the polyurethane foam material, and the using amount of the polyol is about one half of the total material amount. The polyol is prepared by taking petroleum or coal as a raw material through a complex process, China is a poor oil country, most of petroleum resources depend on import, the environment of China has been under great pressure due to the excessive use of fossil energy in recent years, the PU industry is more environment-friendly and sustainable in order to reduce the consumption of fossil resources, the development of bio-based raw materials for the production of polyurethane becomes very important, and the application of biomass in the PU industry gradually becomes a research hotspot.
Currently, the research direction of bio-based polyurethane foams is mainly to use bio-based polyols to partially or completely replace petroleum-based polyols. In the field of polyurethane foam materials, researches on utilization of biomass mainly focus on starch, vegetable oil, lignin, wood, crop waste and the like, and two modes are mainly adopted: (1) preparing liquefied polyol with a plurality of hydroxyl groups on a molecular chain segment from biomass through a series of reactions, and using the liquefied polyol as a polyol raw material for subsequent production of polyurethane foam materials; (2) the biomass is crushed into powder and used as a modified filler of the polyurethane foam material.
Compared with petroleum-based polyol, the vegetable oil-based polyol has the following advantages: (1) the vegetable oil has large amount and stable price. In recent years, the yield of various oil crops in the world is continuously increased, the vegetable oil reserves are very rich, the price is stable, and although the influence of the climate conditions is slightly vibrated, the influence is not obvious under the global economic conditions. (2) The preparation process of the vegetable oil-based polyol is simple. The vegetable oil can obtain the product meeting the conditions only through the early epoxidation reaction and the later hydroxylation reaction. (3) The production process of the vegetable oil-based polyol is more environment-friendly. The energy consumed in the production process of the vegetable oil-based polyol is low, and the carbon emission is greatly reduced. The preliminary environmental analysis is carried out on the production process, and the comparison with petroleum-based and coal-based polyols shows that the total energy consumption in the process of producing the vegetable oil-based polyol is reduced by 23 percent, the consumption of non-renewable resources is reduced by 61 percent, the output of greenhouse gas is reduced by 36 percent, and the method has very obvious environmental and economic benefits.
The lignin is an amorphous aromatic alcohol high polymer with a molecular structure containing abundant hydroxyl groups, is abundant in woody plants, reaches 25 percent, and is arranged in the second place of the reserves of natural organic matters. The lignin contains abundant hydroxyl, so that the lignin can be used for reacting with isocyanate to prepare a PU material, and the sustainability of PU raw material sources can be realized, thereby attracting a plurality of scientific researchers to research the high-efficiency utilization of the lignin in the PU industry.
Wood contains abundant cellulose, hemicellulose and lignin, and all the components contain abundant hydroxyl groups, if a large amount of waste generated in the wood processing process can be directly converted into polyhydroxy alcohol through catalysis, the application of the polyhydroxy alcohol in the production of polyurethane foam can greatly improve the added value of the polyhydroxy alcohol, and the sustainability of the polyol for PU is realized. The preparation of the bio-based polyol by using the wood waste as the raw material through catalytic conversion mainly comprises the following steps: taking polyhydroxy alcohol as a liquefying reagent and acid or alkali as a catalyst, and carrying out liquefying treatment at normal pressure and high temperature. According to the previous reports, polyhydric alcohols mainly comprise polyhydric alcohols such as polyethylene glycol, ethylene glycol and glycerol, acid-base catalysts mainly comprise concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid and sodium hydroxide, and high-temperature heat sources mainly comprise two methods of conventional oil bath heating and microwave radiation heating.
At present, due to the continuous decrease of fossil raw materials and the negative effect thereof on the environment, the development of biological products such as biochemicals, biofuels, biomaterials and the like has become a current development trend. The agricultural waste has the advantages of unique chemical structure, low cost, high yield, reproducibility and the like, and can be used as an environment-friendly and economic raw material to produce biochemicals, biofuels, biomaterials and the like. In addition, the utilization of the agricultural wastes can not compete with food resources, can realize the energy regeneration of the agricultural wastes, produce various sustainable products and materials, can get rid of the dependence on fossil fuels, and effectively relieve the energy crisis faced by human beings.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problem that the existing polyurethane foam material is easy to burn, the preparation method of the composite vegetable oil-based polyurethane foam material is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) adding protein powder and sucrose into deionized water, and stirring at the normal temperature at the rotating speed of 180-200 r/min for 10-12 min to obtain a foaming agent;
(2) adding sesame oil polyalcohol and epoxy soybean oil polyalcohol into hydrogenated castor oil, and stirring at the rotating speed of 200-240 r/min for 20-25 min at normal temperature to obtain mixed vegetable oil polyalcohol;
(3) adding a foaming agent, dimethyl polysiloxane, ethylenediamine and stannous octoate into the mixed vegetable oil polyol, placing the mixture into a high-speed stirrer, and stirring and mixing the mixture at the rotating speed of 3000-3500 r/min for 20-30 min at normal temperature to obtain a mixed foaming system;
(4) slowly adding the diphenylmethane diisocyanate into the mixed foaming system, placing the mixed foaming system in a high-speed stirrer, and stirring for 6-8 s at the constant temperature of 24-28 ℃ at the rotating speed of 3500-4000 r/min to obtain a mixture;
(5) and quickly pouring the mixture into a mold, standing for 1-2 hours at normal temperature, and demolding to obtain the composite vegetable oil-based polyurethane foam material.
The sesame oil polyol, the epoxidized soybean oil polyol, the hydrogenated castor oil, the diphenylmethane diisocyanate, the protein powder, the sucrose, the dimethylpolysiloxane, the ethylenediamine, the stannous octoate, and the deionized water are 20-30 parts by weight of the sesame oil polyol, 20-30 parts by weight of the epoxidized soybean oil polyol, 10-15 parts by weight of the hydrogenated castor oil, 40-60 parts by weight of the diphenylmethane diisocyanate, 2-3 parts by weight of the protein powder, 1.0-1.5 parts by weight of the sucrose, 1.0-1.5 parts by weight of the dimethylpolysiloxane, 0.2-0.3 part by weight of the ethylenediamine, 0.2-0.3 part by weight of the stannous octoate and 8-12 parts by weight of the deionized water.
And (4) adding the diphenylmethane diisocyanate at a rate of 60-80 mL/min.
The specification of the die in the step (5) is 100cm multiplied by 60 cm.
The preparation method of the epoxidized soybean oil polyol in the step (2) comprises the following specific steps:
(1) adding sulfuric acid, zirconium oxide powder and deionized water into anhydrous methanol, and stirring at the rotating speed of 200-240 r/min for 10-20 min at normal temperature to obtain a methanol mixed solution;
(2) slowly adding epoxidized soybean oil into the methanol mixed solution, stirring and reacting for 40-60 min at the rotating speed of 300-350 r/min under the water bath condition of 50-60 ℃, adjusting the pH value to 7, filtering, and taking filtrate to obtain mixed reaction liquid;
(3) and adding trichloromethane into the reaction mixed liquid, standing for 1-2 h at normal temperature for layering, taking an oil layer, and distilling under reduced pressure at 70-80 ℃ under the condition of 300-400 KPa to obtain the epoxidized soybean oil polyol.
The epoxidized soybean oil comprises, by weight, 40-60 parts of epoxidized soybean oil, 60-90 parts of anhydrous methanol, 2-3 parts of sulfuric acid with the mass fraction of 10%, 4-6 parts of zirconia powder, 20-30 parts of deionized water and 60-90 parts of trichloromethane.
The dripping speed of the epoxidized soybean oil in the step (2) is 10-20 mL/min, and a sodium carbonate solution with the mass fraction of 1% is adopted for pH adjustment.
The preparation method of the sesame oil polyol in the step (2) comprises the following specific steps:
(1) adding maleic anhydride into sesame oil, introducing nitrogen at the rate of 40-60 mL/min for protection, and stirring at the rotating speed of 240-280 r/min at the temperature of 200-220 ℃ for reaction for 2-4 hours to obtain maleic anhydride modified sesame oil;
(2) adding glycerol and sodium hydroxide into the maleic anhydride modified sesame oil, introducing nitrogen at the rate of 60-80 mL/min for protection, and stirring at the rotating speed of 300-340 r/min at the temperature of 220-240 ℃ for reaction for 4-6 hours to obtain a reaction solution;
(3) adding deionized water into the reaction solution, adjusting the pH value to 7, adding anhydrous calcium chloride, filtering, taking the filtrate, and carrying out reduced pressure distillation at 160-180 ℃ under the condition of 400-600 KPa to obtain the sesame oil polyalcohol.
The sesame oil, the maleic anhydride, the glycerol, the sodium hydroxide, the anhydrous calcium chloride and the deionized water are 40-60 parts by weight of sesame oil, 24-36 parts by weight of maleic anhydride, 32-48 parts by weight of glycerol, 8-12 parts by weight of sodium hydroxide, 20-30 parts by weight of anhydrous calcium chloride and 8-12 parts by weight of deionized water.
Hydrochloric acid with the mass fraction of 1% is adopted for pH adjustment in the step (3).
Compared with other methods, the method has the beneficial technical effects that:
(1) the invention takes sesame oil and epoxidized soybean oil as raw materials to prepare vegetable oil polyol, and then hydrogenated castor oil is added to prepare the composite vegetable oil-based polyurethane foam material, the vegetable oil is a renewable energy source, the supply amount is not exhausted, and the vegetable oil is non-toxic, has the advantages of good biodegradability, reproducibility, low volatility and the like, the sesame oil, the epoxidized soybean oil and the hydrogenated castor oil all belong to vegetable oil, the sesame oil and the epoxidized soybean oil all contain unsaturated double bonds, and can react with micromolecule polyol under certain conditions to generate the vegetable oil polyol with a certain hydroxyl value, the vegetable oil polyol prepared by taking the sesame oil and the epoxidized soybean oil as raw materials can replace petroleum-based polyol, compared with the traditional petroleum-based polyol, the vegetable oil is taken as the raw material to prepare the polyurethane foam material, so that the utilization of petroleum resources can be reduced, the use of non-renewable resources and the emission of greenhouse gases are reduced, the development and utilization of renewable new energy sources are improved, the energy structure is further updated, a new substitute can be found for a polyol raw material for synthesizing a polyurethane foam material, the production cost is reduced, the nontoxic and safe production of the polyurethane foam is realized, hydrogenated castor oil is a compound containing a plurality of hydroxyl groups and can be directly used for producing the polyurethane material, the hydrogenated castor oil has a long-chain fat base, the polyurethane material prepared by adding the hydrogenated castor oil has good water resistance, flexibility, low-temperature performance and electric insulation, the polyurethane foam material produced by taking vegetable oil polyol as a raw material has good degradability, toxic smoke is not generated during combustion, and the safety and the recyclability of the polyurethane foam are improved;
(2) the invention takes diphenylmethane diisocyanate as raw material to prepare the composite vegetable oil-based polyurethane foam material, the diphenylmethane diisocyanate has high reaction activity, and can reduce the dosage of catalyst, thereby reducing the content of harmful volatile organic compounds of the polyurethane foam, improving the safety of the polyurethane foam, and the diphenylmethane diisocyanate has low steam pressure, is convenient in storage, transportation and production processes, improves the safety of the production process, and reduces the risk coefficient of the polyurethane foam in the production process.
Detailed Description
Weighing 40-60 parts of sesame oil, 24-36 parts of maleic anhydride, 32-48 parts of glycerol, 8-12 parts of sodium hydroxide, 20-30 parts of anhydrous calcium chloride and 8-12 parts of deionized water respectively, adding the maleic anhydride into the sesame oil, introducing nitrogen at the rate of 40-60 mL/min for protection, stirring and reacting at the temperature of 200-220 ℃ at the rotating speed of 240-280 r/min for 2-4 hours to obtain maleic anhydride modified sesame oil, adding the glycerol and the sodium hydroxide into the maleic anhydride modified sesame oil, introducing nitrogen at the rate of 60-80 mL/min for protection, stirring and reacting at the rotating speed of 300-340 r/min at the temperature of 220-240 ℃ for 4-6 hours to obtain a reaction liquid, adding the deionized water into the reaction liquid, dropwise adding hydrochloric acid with the mass concentration of 1% to adjust the pH to 7, adding the anhydrous calcium chloride, filtering, taking filtrate, placing the filtrate at the temperature of 160-180 ℃ and adding the deionized water to the mixture, Distilling under reduced pressure under the condition of 400-600 KPa to obtain sesame oil polyalcohol; then respectively weighing 40-60 parts of epoxidized soybean oil, 60-90 parts of anhydrous methanol, 2-3 parts of sulfuric acid with the mass fraction of 10%, 4-6 parts of zirconia powder, 20-30 parts of deionized water and 60-90 parts of trichloromethane according to parts by weight, adding the sulfuric acid, the zirconia powder and the deionized water into the anhydrous methanol, stirring at the rotating speed of 200-240 r/min for 10-20 min at normal temperature to obtain a methanol mixed solution, slowly adding the epoxidized soybean oil into the methanol mixed solution at the dropping speed of 10-20 mL/min, stirring and reacting at the rotating speed of 300-350 r/min for 40-60 min under the water bath condition of 50-60 ℃, dropping a sodium carbonate solution with the mass fraction of 1% to adjust the pH to 7, filtering to obtain a filtrate, adding the trichloromethane into the reaction mixed solution, standing for 1-2 h at normal temperature for layering, taking an oil layer, distilling under reduced pressure at the temperature of 70-80 ℃ and the pressure of 300-400 a, obtaining epoxidized soybean oil polyol; respectively weighing 20-30 parts by weight of sesame oil polyol, 20-30 parts by weight of epoxy soybean oil polyol, 10-15 parts by weight of hydrogenated castor oil, 40-60 parts by weight of diphenylmethane diisocyanate, 2-3 parts by weight of protein powder, 1.0-1.5 parts by weight of sucrose, 1.0-1.5 parts by weight of dimethylpolysiloxane, 0.2-0.3 part by weight of ethylenediamine, 0.2-0.3 part by weight of stannous octoate and 8-12 parts by weight of deionized water, adding the protein powder and the sucrose into the deionized water, stirring at the normal temperature at the rotating speed of 180-200 r/min for 10-12 min to obtain a foaming agent, adding the sesame oil polyol and the epoxy soybean oil polyol into the hydrogenated castor oil, stirring at the normal temperature at the rotating speed of 200-240 r/min for 20-25 min to obtain mixed vegetable oil polyol, adding the foaming agent, the dimethylpolysiloxane, the ethylenediamine and the stannous octoate into the mixed vegetable oil polyol, placing the mixed vegetable oil polyol into a high-speed stirrer, stirring at the normal temperature at the, and (3) obtaining a mixed foaming system, slowly adding the diphenylmethane diisocyanate into the mixed foaming system at the speed of 60-80 mL/min, placing the mixed foaming system in a high-speed stirrer, stirring for 6-8 s at the constant temperature of 24-28 ℃ at the rotating speed of 3500-4000 r/min to obtain a mixture, quickly pouring the mixture into a mold with the specification of 100cm × 60cm × 60cm, standing for 1-2 h at normal temperature, and demolding to obtain the composite plant oil-based polyurethane foam material.
Example 1
Respectively weighing 40 parts of sesame oil, 24 parts of maleic anhydride, 32 parts of glycerol, 8 parts of sodium hydroxide, 20 parts of anhydrous calcium chloride and 8 parts of deionized water according to parts by weight, adding the maleic anhydride into the sesame oil, introducing nitrogen protection at the rate of 40mL/min, stirring and reacting for 2 hours at the temperature of 200 ℃ at the rotating speed of 240r/min to obtain maleic anhydride modified sesame oil, adding the glycerol and the sodium hydroxide into the maleic anhydride modified sesame oil, introducing nitrogen protection at the rate of 60mL/min, stirring and reacting for 4 hours at the temperature of 220 ℃ at the rotating speed of 300r/min to obtain a reaction solution, adding the deionized water into the reaction solution, dropwise adding hydrochloric acid with the mass concentration of 1% to adjust the pH value to 7, adding the anhydrous calcium chloride, filtering, taking filtrate, and distilling under the conditions of 160 ℃ and 400KPa under reduced pressure to obtain sesame oil polyalcohol; respectively weighing 40 parts of epoxidized soybean oil, 60 parts of anhydrous methanol, 2 parts of sulfuric acid with the mass fraction of 10%, 4 parts of zirconia powder, 20 parts of deionized water and 60 parts of trichloromethane according to parts by weight, adding the sulfuric acid, the zirconia powder and the deionized water into the anhydrous methanol, stirring for 10min at the normal temperature at the rotating speed of 200r/min to obtain a methanol mixed solution, slowly adding the epoxidized soybean oil into the methanol mixed solution at the dropping speed of 10mL/min, stirring and reacting for 40min at the water bath condition of 50 ℃ at the rotating speed of 300r/min, dropping a sodium carbonate solution with the mass fraction of 1% to adjust the pH to 7, filtering, taking a filtrate to obtain a mixed reaction solution, adding the trichloromethane into the reaction mixed solution, standing for 1h at the normal temperature for layering, taking an oil layer, and distilling under the reduced pressure condition of 70 ℃ and 300KPa to obtain an epoxidized soybean oil polyol; respectively weighing 20 parts of sesame oil polyol, 20 parts of epoxy soybean oil polyol, 10 parts of hydrogenated castor oil, 40 parts of diphenylmethane diisocyanate, 2 parts of protein powder, 1.0 part of cane sugar, 1.0 part of dimethylpolysiloxane, 0.2 part of ethylenediamine, 0.2 part of stannous octoate and 8 parts of deionized water, adding the protein powder and the cane sugar into the deionized water, stirring at 180r/min for 10min at normal temperature to obtain a foaming agent, adding the sesame oil polyol and the epoxy soybean oil polyol into the hydrogenated castor oil, stirring at 200r/min at normal temperature for 20min to obtain a mixed vegetable oil polyol, adding the foaming agent, the dimethylpolysiloxane, the ethylenediamine and the stannous octoate into the mixed vegetable oil polyol, placing the mixed vegetable oil polyol into a high-speed stirrer, stirring and mixing at 3000r/min at normal temperature for 20min to obtain a mixed foaming system, slowly adding the diphenylmethane diisocyanate into the mixed foaming system at a speed of 60mL/min, placing in a high-speed stirrer, stirring at constant temperature of 24 deg.C at 3500r/min for 6s to obtain mixture, rapidly pouring the mixture into a mold with specification of 100cm × 60cm × 60cm, standing at normal temperature for 1h, and demolding to obtain the composite plant oil-based polyurethane foam material.
Example 2
Respectively weighing 50 parts of sesame oil, 30 parts of maleic anhydride, 40 parts of glycerol, 10 parts of sodium hydroxide, 25 parts of anhydrous calcium chloride and 10 parts of deionized water according to parts by weight, adding the maleic anhydride into the sesame oil, introducing nitrogen protection at the rate of 50mL/min, stirring and reacting for 3 hours at the condition of 210 ℃ at the rotating speed of 260r/min to obtain maleic anhydride modified sesame oil, adding the glycerol and the sodium hydroxide into the maleic anhydride modified sesame oil, introducing nitrogen protection at the rate of 70mL/min, stirring and reacting for 5 hours at the condition of 230 ℃ at the rotating speed of 320/min to obtain a reaction liquid, adding the deionized water into the reaction liquid, dropwise adding hydrochloric acid with the mass concentration of 1% to adjust the pH to 7, adding the anhydrous calcium chloride, filtering, taking filtrate, and carrying out reduced pressure distillation at the condition of 170 ℃ and 500KPa to obtain sesame oil polyalcohol; respectively weighing 50 parts of epoxidized soybean oil, 75 parts of anhydrous methanol, 2 parts of sulfuric acid with the mass fraction of 10%, 5 parts of zirconium oxide powder, 25 parts of deionized water and 75 parts of trichloromethane according to parts by weight, adding the sulfuric acid, the zirconium oxide powder and the deionized water into the anhydrous methanol, stirring for 15min at the normal temperature at the rotating speed of 220r/min to obtain a methanol mixed solution, slowly adding the epoxidized soybean oil into the methanol mixed solution at the dropping speed of 15mL/min, stirring and reacting for 50min at the water bath condition of 55 ℃ at the rotating speed of 325r/min, dropping a sodium carbonate solution with the mass fraction of 1% to adjust the pH to 7, filtering, taking a filtrate to obtain a mixed reaction solution, adding the trichloromethane into the reaction mixed solution, standing for 1h at the normal temperature for layering, taking an oil layer, and distilling under the conditions of 75 ℃ and 350KPa under reduced pressure to obtain an epoxidized soybean oil polyol; respectively weighing 25 parts of sesame oil polyol, 25 parts of epoxy soybean oil polyol, 12 parts of hydrogenated castor oil, 50 parts of diphenylmethane diisocyanate, 2 parts of protein powder, 1.2 parts of sucrose, 1.2 parts of dimethylpolysiloxane, 0.2 part of ethylenediamine, 0.2 part of stannous octoate and 10 parts of deionized water, adding the protein powder and the sucrose into the deionized water, stirring at the normal temperature and the rotating speed of 190r/min for 11min to obtain a foaming agent, adding the sesame oil polyol and the epoxy soybean oil polyol into the hydrogenated castor oil, stirring at the normal temperature and the rotating speed of 220r/min for 22min to obtain mixed vegetable oil polyol, adding the foaming agent, the dimethylpolysiloxane, the ethylenediamine and the stannous octoate into the mixed vegetable oil polyol, placing the mixed vegetable oil polyol into a high-speed stirrer, stirring and mixing at the normal temperature and the rotating speed of 3250r/min for 25min to obtain a mixed foaming system, slowly adding the diphenylmethane diisocyanate into the mixed foaming system at the speed of 70mL/min, placing in a high-speed stirrer, stirring at constant temperature of 26 deg.C at 3750r/min for 7s to obtain mixture, rapidly pouring the mixture into a mold with specification of 100cm × 60cm × 60cm, standing at normal temperature for 1h, and demolding to obtain the composite plant oil-based polyurethane foam material.
Example 3
Respectively weighing 60 parts of sesame oil, 36 parts of maleic anhydride, 48 parts of glycerol, 12 parts of sodium hydroxide, 30 parts of anhydrous calcium chloride and 12 parts of deionized water according to parts by weight, adding the maleic anhydride into the sesame oil, introducing nitrogen protection at the rate of 60mL/min, stirring and reacting for 4 hours at the condition of 220 ℃ at the rotating speed of 280r/min to obtain maleic anhydride modified sesame oil, adding the glycerol and the sodium hydroxide into the maleic anhydride modified sesame oil, introducing nitrogen protection at the rate of 80mL/min, stirring and reacting for 6 hours at the condition of 240 ℃ at the rotating speed of 340r/min to obtain a reaction solution, adding the deionized water into the reaction solution, dropwise adding hydrochloric acid with the mass concentration of 1% to adjust the pH value to 7, adding the anhydrous calcium chloride, filtering, taking filtrate, and distilling under the conditions of 180 ℃ and 600KPa under reduced pressure to obtain sesame oil polyol; respectively weighing 60 parts of epoxidized soybean oil, 90 parts of anhydrous methanol, 3 parts of sulfuric acid with the mass fraction of 10%, 6 parts of zirconium oxide powder, 30 parts of deionized water and 90 parts of trichloromethane according to parts by weight, adding the sulfuric acid, the zirconium oxide powder and the deionized water into the anhydrous methanol, stirring at the normal temperature at the rotating speed of 240r/min for 20min to obtain a methanol mixed solution, slowly adding the epoxidized soybean oil into the methanol mixed solution at the dropping speed of 20mL/min, stirring and reacting at the water bath condition of 60 ℃ at the rotating speed of 350r/min for 60min, dropping a sodium carbonate solution with the mass fraction of 1% to adjust the pH to 7, filtering, taking a filtrate to obtain a mixed reaction solution, adding the trichloromethane into the reaction mixed solution, standing at the normal temperature for 2h for layering, taking an oil layer, and distilling under the reduced pressure at the condition of 80 ℃ and 400KPa to obtain the epoxidized soybean oil polyol; respectively weighing 30 parts of sesame oil polyol, 30 parts of epoxy soybean oil polyol, 15 parts of hydrogenated castor oil, 60 parts of diphenylmethane diisocyanate, 3 parts of protein powder, 1.5 parts of cane sugar, 1.5 parts of dimethylpolysiloxane, 0.3 part of ethylenediamine, 0.3 part of stannous octoate and 12 parts of deionized water, adding the protein powder and the cane sugar into the deionized water, stirring at the normal temperature at the rotating speed of 200r/min for 12min to obtain a foaming agent, adding the sesame oil polyol and the epoxy soybean oil polyol into the hydrogenated castor oil, stirring at the normal temperature at the rotating speed of 240r/min for 25min to obtain mixed vegetable oil polyol, adding the foaming agent, the dimethylpolysiloxane, the ethylenediamine and the stannous octoate into the mixed vegetable oil polyol, placing the mixed vegetable oil polyol into a high-speed stirrer, stirring and mixing at the normal temperature at the rotating speed of 3500r/min for 30min to obtain a mixed foaming system, slowly adding the diphenylmethane diisocyanate into the mixed foaming system at the speed of 80mL/min, and (3) placing the mixture into a high-speed stirrer, stirring for 8s at a constant temperature of 28 ℃ at a rotating speed of 4000r/min to obtain a mixture, quickly pouring the mixture into a mold with the specification of 100cm multiplied by 60cm, standing for 2h at normal temperature, and demolding to obtain the composite plant oil-based polyurethane foam material.
Comparative example: polyurethane foams from Dongguan company.
The polyurethane foam materials prepared in the examples and the comparative examples were tested, specifically as follows:
mechanical properties: detection is carried out according to GB/T8813-2008, and the instrument models are as follows: shenzhen Xinsansi CMT4000 model microcomputer controlled electronic universal tester, the compression deformation is 10%, the testing temperature is 25 ℃, and the sample specification is 5cm multiplied by 5 cm.
Coefficient of thermal conductivity: the specification of the sample is 3cm multiplied by 2cm, the model of the instrument is HotDiskTSP2500, a transient heat source method is adopted, and the output power is 0.005 w.
Critical oxygen index: testing according to the GB/T2406-1993 method, wherein the specification of the sample is 15cm multiplied by 1cm, 5 samples are obtained, and the average value is taken; the instrument model is JF-3 type oxygen index tester, Nanjing Jiangning analytical instrument factory.
The specific test results are shown in table 1.
Table 1 comparative table of property characterization
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example |
| Relative compressive strength/MPa | 7.31 | 7.14 | 7.05 | 5.35 |
| Thermal conductivity/W/m.K | 0.021 | 0.022 | 0.028 | 0.030 |
| Oxygen index/% | 29.5 | 29.0 | 29.1 | 20.4 |
As can be seen from Table 1, the polyurethane foam material prepared by the invention has good mechanical properties, thermal conductivity and flame retardant properties.
Claims (10)
1. The preparation method of the composite vegetable oil-based polyurethane foam material is characterized by comprising the following specific preparation steps:
(1) adding protein powder and sucrose into deionized water, and stirring at the normal temperature at the rotating speed of 180-200 r/min for 10-12 min to obtain a foaming agent;
(2) adding sesame oil polyalcohol and epoxy soybean oil polyalcohol into hydrogenated castor oil, and stirring at the rotating speed of 200-240 r/min for 20-25 min at normal temperature to obtain mixed vegetable oil polyalcohol;
(3) adding a foaming agent, dimethyl polysiloxane, ethylenediamine and stannous octoate into the mixed vegetable oil polyol, placing the mixture into a high-speed stirrer, and stirring and mixing the mixture at the rotating speed of 3000-3500 r/min for 20-30 min at normal temperature to obtain a mixed foaming system;
(4) slowly adding the diphenylmethane diisocyanate into the mixed foaming system, placing the mixed foaming system in a high-speed stirrer, and stirring for 6-8 s at the constant temperature of 24-28 ℃ at the rotating speed of 3500-4000 r/min to obtain a mixture;
(5) and quickly pouring the mixture into a mold, standing for 1-2 hours at normal temperature, and demolding to obtain the composite vegetable oil-based polyurethane foam material.
2. The preparation method of the composite vegetable oil-based polyurethane foam material as claimed in claim 1, wherein the sesame oil polyol, the epoxidized soybean oil polyol, the hydrogenated castor oil, the diphenylmethane diisocyanate, the protein powder, the sucrose, the dimethylpolysiloxane, the ethylenediamine, the stannous octoate and the deionized water are 20-30 parts by weight of the sesame oil polyol, 20-30 parts by weight of the epoxidized soybean oil polyol, 10-15 parts by weight of the hydrogenated castor oil, 40-60 parts by weight of the diphenylmethane diisocyanate, 2-3 parts by weight of the protein powder, 1.0-1.5 parts by weight of the sucrose, 1.0-1.5 parts by weight of the dimethylpolysiloxane, 0.2-0.3 part by weight of the ethylenediamine, 0.2-0.3 part by weight of the stannous octoate and 8-12 parts by weight of the deionized water.
3. The method for preparing the composite vegetable oil-based polyurethane foam material according to claim 1, wherein the addition rate of the diphenylmethane diisocyanate in the step (4) is 60-80 mL/min.
4. The method of claim 1, wherein the mold size of step (5) is 100cm x 60 cm.
5. The method for preparing the composite vegetable oil-based polyurethane foam material according to claim 1, wherein the step (2) of preparing the epoxidized soybean oil polyol comprises the following steps:
(1) adding sulfuric acid, zirconium oxide powder and deionized water into anhydrous methanol, and stirring at the rotating speed of 200-240 r/min for 10-20 min at normal temperature to obtain a methanol mixed solution;
(2) slowly adding epoxidized soybean oil into the methanol mixed solution, stirring and reacting for 40-60 min at the rotating speed of 300-350 r/min under the water bath condition of 50-60 ℃, adjusting the pH value to 7, filtering, and taking filtrate to obtain mixed reaction liquid;
(3) and adding trichloromethane into the reaction mixed liquid, standing for 1-2 h at normal temperature for layering, taking an oil layer, and distilling under reduced pressure at 70-80 ℃ under the condition of 300-400 KPa to obtain the epoxidized soybean oil polyol.
6. The preparation method of the composite vegetable oil-based polyurethane foam material as claimed in claim 5, wherein the weight parts of the epoxidized soybean oil, the anhydrous methanol, the sulfuric acid, the zirconia powder, the deionized water and the trichloromethane are 40-60 parts of the epoxidized soybean oil, 60-90 parts of the anhydrous methanol, 2-3 parts of the sulfuric acid with the mass fraction of 10%, 4-6 parts of the zirconia powder, 20-30 parts of the deionized water and 60-90 parts of the trichloromethane.
7. The preparation method of the composite vegetable oil-based polyurethane foam material as claimed in claim 5, wherein the epoxidized soybean oil in the step (2) is added dropwise at a rate of 10-20 mL/min, and a sodium carbonate solution with a mass fraction of 1% is used for pH adjustment.
8. The preparation method of the composite vegetable oil-based polyurethane foam material as claimed in claim 1, wherein the sesame oil polyol of step (2) is prepared by the following steps:
(1) adding maleic anhydride into sesame oil, introducing nitrogen at the rate of 40-60 mL/min for protection, and stirring at the rotating speed of 240-280 r/min at the temperature of 200-220 ℃ for reaction for 2-4 hours to obtain maleic anhydride modified sesame oil;
(2) adding glycerol and sodium hydroxide into the maleic anhydride modified sesame oil, introducing nitrogen at the rate of 60-80 mL/min for protection, and stirring at the rotating speed of 300-340 r/min at the temperature of 220-240 ℃ for reaction for 4-6 hours to obtain a reaction solution;
(3) adding deionized water into the reaction solution, adjusting the pH value to 7, adding anhydrous calcium chloride, filtering, taking the filtrate, and carrying out reduced pressure distillation at 160-180 ℃ under the condition of 400-600 KPa to obtain the sesame oil polyalcohol.
9. The method for preparing the composite vegetable oil-based polyurethane foam material according to claim 8, wherein the sesame oil, the maleic anhydride, the glycerol, the sodium hydroxide, the anhydrous calcium chloride and the deionized water are 40-60 parts by weight of sesame oil, 24-36 parts by weight of maleic anhydride, 32-48 parts by weight of glycerol, 8-12 parts by weight of sodium hydroxide, 20-30 parts by weight of anhydrous calcium chloride and 8-12 parts by weight of deionized water.
10. The method of claim 8, wherein hydrochloric acid is used in the step (3) to adjust the pH at a mass fraction of 1%.
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