CN119320484A - Modified hemp core powder composite polyurethane foaming material and preparation method thereof - Google Patents
Modified hemp core powder composite polyurethane foaming material and preparation method thereof Download PDFInfo
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Abstract
本发明属于聚氨酯发泡材料技术领域，具体涉及一种改性汉麻芯粉复合聚氨酯发泡材料，其质量配比包括：聚合物多元醇30‑50份、改性汉麻芯粉10‑40份、阻燃剂20‑30份、催化剂1‑2份、发泡剂3‑4份、泡沫稳定剂1‑2份、有机多异氰酸酯65‑80份、白油0.5‑1份；所述改性汉麻芯粉采用钛氧改性汉麻芯粉；并提供了发泡材料的制备方法。本发明解决了汉麻改性聚氨酯发泡体的抗菌持久性问题，利用钛氧材料的包裹性、抗菌抑菌性和可恢复性，能够与汉麻芯内的抗菌材料形成有机‑无机复合抗菌抑菌体系，且抗菌材料被硅氧材料包裹，有效的解决了抗菌材料的散失问题。The present invention belongs to the technical field of polyurethane foam materials, and specifically relates to a modified hemp core powder composite polyurethane foam material, the mass ratio of which includes: 30-50 parts of polymer polyol, 10-40 parts of modified hemp core powder, 20-30 parts of flame retardant, 1-2 parts of catalyst, 3-4 parts of foaming agent, 1-2 parts of foam stabilizer, 65-80 parts of organic polyisocyanate, and 0.5-1 parts of white oil; the modified hemp core powder adopts titanium oxide modified hemp core powder; and a preparation method of the foaming material is provided. The present invention solves the problem of antibacterial persistence of hemp modified polyurethane foam, and utilizes the encapsulation, antibacterial and antibacterial properties and recoverability of titanium oxide materials to form an organic-inorganic composite antibacterial and antibacterial system with the antibacterial material in the hemp core, and the antibacterial material is wrapped by silicon oxide materials, which effectively solves the problem of loss of antibacterial materials.
Description
Technical Field
The invention belongs to the technical field of polyurethane foaming materials, and particularly relates to a modified hemp core powder composite polyurethane foaming material and a preparation method thereof.
Background
Polyurethane is a polymer which is formed by gradually adding and polymerizing polyether, polyester polyol and polyisocyanate containing hydroxyl, and the polymer is widely applied to the aspects of foamed plastics, coatings, elastomers, elastic fibers and the like due to excellent performance. Wherein, the polyurethane foam plastic accounts for 70 percent of the total polyurethane, and is a main product in polyurethane materials. In use, the polyurethane foam material does not have antibacterial performance, bacteria breeding is easy to form, and the hemp modified polyurethane foam material is formed by transporting the hemp modified polyurethane foam material aiming at the problem, and the hemp modified polyurethane foam material not only has good antibacterial effect, but also has excellent hardness and strength, and improves the practicability of the hemp modified polyurethane foam material. However, the hemp has good antibacterial and bacteriostatic properties at an early stage, and the properties are derived from the fact that the hemp also contains unique antibacterial substances such as alkaloids, phenols and the like, but the antibacterial properties are linearly reduced along with the loss of the antibacterial substances with the increase of the service time until the antibacterial properties are lost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the modified hemp core powder composite polyurethane foam material, which solves the problem of antibacterial durability of a hemp modified polyurethane foam body, can form an organic-inorganic composite antibacterial and bacteriostatic system with an antibacterial material in a hemp core by utilizing the wrapping property, antibacterial and bacteriostatic properties and restorability of a titanium oxide material, and effectively solves the problem of dissipation of the antibacterial material by wrapping the antibacterial material with a silicon oxide material.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
The mass ratio of the modified hemp core powder composite polyurethane foaming material is as follows:
30-50 parts of polymer polyol, 10-40 parts of modified hemp core powder, 20-30 parts of flame retardant, 1-2 parts of catalyst, 3-4 parts of foaming agent, 1-2 parts of foam stabilizer, 65-80 parts of organic polyisocyanate and 0.5-1 part of white oil.
The polymer polyol adopts LPOP-36/30 or LPOP-36/28G.
The modified hemp core powder adopts the titanium oxide modified hemp core powder, the hemp core is an absorption core made of purely natural plant fiber extracted from hemp stems, has multiple cavities and pores inside, and contains unique alkaloid, Antibacterial substances such as phenols, etc. have serious loss of antibacterial substances in the hemp core with the increase of the use time and the cleaning times, and can cause rapid decrease of the antibacterial performance; the titanium oxide material is a titanium dioxide-based material, belongs to an inorganic antibacterial material, can realize a wide-area antibacterial effect, is wrapped on the surface of the hemp core powder, can utilize a surface pore structure formed by condensation polymerization of silica, reduces release of antibacterial substances, and improves the service life of an organic-inorganic composite antibacterial system; the preparation method of the titanium oxide modified hemp core powder comprises the steps of a1, grinding the hemp core at a constant temperature, screening to obtain the hemp core powder, wherein the constant temperature grinding temperature is 5-30 ℃ and the grinding pressure is 0.3-0.5MPa, grinding the hemp core particles in a constant pressure extrusion mode, controlling the friction heat problem of grinding by constant temperature, obtaining refined materials with a structure similar to that of substances, finally screening grinding impurities, removing chips generated by grinding in a pore mode, ensuring that the particle size of the hemp core powder is similar to that of the diethyl ether, a2, dissolving tetraethyl titanate in diethyl ether to obtain a homogeneous liquid, rapidly stirring the hemp core powder, taking out the diethyl ether to obtain coated hemp core powder, wherein the mass ratio of the tetraethyl titanate to the diethyl ether is 1-3, the mass ratio of the diethyl ether is uniformly stirring at a speed of 1:3-5, the mass ratio of the diethyl ether is 1:300, the mass ratio is uniformly stirring at a speed of 1:300:1000-1000 r/1000 min, and the mass ratio is uniformly stirring at a speed of 1:300:1000-1000 r/min, the time is 5-10s, and the standing temperature is 30-35 ℃; the method comprises the steps of forming a homogeneous diethyl ether solution of tetraethyl titanate by utilizing the miscibility of the tetraethyl titanate in diethyl ether; then adding the hemp core powder into the fast stirring, wherein the fast stirring is based on the fact that the hemp core powder contains a large number of bubbles in the holes and pores of the hemp core powder, and the bubbles can not be rapidly discharged in a short period of time, so that the bubbles in the hemp core powder are not discharged when the hemp core powder is taken out, a tetraethyl titanate-diethyl ether liquid film is formed on the surface, and diethyl ether is gradually volatilized at a standing temperature, so that the tetraethyl titanate coated hemp core powder is formed, and meanwhile, in the standing process, the liquid flowability of the tetraethyl titanate can fill gaps after the diethyl ether is evaporated, so that a homogeneous tetraethyl titanate liquid film is formed; 3, standing the coated hemp core powder for 20-30min to obtain titanic acid coated hemp core powder, wherein the standing atmosphere is a mixed atmosphere of nitrogen and steam, the volume ratio of the nitrogen to the steam is 8-10:1, and the temperature is 30-50 ℃, the hydrolysis characteristic of the tetraethyl titanate is utilized, the water steam in the atmosphere and the hygroscopicity in the hemp core powder are matched, the hydrolysis speed of the tetraethyl titanate is improved, in-situ hydrolysis of the tetraethyl titanate is formed, thus obtaining the titanic acid modified hemp core powder, a4, adding 3-aminopropyl triethoxysilane and ethyl cellulose into diethyl ether, stirring uniformly, then adding the titanic acid coated hemp core powder, stirring for 2-4min at low temperature, taking out, drying to obtain secondary coated hemp core powder, the mass ratio of the 3-aminopropyl triethoxysilane to the ethyl cellulose is 10-14:1, the mass ratio of the 3-aminopropyl triethoxysilane to the diethyl ether is 1:13-15, the stirring speed of the uniform stirring is 100-400r/min, the mass ratio of the titanic acid coated hemp core powder to the diethyl ether is 1:18-20, the low-temperature stirring temperature is 5-10 ℃, the stirring speed is 100-200r/min, and the drying temperature is 40-50 ℃; the preparation method comprises the steps of utilizing the solubility of 3-aminopropyl triethoxysilane and ethyl cellulose in diethyl ether to form a homogeneous dispersion effect, wrapping the surface of hemp core powder by titanic acid to form a liquid film in a low-temperature low-speed stirring process, removing diethyl ether in a drying process to form a composite film of ethyl cellulose and 3-aminopropyl triethoxysilane, standing the secondary coating hemp core powder for 20-30min, carrying out sealing sintering treatment and ethanol soaking treatment, taking out and drying to obtain the titanium oxide modified hemp core powder, wherein the standing atmosphere is an atmosphere of nitrogen and water vapor, the volume ratio of the nitrogen and the water vapor is 1:8-10, the standing temperature is 60-70 ℃, the sealing sintering adopts dual gradient heating, the first gradient heating temperature is 100-120 ℃, the time is 0.5-1h, the second gradient heating temperature is 180-200 ℃, the atmosphere is 1-2h, the solid-liquid mass ratio in the soaking treatment is 1:5-7, the secondary coating hemp core powder is subjected to water vapor atmosphere, the 3-aminopropyl triethoxysilane in the primary coating is subjected to in-situ, the thermal condensation of the primary coating is well-formed, and the hydroxyl-terminated silicon is subjected to in-situ, the thermal condensation of the hydroxyl-terminated silicon is well-terminated in the primary coating, and the in-situ silicon-phase is formed, the surface coating film can form a silicon-oxygen composite pore film taking ethyl cellulose as a spacing material, the composite pore film is rich in silicon hydroxyl and amino, and along with the second gradient heating reaction, titanium hydroxyl on titanic acid and silicon hydroxyl form a polycondensation reaction of a hydroxyl system, so that good connectivity is achieved. The titanium oxide modified hemp core powder prepared by the process takes hemp core powder as an inner core, a titanium oxide film and a silicon oxide film are sequentially coated from inside to outside, and the titanium oxide film and the silicon oxide film form polycondensation connection. The titanium oxide film contains a mesoporous structure, has good circulation, forms an organic-inorganic composite structure with antibacterial substances in inner core cavities, contains mesopores and micropores to form a composite pore structure, keeps good gas circulation, and further, the titanium oxide modified hemp core powder is in a porous state and is completely wrapped by the titanium oxide film, so that the weight of the titanium oxide modified hemp core powder is reduced under a pore structure system.
The flame retardant is made of porous silica material, and the porous silica material is rich in silicon hydroxyl. The inorganic flame retardant material has good and stable flame retardant effect, but certain inertia exists on the surface of the inorganic flame retardant, which can cause poor stability of the inorganic flame retardant on the polyurethane foaming material and can bring about the problem of falling off of the inorganic material, in order to solve the problem, the flame retardant adopts a porous silica material which has a porous structure and a large number of pore structures to form good physical permeation and clamping effects, meanwhile, the porous silica material is rich in silicon hydroxyl groups, can form chemical connection in polyurethane prepolymerization reaction, and improves the connection stability of the silica material in the polyurethane foaming material, the preparation method of the porous silica material comprises the following steps of b1, adding 3-chloropropyl trichlorosilane and isobutyl triethoxysilane into diethyl ether, stirring uniformly to obtain a composite solution, wherein the mass ratio of the 3-chloropropyl trichlorosilane to the isobutyl triethoxysilane is 3:1-2, the concentration of the 3-chloropropyl trichlorosilane in diethyl ether is 300-500g/L, the stirring uniformly speed is 400-600r/min, and the temperature is 5-10 ℃; the step utilizes the solubility of 3-chloropropyl trichlorosilane and isobutyl triethoxysilane in diethyl ether to ensure the full mixing of the 3-chloropropyl trichlorosilane and the isobutyl triethoxysilane, b2, adding ethyl cellulose into the composite dissolving solution, carrying out low-temperature ultrasonic treatment for 20-30min, then standing for 2-3h to obtain viscous liquid, wherein the concentration of the ethyl cellulose in the composite dissolving solution is 500-800g/L, the temperature of the low-temperature ultrasonic treatment is 5-10 ℃, the ultrasonic frequency is 60-80kHz, the standing treatment is carried out at 30-35 ℃ and at 90-95% of atmospheric pressure, the step utilizes the good solubility of ethyl cellulose in diethyl ether, can be rapidly dispersed in mixed solution, achieves the effect of full mixing, and improves the dissolution rate of 3-chloropropyl trichlorosilane by matching with high-frequency vibration of low-temperature ultrasound, the preparation method comprises the steps of fully mixing isobutyl triethoxysilane and ethylcellulose in diethyl ether, homogenizing and dispersing, wherein in standing treatment, diethyl ether plays a good role in volatility, the purpose of effectively controlling solvent removal is achieved, the overall viscosity is effectively controlled, b3, spraying viscous liquid into a reaction kettle, depositing to obtain deposited particles, wherein the spraying speed is 3-5mL/min, the spraying area is 200-400cm 2, the atmosphere of the reaction kettle is a mixed atmosphere of nitrogen and water vapor, the volume ratio of the nitrogen to the water vapor is 10-12:1, the depositing temperature is 40-45 ℃, the step comprises the steps of spraying viscous liquid into the reaction kettle in a spraying mode, forming diethyl ether fast evaporation under a temperature system, and forming solid particles after the viscous liquid is sprayed, wherein the solid particles are formed by ethylcellulose, The 3-chloropropyl trichlorosilane and the isobutyl triethoxysilane are formed, the atmosphere in the reaction kettle contains water vapor, and can form hydrolysis reaction with the 3-chloropropyl trichlorosilane and the isobutyl triethoxysilane, namely, the deposited particles are formed by 2-hydroxypropyl trihydroxy silane, and b4, standing the deposited particles at a constant temperature for 2-4h, then placing the deposited particles in ethanol for ultrasonic treatment for 20-30min, filtering and drying to obtain a porous silica material, wherein the constant temperature standing temperature is 110-120 ℃, the atmosphere is nitrogen atmosphere, the solid-liquid mass ratio of ultrasonic treatment is 1:5-7, the temperature is 20-30 ℃, the ultrasonic frequency is 60-90kHz, the drying temperature is 80-90 ℃, the step utilizes a constant temperature standing mode to promote the polycondensation reaction of the hydrolysate of 3-chloropropyl trichlorosilane and isobutyl triethoxysilane, the stability and inertia of the ethyl cellulose are kept, the polycondensation reaction is in-situ, the solubility of the ethanol to the ethyl cellulose and the insolubility of the ethyl cellulose to the silica polycondensate are ensured, the ethyl cellulose can be rapidly peeled into the ethanol under an ultrasonic environment, and the modified silica material is prepared by polycondensating silicon hydroxyl groups, and the surface area can contain a large amount of hydroxyl groups.
The catalyst adopts triethylene diamine.
The foaming agent adopts water.
The foam stabilizer adopts silicone oil AK8805.
The organic polyisocyanate adopts toluene diisocyanate.
The preparation method of the modified hemp core powder composite polyurethane foaming material comprises the following steps:
Step 1, stirring and mixing polymer polyol, modified hemp core powder and a flame retardant to form a mixture, wherein the stirring speed of stirring and mixing is 300-500r/min, and the stirring temperature is normal temperature;
Step 2, putting a catalyst, white oil, a foaming agent and a foam stabilizer into the mixture, and rapidly stirring to obtain a prepolymerized mixture, wherein the rapid stirring speed is 1000-2000r/min, and the time is 20-40s;
and 3, adding the organic polyisocyanate into the prepolymerization mixture, stirring at a high speed, foaming and curing to obtain the modified hemp core powder composite polyurethane foam material, wherein the high-speed stirring speed is 2000-3000r/min, the time is 7-10s, the foaming adopts standing free foaming, and the curing temperature is room temperature and the time is 20-24h.
From the above description, it can be seen that the present invention has the following advantages:
1. The invention solves the problem of antibacterial persistence of the hemp modified polyurethane foam, and can form an organic-inorganic composite antibacterial system with the antibacterial material in the hemp core by utilizing the wrapping property, antibacterial bacteriostasis and restorability of the titanium oxide material, and the antibacterial material is wrapped by the silica material, thereby effectively solving the problem of dissipation of the antibacterial material.
2. According to the invention, the silicon oxide layer is formed on the surface of the titanium oxide film, so that stable connectivity is ensured between the silicon oxide layer and the titanium oxide film, and meanwhile, the silicon oxide layer wraps the titanium oxide film, so that the corrosion problem of the titanium oxide material after excitation and activation is effectively solved.
3. The silicon oxide layer coated on the surface of the titanium oxide film is rich in silicon hydroxyl, so that the polyurethane prepolymer is promoted to be in a polyhydroxy structure.
Detailed Description
The invention is described in detail with reference to examples, but without any limitation to the claims of the invention.
Example 1 a modified hemp core powder composite polyurethane foaming material comprises the following components in percentage by mass:
30 parts of polymer polyol, 10 parts of modified hemp core powder, 20 parts of flame retardant, 1-2 parts of catalyst, 3 parts of foaming agent, 1 part of foam stabilizer, 65 parts of organic polyisocyanate and 0.5 part of white oil.
The polymer polyol used was LPOP-36/30 from Shandong Long Hua New Material Co., ltd.
The preparation method of the modified hemp core powder adopts the titanium oxide modified hemp core powder, and comprises the following steps that a1, the hemp core is ground at a constant temperature, the temperature of the constant temperature grinding is 5 ℃, the grinding pressure is 0.3MPa, a2, tetraethyl titanate is dissolved in diethyl ether and uniformly stirred to obtain homogeneous liquid, then the hemp core powder is rapidly stirred, taken out and then kept stand for 1h to obtain coated hemp core powder, the mass ratio of the tetraethyl titanate to the diethyl ether is 1:3, the stirring speed is 100r/min, the mass ratio of the hemp core powder to the diethyl ether is 1:10, the rapid stirring speed is 1000r/min, the time is 5-10s, and the standing temperature is 30 ℃; a3, standing the coated hemp core powder for 20min to obtain titanic acid coated hemp core powder, wherein the standing atmosphere is a mixed atmosphere of nitrogen and steam, the volume ratio of the nitrogen to the steam is 8:1, the temperature is 30 ℃, a4, adding 3-aminopropyl triethoxysilane and ethylcellulose into diethyl ether, uniformly stirring, then adding the titanic acid coated hemp core powder, stirring for 2min at a low temperature, taking out, drying to obtain secondary coated hemp core powder, the mass ratio of the 3-aminopropyl triethoxysilane to the ethylcellulose is 10:1, the mass ratio of the 3-aminopropyl triethoxysilane to the diethyl ether is 1:13, the uniform stirring speed is 100r/min, the mass ratio of the titanic acid coated hemp core powder to the diethyl ether is 1:18, the temperature of low-temperature stirring is 5 ℃, the stirring speed is 100r/min, the temperature of drying is 40 ℃, a5, standing the secondary coated hemp core powder for 20min, sealing, sintering treatment and ethanol soaking, taking out, drying to obtain the modified titanium modified hemp core powder, the atmosphere of standing is the atmosphere of nitrogen and vapor, the volume ratio of the nitrogen to the vapor is 1:8, the temperature of standing is 60 ℃, the sealed sintering adopts double gradient heating, the temperature of the first gradient heating is 100 ℃, the time is 0.5h, the temperature of the second gradient heating is 180 ℃, the time is 1h, the atmosphere is the nitrogen atmosphere, and the solid-liquid mass ratio in the soaking treatment is 1:5.
The preparation method of the porous silica material comprises the steps of b1, adding 3-chloropropyl trichlorosilane and isobutyl triethoxy silane into diethyl ether, stirring uniformly to obtain a composite solution, wherein the mass ratio of the 3-chloropropyl trichlorosilane to the isobutyl triethoxy silane is 3:1, the concentration of the 3-chloropropyl trichlorosilane in the diethyl ether is 300g/L, the stirring speed of the uniform stirring is 400r/min, the temperature is 5 ℃, b2, adding ethyl cellulose into the composite solution, conducting low-temperature ultrasonic treatment for 20min, then conducting standing treatment for 2h, obtaining a viscous liquid, the concentration of the ethyl cellulose in the composite solution is 500g/L, the temperature of the low-temperature ultrasonic treatment is 5 ℃, the ultrasonic frequency is 60kHz, the temperature of the standing treatment is 30 ℃, the pressure is 90% of the atmosphere, b3, spraying the viscous liquid into a reaction kettle, depositing to obtain deposited particles, the spray rate is 5 kHz, the spray rate is 200 mL, the mass ratio of the water to the solid vapor is 20:20, the vacuum ratio of the vapor is 20:20, the vapor is obtained after the constant temperature is 2 ℃, the vacuum ratio of the vapor is 20:20, the vacuum ratio of the vapor is 20, the vapor is obtained after the vacuum deposition is carried out, and the vacuum ratio of the vapor is 20:20, and the vacuum ratio of the vapor is 20.
The catalyst adopts triethylene diamine.
The foaming agent adopts water.
The foam stabilizer adopts silicone oil AK8805.
The organic polyisocyanate adopts toluene diisocyanate.
The preparation method of the modified hemp core powder composite polyurethane foaming material comprises the following steps:
Step 1, stirring and mixing polymer polyol, modified hemp core powder and a flame retardant to form a mixture, wherein the stirring speed of stirring and mixing is 300r/min, and the stirring temperature is normal temperature;
Step 2, putting a catalyst, white oil, a foaming agent and a foam stabilizer into the mixture, and rapidly stirring to obtain a prepolymerized mixture, wherein the rapid stirring speed is 1000r/min, and the time is 20s;
And 3, adding the organic polyisocyanate into the prepolymerization mixture, stirring at a high speed, foaming and curing to obtain the modified hemp core powder composite polyurethane foam material, wherein the high-speed stirring speed is 2000r/min, the time is 7s, the foaming adopts standing free foaming, the curing temperature is room temperature, and the time is 20h.
Example 2a modified hemp core powder composite polyurethane foaming material comprises the following components in percentage by mass:
50 parts of polymer polyol, 40 parts of modified hemp core powder, 30 parts of flame retardant, 2 parts of catalyst, 4 parts of foaming agent, 2 parts of foam stabilizer, 80 parts of organic polyisocyanate and 1 part of white oil.
The polymer polyol is LPOP-36/28G.
The preparation method of the modified hemp core powder adopts the titanium oxide modified hemp core powder, and comprises the following steps of a1, grinding the hemp core at a constant temperature, screening to obtain the hemp core powder, wherein the constant temperature grinding temperature is 30 ℃, the grinding pressure is 0.5MPa, a2, dissolving tetraethyl titanate in diethyl ether, uniformly stirring to obtain homogeneous liquid, then rapidly stirring the hemp core powder, taking out and standing for 3h to obtain coated hemp core powder, wherein the mass ratio of the tetraethyl titanate to the diethyl ether is 1:5, the stirring speed is 300r/min, the mass ratio of the hemp core powder to the diethyl ether is 1:15, the rapid stirring speed is 3000r/min, the time is 10s, and the standing temperature is 35 ℃; a3, standing the coated hemp core powder for 30min to obtain titanic acid coated hemp core powder, wherein the standing atmosphere is a mixed atmosphere of nitrogen and steam, the volume ratio of the nitrogen to the steam is 10:1, the temperature is 50 ℃, a4, adding 3-aminopropyl triethoxysilane and ethylcellulose into diethyl ether, uniformly stirring, then adding the titanic acid coated hemp core powder, stirring for 4min at a low temperature, taking out, drying to obtain secondary coated hemp core powder, the mass ratio of the 3-aminopropyl triethoxysilane to the ethylcellulose is 14:1, the mass ratio of the 3-aminopropyl triethoxysilane to the diethyl ether is 1:15, the uniform stirring speed is 400r/min, the mass ratio of the titanic acid coated hemp core powder to the diethyl ether is 1:20, the temperature of low-temperature stirring is 10 ℃, the stirring speed is 200r/min, the temperature of drying is 50 ℃, a5, standing the secondary coated hemp core powder for 30min, sealing, sintering treatment and ethanol soaking, taking out, drying to obtain the modified titanium modified hemp core powder, the atmosphere of standing is the atmosphere of nitrogen and vapor, the volume ratio of the nitrogen to the vapor is 1:10, the temperature of standing is 70 ℃, the sealed sintering adopts double-gradient heating, the temperature of the first gradient heating is 120 ℃, the time is 1h, the temperature of the second gradient heating is 200 ℃, the time is 2h, the atmosphere is the nitrogen atmosphere, and the solid-liquid mass ratio in the soaking treatment is 1:7.
The flame retardant is made of a porous silica material, and the porous silica material is rich in silicon hydroxyl; the preparation method of the porous silica material comprises the following steps of b1, adding 3-chloropropyl trichlorosilane and isobutyl triethoxysilane into diethyl ether, stirring uniformly to obtain a composite solution, wherein the mass ratio of the 3-chloropropyl trichlorosilane to the isobutyl triethoxysilane is 3:2, the concentration of the 3-chloropropyl trichlorosilane in the diethyl ether is 500g/L, the stirring speed of the stirring uniformly is 600r/min, the temperature is 10 ℃, b2, adding ethylcellulose into the composite solution, performing low-temperature ultrasonic treatment for 30min, then performing standing treatment for 3h to obtain a viscous liquid, the concentration of the ethylcellulose in the composite solution is 800g/L, the temperature of the low-temperature ultrasonic treatment is 10 ℃, the ultrasonic frequency is 80kHz, the temperature of the standing treatment is 35 ℃, the pressure is 95% of atmospheric pressure, b3, spraying the viscous liquid into a reaction kettle, depositing to obtain deposited particles, the spraying speed is 5mL/min, the spraying area is 400cm 2, the temperature of the reaction kettle is 10 ℃ and the ultrasonic treatment atmosphere, the ratio of the water to the porous silica material is 90 ℃ and the vapor is obtained after the ultrasonic treatment, the temperature is 1:90 ℃ and the vacuum ratio of the vapor is 90 ℃ and the vapor is dried, the temperature is 90 ℃ and the vacuum ratio of the vapor is 90.
The catalyst adopts triethylene diamine.
The foaming agent adopts water.
The foam stabilizer adopts silicone oil AK8805.
The organic polyisocyanate adopts toluene diisocyanate.
The preparation method of the modified hemp core powder composite polyurethane foaming material comprises the following steps:
Step 1, stirring and mixing polymer polyol, modified hemp core powder and a flame retardant to form a mixture, wherein the stirring speed of stirring and mixing is 500r/min, and the stirring temperature is normal temperature;
step 2, putting a catalyst, white oil, a foaming agent and a foam stabilizer into the mixture, and rapidly stirring to obtain a prepolymerized mixture, wherein the rapid stirring speed is 2000r/min, and the time is 40s;
And step 3, adding the organic polyisocyanate into the prepolymerization mixture, stirring at a high speed, foaming and curing to obtain the modified hemp core powder composite polyurethane foam material, wherein the high-speed stirring speed is 3000r/min, the time is 10s, the foaming adopts standing free foaming, the curing temperature is room temperature, and the time is 24h.
Example 3a modified hemp core powder composite polyurethane foaming material comprises the following components in percentage by mass:
40 parts of polymer polyol, 30 parts of modified hemp core powder, 25 parts of flame retardant, 2 parts of catalyst, 3 parts of foaming agent, 2 parts of foam stabilizer, 75 parts of organic polyisocyanate and 0.8 part of white oil.
The polymer polyol is LPOP-36/30.
The preparation method of the modified hemp core powder adopts the titanium oxide modified hemp core powder, and comprises the following steps that a1, the hemp core is ground at a constant temperature, the temperature of the constant temperature grinding is 20 ℃, the grinding pressure is 0.4MPa, a2, tetraethyl titanate is dissolved in diethyl ether and uniformly stirred to obtain homogeneous liquid, then the hemp core powder is rapidly stirred, taken out and then kept stand for 2 hours to obtain coated hemp core powder, the mass ratio of the tetraethyl titanate to the diethyl ether is 1:4, the stirring speed is 200r/min, the mass ratio of the hemp core powder to the diethyl ether is 1:13, the rapid stirring speed is 2000r/min, the time is 8s, and the standing temperature is 33 ℃; a3, standing the coated hemp core powder for 25min to obtain titanic acid coated hemp core powder, wherein the standing atmosphere is a mixed atmosphere of nitrogen and steam, the volume ratio of the nitrogen to the steam is 9:1, the temperature is 40 ℃, a4, adding 3-aminopropyl triethoxysilane and ethylcellulose into diethyl ether, uniformly stirring, then adding the titanic acid coated hemp core powder, stirring for 3min at a low temperature, taking out, drying to obtain secondary coated hemp core powder, the mass ratio of the 3-aminopropyl triethoxysilane to the ethylcellulose is 12:1, the mass ratio of the 3-aminopropyl triethoxysilane to the diethyl ether is 1:14, the uniform stirring speed is 300r/min, the mass ratio of the titanic acid coated hemp core powder to the diethyl ether is 1:19, the temperature of low-temperature stirring is 8 ℃, the stirring speed is 150r/min, the drying temperature is 45 ℃, a5, standing the secondary coated hemp core powder for 25min, carrying out sealing sintering treatment and ethanol soaking treatment, taking out, drying to obtain the modified titanium modified hemp core powder, the atmosphere of standing is the atmosphere of nitrogen and vapor, the volume ratio of nitrogen to vapor is 1:9, the temperature of standing is 65 ℃, the sealed sintering adopts double-gradient heating, the temperature of the first gradient heating is 110 ℃, the time is 1h, the temperature of the second gradient heating is 190 ℃, the time is 2h, the atmosphere is the nitrogen atmosphere, and the solid-liquid mass ratio in the soaking treatment is 1:6.
The preparation method of the porous silica material comprises the steps of b1, adding 3-chloropropyl trichlorosilane and isobutyl triethoxy silane into diethyl ether, stirring uniformly to obtain a composite solution, wherein the mass ratio of the 3-chloropropyl trichlorosilane to the isobutyl triethoxy silane is 3:1, the concentration of the 3-chloropropyl trichlorosilane in the diethyl ether is 400g/L, the stirring speed of the uniform stirring is 500r/min, the temperature is 8 ℃, b2, adding ethyl cellulose into the composite solution, carrying out low-temperature ultrasonic treatment for 25min, then carrying out standing treatment for 3h, obtaining a viscous liquid, the concentration of the ethyl cellulose in the composite solution is 700g/L, the temperature of the low-temperature ultrasonic treatment is 8 ℃, the ultrasonic frequency is 70kHz, the temperature of the standing treatment is 33 ℃, the pressure is 93% of the atmosphere, b3, spraying the viscous liquid into a reaction kettle, depositing particles are obtained, the constant temperature is 574 kHz, the stirring speed is 500r/min, the temperature is 25 ℃ and the vacuum ratio of the vapor is 80:3:85 ℃, the vacuum ratio of the nitrogen is obtained by mixing the ultrasonic liquid with the nitrogen, the vacuum vapor is 80:3, the vacuum ratio of the vacuum deposition particles is 80:3, the vacuum ratio is the vacuum ratio of the vacuum deposition material is 80, and the vacuum ratio is the vacuum ratio of the vacuum deposition material is 80:3, and the vacuum ratio is the vacuum condition.
The catalyst adopts triethylene diamine.
The foaming agent adopts water.
The foam stabilizer adopts silicone oil AK8805.
The organic polyisocyanate adopts toluene diisocyanate.
The preparation method of the modified hemp core powder composite polyurethane foaming material comprises the following steps:
Step 1, stirring and mixing polymer polyol, modified hemp core powder and a flame retardant to form a mixture, wherein the stirring speed of stirring and mixing is 400r/min, and the stirring temperature is normal temperature;
Step 2, putting a catalyst, white oil, a foaming agent and a foam stabilizer into the mixture, and rapidly stirring to obtain a prepolymerized mixture, wherein the rapid stirring speed is 1500r/min, and the time is 30s;
and 3, adding the organic polyisocyanate into the prepolymerization mixture, stirring at a high speed, foaming and curing to obtain the modified hemp core powder composite polyurethane foam material, wherein the high-speed stirring speed is 2500r/min, the time is 9s, the foaming adopts standing free foaming, the curing temperature is room temperature, and the time is 22h.
Example 4 a modified hemp core powder composite polyurethane foaming material comprises the following components in percentage by mass:
40 parts of polymer polyol, 30 parts of modified hemp core powder, 25 parts of flame retardant, 2 parts of catalyst, 3 parts of foaming agent, 2 parts of foam stabilizer, 75 parts of organic polyisocyanate and 0.8 part of white oil.
The polymer polyol is LPOP-36/30.
The preparation method of the modified hemp core powder adopts the titanium oxide modified hemp core powder, and comprises the following steps that a1, the hemp core is ground at a constant temperature, the temperature of the constant temperature grinding is 20 ℃, the grinding pressure is 0.4MPa, a2, tetraethyl titanate is dissolved in diethyl ether and uniformly stirred to obtain homogeneous liquid, then the hemp core powder is rapidly stirred, taken out and then kept stand for 2 hours to obtain coated hemp core powder, the mass ratio of the tetraethyl titanate to the diethyl ether is 1:4, the stirring speed is 200r/min, the mass ratio of the hemp core powder to the diethyl ether is 1:13, the rapid stirring speed is 2000r/min, the time is 8s, and the standing temperature is 33 ℃; a3, standing the coated hemp core powder for 25min to obtain titanic acid coated hemp core powder, wherein the standing atmosphere is a mixed atmosphere of nitrogen and steam, the volume ratio of the nitrogen to the steam is 9:1, the temperature is 40 ℃, a4, adding 3-aminopropyl triethoxysilane and ethylcellulose into diethyl ether, uniformly stirring, then adding the titanic acid coated hemp core powder, stirring for 3min at a low temperature, taking out, drying to obtain secondary coated hemp core powder, the mass ratio of the 3-aminopropyl triethoxysilane to the ethylcellulose is 12:1, the mass ratio of the 3-aminopropyl triethoxysilane to the diethyl ether is 1:14, the uniform stirring speed is 300r/min, the mass ratio of the titanic acid coated hemp core powder to the diethyl ether is 1:19, the temperature of low-temperature stirring is 8 ℃, the stirring speed is 150r/min, the drying temperature is 45 ℃, a5, standing the secondary coated hemp core powder for 25min, carrying out sealing sintering treatment and ethanol soaking treatment, taking out, drying to obtain the modified titanium modified hemp core powder, the atmosphere of standing is the atmosphere of nitrogen and vapor, the volume ratio of nitrogen to vapor is 1:9, the temperature of standing is 65 ℃, the sealed sintering adopts double-gradient heating, the temperature of the first gradient heating is 110 ℃, the time is 1h, the temperature of the second gradient heating is 190 ℃, the time is 2h, the atmosphere is the nitrogen atmosphere, and the solid-liquid mass ratio in the soaking treatment is 1:6.
The flame retardant adopts nano silicon dioxide, and the particle size is 300-500nm.
The catalyst adopts triethylene diamine.
The foaming agent adopts water.
The foam stabilizer adopts silicone oil AK8805.
The organic polyisocyanate adopts toluene diisocyanate.
The preparation method of the modified hemp core powder composite polyurethane foaming material comprises the following steps:
Step 1, stirring and mixing polymer polyol, modified hemp core powder and a flame retardant to form a mixture, wherein the stirring speed of stirring and mixing is 400r/min, and the stirring temperature is normal temperature;
Step 2, putting a catalyst, white oil, a foaming agent and a foam stabilizer into the mixture, and rapidly stirring to obtain a prepolymerized mixture, wherein the rapid stirring speed is 1500r/min, and the time is 30s;
and 3, adding the organic polyisocyanate into the prepolymerization mixture, stirring at a high speed, foaming and curing to obtain the modified hemp core powder composite polyurethane foam material, wherein the high-speed stirring speed is 2500r/min, the time is 9s, the foaming adopts standing free foaming, the curing temperature is room temperature, and the time is 22h.
Comparative example 1
The mass ratio of the modified hemp core powder composite polyurethane foaming material is as follows:
40 parts of polymer polyol, 30 parts of hemp core powder, 25 parts of flame retardant, 2 parts of catalyst, 3 parts of foaming agent, 2 parts of foam stabilizer, 75 parts of organic polyisocyanate and 0.8 part of white oil.
The polymer polyol is LPOP-36/30.
The flame retardant adopts multi-nano silicon dioxide, and the particle size is 300-500nm.
The catalyst adopts triethylene diamine.
The foaming agent adopts water.
The foam stabilizer adopts silicone oil AK8805.
The organic polyisocyanate adopts toluene diisocyanate.
The preparation method of the modified hemp core powder composite polyurethane foaming material comprises the following steps:
Step 1, stirring and mixing polymer polyol, modified hemp core powder and a flame retardant to form a mixture, wherein the stirring speed of stirring and mixing is 400r/min, and the stirring temperature is normal temperature;
Step 2, putting a catalyst, white oil, a foaming agent and a foam stabilizer into the mixture, and rapidly stirring to obtain a prepolymerized mixture, wherein the rapid stirring speed is 1500r/min, and the time is 30s;
and 3, adding the organic polyisocyanate into the prepolymerization mixture, stirring at a high speed, foaming and curing to obtain the modified hemp core powder composite polyurethane foam material, wherein the high-speed stirring speed is 2500r/min, the time is 9s, the foaming adopts standing free foaming, the curing temperature is room temperature, and the time is 22h.
Comparative example 2
A commercially available polyurethane foam material was used for comparative example 2.
Performance detection
The products of examples 1 to 4 and comparative examples 1 to 2 were used as test samples for performance test, and the results were as follows:
it is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those skilled in the art that the present invention may be modified or substituted for others to achieve the same technical effects, and that it is within the scope of the invention as long as the use needs are satisfied.
Claims (9)
1. The modified hemp core powder composite polyurethane foam material is characterized by comprising the following components in parts by mass:
30-50 parts of polymer polyol, 10-40 parts of modified hemp core powder, 20-30 parts of flame retardant, 1-2 parts of catalyst, 3-4 parts of foaming agent, 1-2 parts of foam stabilizer, 65-80 parts of organic polyisocyanate and 0.5-1 part of white oil, wherein the modified hemp core powder adopts titanium oxide modified hemp core powder.
2. The modified hemp core powder composite polyurethane foam material of claim 1, wherein the polymer polyol is LPOP-36/30 or LPOP-36/28G.
3. The modified hemp core powder composite polyurethane foam material of claim 1, wherein the titanium-oxygen modified hemp core powder takes hemp core powder as an inner core, a titanium-oxygen film and a silicon-oxygen film are sequentially coated from inside to outside, and the titanium-oxygen film and the silicon-oxygen film form polycondensation connection.
4. The modified hemp core powder composite polyurethane foam material of claim 1, wherein the flame retardant is a porous silica material, and the porous silica material is rich in silicon hydroxyl groups.
5. The modified hemp core powder composite polyurethane foam material of claim 1, wherein the catalyst is triethylene diamine.
6. The modified hemp core powder composite polyurethane foam material of claim 1, wherein the foaming agent is water.
7. The modified hemp core powder composite polyurethane foam material of claim 1, wherein the foam stabilizer is silicone oil AK8805.
8. The modified hemp core powder composite polyurethane foam material of claim 1, wherein the organic polyisocyanate is toluene diisocyanate.
9. The method for preparing the modified hemp core powder composite polyurethane foam material as claimed in claim 1, which is characterized by comprising the following steps:
Step 1, stirring and mixing polymer polyol, modified hemp core powder and a flame retardant to form a mixture, wherein the stirring speed of stirring and mixing is 300-500r/min, and the stirring temperature is normal temperature;
Step 2, putting a catalyst, white oil, a foaming agent and a foam stabilizer into the mixture, and rapidly stirring to obtain a prepolymerized mixture, wherein the rapid stirring speed is 1000-2000r/min, and the time is 20-40s;
and 3, adding the organic polyisocyanate into the prepolymerization mixture, stirring at a high speed, foaming and curing to obtain the modified hemp core powder composite polyurethane foam material, wherein the high-speed stirring speed is 2000-3000r/min, the time is 7-10s, the foaming adopts standing free foaming, and the curing temperature is room temperature and the time is 20-24h.
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