A bio-based polyurethane material and its preparation method and application
By using green tea seed oil to prepare bio-based polyether polyols and adding poly to isocyanate, the problem of polyurethane material production depends on petrochemical resources, and the effect of resource conservation and sustainable development is achieved.
Patent Information
- Application Number
- CN202411900582.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-23
- Publication Date
- 2025-04-01
AI Technical Summary
The production of existing polyurethane materials depends on petrochemical resources, resulting in resource depletion and unsustainable development.
Green tea seed oil is used as the biomass raw material, and bio-based polyether polyol is prepared by preparing green tea seed oil-based polyether polyol and combining isocyanate for addition to polypolytics.
Effectively save petrochemical resources, promote the sustainable development of polyurethane materials, and do not use polyols, which simplifies the preparation process.
Smart Images
Figure CN119735778A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of polyurethane material synthesis, and specifically relates to a bio-based polyurethane material and a preparation method and application thereof. Background Art
[0002] Polyurethane is the abbreviation of polyurethane, which is formed by the addition polymerization of polyols and isocyanates. It is a polymer compound containing many repeated carbamate segments on the polymer main chain. It is known as the fifth largest polymer material in the world. Due to its excellent properties, it is widely used in light industry, chemical industry, electronics, textiles, medical treatment, construction, building materials, automobiles, national defense and other fields. With the increasing use of polyurethane materials year by year, a series of problems have also been brought about.
[0003] As one of the two main raw materials for synthetic polyurethane foam materials, polyols are currently mostly derived from petrochemical resources. Due to the depletion and non-renewability of petrochemical resources, the sustainable development of the polyurethane industry is seriously restricted. Therefore, starting from renewable biomass raw materials, developing bio-based polyols for the preparation of bio-based polyurethane materials has become the future development direction of the polyurethane industry.
[0004] Green tea seed oil is a vegetable oil extracted from tea tree seeds. It is a biomass raw material, and its main components are oleic acid, linoleic acid, linolenic acid, etc. It can be used as a raw material for preparing bio-based polyols, thereby preparing bio-based polyurethane materials. The existing technology has not reported the use of green tea seed oil to prepare bio-based polyurethane materials. Summary of the invention
[0005] In view of the deficiencies in the prior art, the present invention provides a bio-based polyurethane material and a preparation method and application thereof, with the purpose of utilizing the biomass raw material green tea seed oil to prepare bio-based polyols, and then preparing bio-based polyurethane materials, which can save petrochemical resources and is conducive to the beneficial development of polyurethane materials.
[0006] In order to achieve the above object, the present invention provides a method for preparing a bio-based polyurethane material, comprising the following steps: Step S1, preparation of green tea seed oil-based polyether polyol, adding green tea seed oil and a first catalyst to a glass reactor, stirring, then dropping 30% hydrogen peroxide to react, then heating and reflux, standing for stratification, separating acid water, washing twice, and reducing the pressure to less than 0.1% of the water content to obtain hydroxylated green tea seed oil; adding the obtained hydroxylated green tea seed oil and the second catalyst to a high-pressure reactor, evacuating, replacing with nitrogen twice, then adding propylene oxide / ethylene oxide to react, refining, neutralizing and dehydrating with acid to obtain green tea seed oil-based polyether polyol; Step S2, preparation of bio-based polyurethane material, taking the green tea seed oil-based polyether polyol obtained in step S1 into a foaming mold, adding a blowing agent, a catalyst, a chain extender, and a foam stabilizer thereto, stirring, then adding isocyanate thereto and stirring, free foaming to obtain a crude product, and ripening and curing the crude product to obtain a bio-based polyurethane material.
[0007] Furthermore, in step S1, the first catalyst is one of formic acid or acetic acid; the second catalyst is one of alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, metal halides and aluminum oxide; and the acid is one of phosphoric acid or pyrophosphoric acid.
[0008] Furthermore, in step S1, the mass of the first catalyst is 0.1-2.0% of the total mass of the reactants; the mass of the second catalyst is 0.1-1.0% of the total mass of the reactants; the molar ratio of 30% hydrogen peroxide to green tea seed oil is 1.0-4.0:1; and the mass ratio of hydroxylated green tea seed oil to propylene oxide / ethylene oxide is 1:0.9-13.
[0009] Further, in step S1, green tea seed oil and the first catalyst are added to the glass reactor, and the stirring time is 10 to 20 minutes; 30% hydrogen peroxide is added dropwise for reaction at a temperature of 40 to 60°C for 6 to 8 hours; the heating temperature is 100 to 110°C; the reflux time is 6 hours; the propylene oxide / ethylene oxide is added for reaction for 2 to 4 hours; the pH value for neutralization with acid is 5.5 to 7.0; the temperature for dehydration with acid is 90 to 120°C for 60 to 140 minutes.
[0010] Furthermore, in step S2, the catalyst is one of stannous octoate, dibutyltin dilaurate, ethylene glycol antimony, triethylenediamine, dibutyltin diacetate and triethanolamine; the chain extender is one of ethylene glycol, 1,4-butanediol, 2,3-butanediol, propylene glycol and 1,2-propylene glycol; and the foam stabilizer is one of the silicone surfactants B8462, B8409, B8510 and B8545.
[0011] Furthermore, in step S2, the isocyanate is one of diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate and hexamethylene diisocyanate.
[0012] Furthermore, in step S2, the mass ratio of bio-based polyether polyol: water: catalyst: chain extender: foam stabilizer: isocyanate is 100-120: 4-6: 1-2: 1-4: 1-3: 200-220.
[0013] Furthermore, in step S2, a blowing agent, a catalyst, a chain extender, and a foam stabilizer are added, and the stirring speed is 1000-2500 r / min for 10-15 s; the isocyanate is added and stirred for 8-12 s; the aging temperature is 25-35° C. for 1-2 hours; and the curing temperature is 50-60° C. for 5-8 hours.
[0014] The present invention also provides a bio-based polyurethane material, which is prepared by the above-mentioned method for preparing the bio-based polyurethane material.
[0015] The present invention also provides an application of a bio-based polyurethane material, wherein the bio-based polyurethane material is applied to one or more of the fields of construction, automobiles, electronics and furniture.
[0016] Beneficial Effects The invention discloses a method for preparing a bio-based polyurethane material. The method can use green tea seed oil, a biomass raw material, to prepare a bio-based polyol, and then polyadd the bio-based polyol with isocyanate under the action of other reagents to obtain the bio-based polyurethane material. The method for preparing a bio-based polyurethane material does not use polyols during the preparation process, can effectively save petrochemical resources, and is conducive to the sustainable development of polyurethane materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 The present invention is a flow chart of a method for preparing a bio-based polyurethane material. DETAILED DESCRIPTION
[0018] The present invention is further illustrated by specific examples below. These examples are exemplary and are intended to illustrate the problem and explain the present invention, but are not intended to be limiting.
[0019] Example 1 A method for preparing a bio-based polyurethane material comprises the following steps: Step S1, preparation of green tea seed oil-based polyether polyol, adding 300g of green tea seed oil and 4.6g of the first catalyst formic acid into a 1L glass reactor, stirring for 15 minutes, adding 110g of 30% hydrogen peroxide dropwise, reacting at 50°C for 7 hours, heating to 105°C, reflux for 6 hours, standing and stratifying, separating acid water, washing twice, and reducing the pressure to less than 0.1% of the water content to obtain hydroxylated green tea seed oil with a hydroxyl value of 183mgKOH / g; 200 g of the obtained hydroxylated green tea seed oil and 3 g of the second catalyst sodium hydroxide were added to a high-pressure reactor, vacuumed, replaced with nitrogen twice, and then 500 g of propylene oxide / ethylene oxide (9.4 / 0.6) was added, reacted for 3 hours, refined, neutralized and dehydrated with phosphoric acid, neutralized to pH=6, and dehydrated at a temperature of 90°C for 120 minutes to obtain a green tea seed oil-based polyether polyol with a hydroxyl value of 39.1 mgKOH / g; Step S2, preparation of bio-based polyurethane material, taking 100g of the green tea seed oil-based polyether polyol obtained in step S1 into a foaming mold, adding 4g of foaming agent water, 1.5g of catalyst dibutyltin dilaurate, 3g of chain extender ethylene glycol, 2g of foam stabilizer B8462, stirring at a stirring speed of 1500r / min for 10s, then adding 203g of toluene diisocyanate thereto, stirring for 8s, free foaming to obtain a crude product, and ripening and curing the crude product, wherein the ripening temperature is 27°C, the time is 1.5 hours, and the curing temperature is 52°C, the time is 6 hours, to obtain a bio-based polyurethane material.
[0020] Example 2 Step S1, preparation of green tea seed oil-based polyether polyol, adding green tea seed oil 400g, a first catalyst formic acid 5.2g into a 1L glass reactor, stirring for 15 minutes, adding 30% hydrogen peroxide 161g dropwise, reacting at 50°C for 7 hours, heating to 105°C, reflux for 6 hours, standing for stratification, separating acid water, washing twice, reducing pressure to less than 0.1% of the water content, and obtaining hydroxylated green tea seed oil with a hydroxyl value of 197mgKOH / g; taking 300 g of the obtained hydroxylated green tea seed oil and 4.3 g of the second catalyst sodium hydroxide were added to a high-pressure reactor, vacuumed, replaced with nitrogen twice, and then 600 g of propylene oxide / ethylene oxide (9.4 / 0.6) was added, reacted for 3 hours, refined, neutralized and dehydrated with phosphoric acid, neutralized to pH=7, and dehydrated at a temperature of 100°C for 90 minutes to obtain a green tea seed oil-based polyether polyol with a hydroxyl value of 45.3 mgKOH / g; Step S2, preparation of bio-based polyurethane material, taking 110g of the green tea seed oil-based polyether polyol obtained in step S1 into a foaming mold, adding 4g of foaming agent water, 2g of catalyst stannous octoate, 3g of chain extender 1,4-butanediol, and 2g of foam stabilizer B8510 thereto, stirring at a stirring speed of 1500r / min for 12s, then adding 206g of toluene diisocyanate thereto, stirring for 8s, free foaming to obtain a crude product, and ripening and curing the crude product, wherein the ripening temperature is 29°C, the time is 2 hours, and the curing temperature is 55°C, the time is 6 hours, to obtain a bio-based polyurethane material.
[0021] Example 3 Step S1, preparation of green tea seed oil-based polyether polyol, adding 500g of green tea seed oil and 6.0g of the first catalyst formic acid into a 1L glass reactor, stirring for 15 minutes, adding 214g of 30% hydrogen peroxide dropwise, reacting at 50°C for 7 hours, heating to 105°C, reflux for 6 hours, standing and stratifying, separating acid water, washing twice, and reducing the pressure to less than 0.1% of the water content to obtain hydroxylated green tea seed oil with a hydroxyl value of 218mgKOH / g; taking 400 g of the obtained hydroxylated green tea seed oil and 6.2 g of the second catalyst sodium hydroxide were added to a high-pressure reactor, vacuumed, replaced with nitrogen twice, and then 900 g of propylene oxide / ethylene oxide (9.4 / 0.6) was added, reacted for 3 hours, refined, neutralized and dehydrated with phosphoric acid, neutralized to pH=6, and dehydrated at a temperature of 110°C for 70 minutes to obtain a green tea seed oil-based polyether polyol with a hydroxyl value of 48.3 mgKOH / g; Step S2, preparation of bio-based polyurethane material, taking 120g of the green tea seed oil-based polyether polyol obtained in step S1 into a foaming mold, adding 5g of foaming agent water, 2g of catalyst ethylene glycol antimony, 4g of chain extender 1,2-propylene glycol, 3g of foam stabilizer B8409, stirring at a stirring speed of 2000r / min for 15s, then adding 214g of toluene diisocyanate thereto, stirring for 10s, free foaming to obtain a crude product, and ripening and curing the crude product, wherein the ripening temperature is 30°C, the time is 2 hours, and the curing temperature is 60°C, the time is 7 hours, to obtain a bio-based polyurethane material.
Claims
1. A method for preparing a bio-based polyurethane material, characterized in that: The steps include: Step S1, preparation of green tea seed oil-based polyether polyol, adding green tea seed oil and a first catalyst to a glass reactor, stirring, then dropping 30% hydrogen peroxide to react, then heating and refluxing, standing for stratification, separating acid water, then washing twice with water, reducing pressure and vacuuming to a moisture content of less than 0.1%, and hydroxylating the green tea seed oil; adding the obtained hydroxylated green tea seed oil and the second catalyst to a high-pressure reactor, evacuating, replacing with nitrogen twice, then adding propylene oxide / ethylene oxide to react, refining, neutralizing and dehydrating with acid, and obtaining green tea seed oil-based polyether polyol; Step S2, preparation of bio-based polyurethane material, taking the green tea seed oil-based polyether polyol obtained in step S1 into a foaming mold, adding a blowing agent, a catalyst, a chain extender, and a foam stabilizer thereto, stirring, then adding isocyanate thereto and stirring, free foaming to obtain a crude product, and ripening and curing the crude product to obtain a bio-based polyurethane material.
2. The method for preparing a bio-based polyurethane material according to claim 1, characterized in that: In step S1, the first catalyst is one of formic acid or acetic acid; the second catalyst is one of alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, metal halides and aluminum oxide; the acid is one of phosphoric acid or pyrophosphoric acid.
3. The method for preparing a bio-based polyurethane material according to claim 1, characterized in that: In step S1, the mass of the first catalyst is 0.1-2.0% of the total mass of the reactants; the mass of the second catalyst is 0.1-1.0% of the total mass of the reactants; the molar ratio of the 30% hydrogen peroxide to the green tea seed oil is 1.0-4.0:1; the mass ratio of the hydroxylated green tea seed oil to propylene oxide / ethylene oxide is 1:0.9-13.
4. The method for preparing a bio-based polyurethane material according to claim 1, characterized in that: In step S1, green tea seed oil and a first catalyst are added to a glass reactor, and the stirring time is 10 to 20 minutes; the temperature for dropwise addition of 30% hydrogen peroxide for reaction is 40 to 60°C, and the time is 6 to 8 hours; the temperature for heating is 100 to 110°C; the reflux time is 6 hours; the time for adding propylene oxide / ethylene oxide to react is 2 to 4 hours; the pH value for neutralization with acid is 5.5 to 7.0; the temperature for dehydration with acid is 90 to 120°C, and the time is 60 to 140 minutes.
5. The method for preparing a bio-based polyurethane material according to claim 1, characterized in that: In step S2, the catalyst is one of stannous octoate, dibutyltin dilaurate, ethylene glycol antimony, triethylenediamine, dibutyltin diacetate and triethanolamine; the chain extender is one of ethylene glycol, 1,4-butanediol, 2,3-butanediol, propylene glycol and 1,2-propylene glycol; the foam stabilizer is one of the silicone surfactants B8462, B8409, B8510 and B8545.
6. The method for preparing a bio-based polyurethane material according to claim 1, characterized in that: In step S2, the isocyanate is one of diphenylmethane diisocyanate, liquefied diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate and hexamethylene diisocyanate.
7. The method for preparing a bio-based polyurethane material according to claim 1, characterized in that: In step S2, the mass ratio of the bio-based polyether polyol: water: catalyst: chain extender: foam stabilizer: isocyanate is 100-120: 4-6: 1-2: 1-4: 1-3: 200-220.
8. The method for preparing a bio-based polyurethane material according to claim 1, characterized in that: In step S2, the blowing agent, catalyst, chain extender, and foam stabilizer are added and stirred at a stirring speed of 1000-2500 r / min for 10-15 s; the isocyanate is added and stirred for 8-12 s; the aging temperature is 25-35° C. for 1-2 hours; and the curing temperature is 50-60° C. for 5-8 hours.
9. A bio-based polyurethane material, characterized in that: The bio-based polyurethane material is prepared by the method for preparing the bio-based polyurethane material according to any one of claims 1 to 8.
10. An application of a bio-based polyurethane material, characterized in that: The bio-based polyurethane material according to claim 9 is applied to one or more of the fields of construction, automobile, electronics and furniture.