CN114874428A - Preparation method and application of soybean oil polyalcohol - Google Patents
Preparation method and application of soybean oil polyalcohol Download PDFInfo
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- CN114874428A CN114874428A CN202210707587.4A CN202210707587A CN114874428A CN 114874428 A CN114874428 A CN 114874428A CN 202210707587 A CN202210707587 A CN 202210707587A CN 114874428 A CN114874428 A CN 114874428A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method and application of soybean oil polyol, which comprises the steps of mixing epoxidized soybean oil, small molecular alcohol and a catalyst, carrying out ring-opening reaction at 100-180 ℃, and maintaining for 1-5 h; removing unreacted micromolecule alcohol after the reaction is finished; stirring the obtained reaction mixture, continuously introducing an epoxy compound at 70-130 ℃, and carrying out polymerization reaction for 1-5 h; curing, N 2 And stripping to remove epoxy compound monomers and aldehyde compounds to obtain the soybean oil polyol. According to the invention, the acidic catalyst with high specific surface area and high micropore content is adopted to catalyze epoxidized soybean oil to carry out ring-opening reaction and polymerization modification, so that the soybean oil polyol with odor grade less than or equal to 2.5 and aldehyde content less than or equal to 1ppm is prepared, and the polyurethane foam prepared from the soybean oil polyol has the advantages of excellent mechanical physical properties, high bio-based content and low toxic substance contentNo obvious peculiar smell.
Description
Technical Field
The invention belongs to the field of polyol synthesis, and particularly relates to a preparation method and application of low-odor low-aldehyde-content soybean oil polyol.
Background
The petroleum resources are gradually consumed and tend to be in short supply, the synthesis of polyether polyol by taking natural vegetable oil as a raw material is widely concerned, European and American countries have policy requirements, and the content of bio-based polyurethane materials is required to be more than 5%, so that the production of polyurethane foam by taking natural vegetable oil as a raw material is a trend of future development, but the control and strict strictness of odor of polyurethane materials used in the fields of soft home decoration, automobile interior decoration and the like are required, the use of the polyurethane foam is restricted due to the problem of large odor of vegetable oil, and a preparation process of the bio-based polyether polyol with low odor grade and low aldehyde content is required to be developed aiming at the problem.
Patent CN102731770B discloses a method for preparing soybean oil polyol, which adopts ester exchange and ring-opening reaction to synthesize soybean oil polyol with hydroxyl group, but the method only endows soybean oil with hydroxyl group, and does not perform any modification or post-treatment on the soybean oil, and the original odor of the soybean oil is still remained, and the odor of downstream polyurethane foam is affected. Patent CN113929576A discloses a method for preparing soybean oil polyol, which uses soybean oil as raw material, and performs epoxidation reaction to change double bonds into epoxy bonds, and then performs ring-opening reaction to obtain hydroxyl-containing soybean oil polyol, but this method does not perform any treatment on the synthesized polyol, and the problems of odor and aldehyde content are not solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method and application of soybean oil polyol, wherein the soybean oil polyol with odor grade less than or equal to 2.5 and aldehyde content less than or equal to 1ppm is prepared by catalyzing epoxidized soybean oil to carry out ring-opening reaction and polymerization modification by adopting an acid catalyst with high specific surface area and high micropore content, and polyurethane foam prepared by adopting the soybean oil polyol has excellent mechanical physical properties (tear strength, tensile rate, tensile strength and the like), high biobased content, low content of toxic substances and no obvious peculiar smell.
A preparation method of soybean oil polyalcohol comprises the following steps:
a) and ring-opening reaction: mixing epoxidized soybean oil, small molecular alcohol and a catalyst, and carrying out a ring-opening reaction at 100-180 ℃ for 1-5 h; removing unreacted micromolecule alcohol after the reaction is finished;
b) and polymerization modification: stirring the reaction mixture obtained in step a) at 70-130 deg.CContinuously introducing an epoxy compound to carry out polymerization reaction for 1-5 h; curing, N 2 And stripping to remove epoxy compound monomers and aldehyde compounds to obtain the soybean oil polyol.
Preferably, the small molecular alcohol in the step a) is one or more of methanol, ethanol, ethylene glycol and diethylene glycol, and the adding amount is 10-20% of the mass of the epoxidized soybean oil.
Preferably, the catalyst in step a) is a metallic tin and titanium supported activated carbon catalyst.
The preparation method of the catalyst comprises the following steps:
1) and active carbon modification: refluxing and stirring a modifying reagent, 20-40 mesh coconut shell activated carbon and deionized water at 40-80 ℃ for 5 hours; drying the water by distillation and drying;
2) and active carbon loading: adding the modified activated carbon prepared in the step 1), titanium salt, tin salt and water into a reaction container, stirring and soaking for a period of time, and removing water to obtain loaded activated carbon.
Preferably, in the step (1), the modifying reagent is sulfuric acid or nitric acid, preferably, the added modifying reagent is concentrated sulfuric acid or concentrated nitric acid, and the adding amount of the modifying reagent is 1-10% of the mass of the activated carbon; the adding amount of the deionized water is 1-10 times of the mass of the modifying reagent; the concentrated sulfuric acid or the concentrated nitric acid refers to sulfuric acid or nitric acid with mass fraction of more than 50%.
Preferably, in step (2), the titanium salt is phthalate ester, and can be selected from isobutyl titanate or isopropyl titanate; the tin salt is soluble salt of tin, and is selected from stannic chloride or sodium stannate; the total adding amount of the titanium salt and the tin salt is 1 to 10 percent of the mass of the activated carbon added in the step 1); the mass ratio of the titanium salt to the tin salt is 1: 0.5-3;
preferably, the catalyst is N before use 2 Activation under an atmosphere, N 2 The flow rate is 100-120 mL/min; the activation temperature is 500-600 ℃; the activation time is 5-6 h;
the specific surface area of the catalyst is 1000-1500m 2 /g, specific surface area of micropores 950- 2 Per g, the mesoporous specific surface area is 50-150m 2 Per g, an average pore diameter of 0.8 to 1.5nm and a pH of 1 to 3.
Preferably, in the step a), the adding amount of the catalyst is 1-10% of the mass of the epoxidized soybean oil;
preferably, in the step a), after the reaction is completed, the unreacted small molecular alcohol is removed under the vacuum condition of-0.09 MPa to-0.095 MPa.
Preferably, the epoxy compound in step b) is one or more of ethylene oxide, propylene oxide and butylene oxide; the total addition of the epoxide is 4.4 to 12 times of the mass of the epoxidized soybean oil;
preferably, in the step b), the epoxy compound monomer and the aldehyde compound are removed under the vacuum condition of-0.09 MPa to-0.095 MPa after the reaction is finished.
The soybean oil polyol prepared by the invention contains an X structure, and the general formula of the X structure is as follows:
wherein m is 0-50, n is 0-30, and m + n is not less than 25.
The soybean oil polyol also comprises structures Y and Z, and the general formula is as follows:
wherein, a is 0-50, b is 0-30, a + b is not less than 10;
wherein c is 0-50, d is 0-30, and c + d is not less than 10;
in soybean oil polyol, the ratio of the structure X is more than or equal to 95.0 (wt)%; the proportion of the structure Y is less than or equal to 4.0 (wt)%; the ratio of the structure Z is less than or equal to 1.0 (wt)%.
The soybean oil polyol synthesized by the conventional process is easy to self-polymerize, so that a high molecular weight polymer is formed; the invention adopts a self-made solid acid catalyst, wherein tin element catalyzes the ring-opening reaction of epoxide; titanium element inhibits the polymerization reaction among the molecules of the epoxidized soybean oil, so that the ring-opening reaction of epoxide can be catalyzed, the polymerization reaction among the molecules of the epoxidized soybean oil is avoided, and the content of the ultra-high molecular weight polymer (structure Y, Z) in the final product is not higher than 5 percent;
the invention also provides application of the soybean oil polyol prepared by the method disclosed by the invention in preparation of polyurethane foam.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention prepares soybean oil polyol with odor grade less than or equal to 2.5, aldehyde content less than or equal to 1ppm and ultra-high molecular weight polymer (structure Y, Z) less than or equal to 5.0 (wt%);
2) the invention prepares a product with a specific surface area higher than 1000m 2 A solid catalyst for synthesizing vegetable oil polyalcohol, wherein the solid catalyst has an average pore diameter of less than 1.5 nm; the large specific surface area of the catalyst is beneficial to adsorbing small molecular organic matters (formaldehyde, acetaldehyde, propionaldehyde and the like) in the soybean oil polyalcohol;
3) after the soybean oil is subjected to ring-opening epoxidation by adopting the solid catalyst, the soybean oil is subjected to graft modification by utilizing the epoxide, so that the molecular chain segment of the soybean oil polyol is prolonged, and the odor of the soybean oil polyol is favorably reduced;
4) the soybean oil polyol prepared by the method is used for preparing polyurethane soft foam, the mechanical physical properties (tear strength, tensile rate, tensile strength and the like) of the foam are excellent, the bio-based content is high, the content of toxic substances is low, no obvious peculiar smell exists, and the soybean oil polyol can be widely used in the fields of soft home, automobile seats and the like.
Detailed Description
Aldehyde content test method: the aldehyde ketone content was measured by LC1100 liquid chromatograph using the principle that carbonyl compounds react with 2, 4-Dinitrophenylhydrazine (DNPH) to produce hydrazone derivatives. And (3) drawing external standard method calibration curves of formaldehyde-DNPH, acetaldehyde-DNPH, propionaldehyde-DNPH, acrolein-DNPH and acetone-DNPH, and establishing a high performance liquid chromatography to determine the content of aldehyde substances in the polyether.
Example 1:
the preparation method of the vegetable oil polyalcohol catalyst A comprises the following steps: mixing 20-40 mesh coconut shellAdding 100g of activated carbon, 1g of concentrated sulfuric acid (mass fraction is 98%) and 10g of deionized water into a round-bottom flask, refluxing and stirring at 80 ℃ for 5 hours, evaporating to remove water, and drying in an oven for 24 hours; adding dried active carbon, 0.5g of isobutyl titanate, 0.5g of stannic chloride and 5g of deionized water into a round-bottom flask, stirring for 5 hours at 80 ℃, removing water by rotary evaporation, putting into a tubular activation furnace, and adding 100mL/min N at 500 ℃ in a 100mL/min 2 Activating for 6h in the atmosphere, and cooling to obtain the catalyst A. Characterization of the test catalyst, its specific surface area was 1253m 2 (per gram), specific surface area of micropores 1030m 2 G, mesoporous specific surface area 150m 2 Per g, average pore diameter 1.0nm, catalyst pH 2.93.
Example 2:
the preparation method of the vegetable oil polyalcohol catalyst B comprises the following steps: adding 100g of 20-40-mesh coconut shell activated carbon, 10g of concentrated nitric acid (mass fraction of 68%) and 10g of deionized water into a round-bottom flask, refluxing and stirring at 40 ℃ for 5 hours, evaporating to remove water, and drying in an oven for 24 hours; adding dried activated carbon, 5g of isobutyl titanate, 2.5g of sodium stannate and 50g of deionized water into a round-bottom flask, stirring for 5 hours at 40 ℃, dewatering, putting into a tubular activation furnace, and adding 120mL/min N at 600 ℃ in a 120mL/min 2 And activating for 5 hours in the atmosphere, and cooling to obtain the catalyst B. Characterization of the test catalyst, its specific surface area is 1498m 2 Per g, specific surface area of micro-pores 1369m 2 G, mesoporous specific surface area 112m 2 In g, the average pore diameter was 0.8nm and the catalyst pH was 1.32.
Example 3:
the preparation method of the vegetable oil polyalcohol catalyst C comprises the following steps: adding 100g of 20-40 mesh coconut shell activated carbon, 5g of concentrated nitric acid (mass fraction of 68%) and 10g of deionized water into a round-bottom flask, refluxing and stirring at 60 ℃ for 5 hours, evaporating to remove water, and drying in an oven for 24 hours; adding dried activated carbon, 2.5g of isopropyl titanate, 7.5g of stannic chloride and 50g of deionized water into a round-bottom flask, stirring at 60 ℃ for 5 hours, dewatering, putting into a tubular activation furnace, and adding 120mL/min N at 600 ℃ in a tubular activation furnace 2 And activating for 5 hours in the atmosphere, and cooling to obtain the catalyst C. Characterization of the test catalyst, its specific surface area is 1031m 2 (per gram), specific surface area of micropores 906m 2 /g，Mesoporous specific surface area 52m 2 Per g, average pore diameter 1.5nm, catalyst pH 1.12.
Example 4:
the synthesis method of the soybean oil polyalcohol with low odor and low aldehyde content comprises the following steps: a) adding 500g of epoxidized soybean oil, 50g of methanol and 5g of catalyst A into a high-pressure reaction kettle, fully replacing 10 times with nitrogen, and maintaining the reaction for 1 hour at 180 ℃ under stirring; after the reaction is finished, removing unreacted micromolecule alcohol under the vacuum condition of-0.095 MPa, and maintaining for 1 h; b) continuously introducing a mixture of ethylene oxide and propylene oxide (2420 g of ethylene oxide and 638g of propylene oxide) into the reaction mixture for 5 hours at 70 ℃ under stirring; aging for 2h, adding N 2 Stripping, removing epoxy compound monomers and aldehyde compounds under the vacuum condition of-0.095 MPa, maintaining for 60min, filtering out a solid catalyst, cooling and discharging to prepare the soybean oil polyol.
Example 5:
the synthesis method of the soybean oil polyalcohol with low odor and low aldehyde content comprises the following steps: a) adding 500g of epoxidized soybean oil, 20g of methanol, 80g of ethanol and 50g of catalyst B into a high-pressure reaction kettle, fully replacing 10 times with nitrogen, and maintaining the reaction for 5 hours under stirring at 100 ℃; after the reaction is finished, removing unreacted micromolecule alcohol under the vacuum condition of-0.093 MPa, and maintaining for 1 h; b) continuously introducing a mixture of ethylene oxide and propylene oxide (360 g of ethylene oxide and 5742g of propylene oxide) into the reaction mixture for 3 hours at 100 ℃ under stirring; aging for 2h, adding N 2 Stripping, removing epoxy compound monomers and aldehyde compounds under the vacuum condition of-0.090 MPa, maintaining for 60min, filtering out the solid catalyst, cooling and discharging to obtain the soybean oil polyol.
Example 6:
the synthesis method of the soybean oil polyalcohol with low odor and low aldehyde content comprises the following steps: a) adding 500g of epoxidized soybean oil, 40g of methanol, 30g of diethylene glycol and 25g of catalyst C into a high-pressure reaction kettle, fully replacing 10 times with nitrogen, and maintaining the reaction for 3 hours under stirring at 130 ℃; after the reaction is finished, removing unreacted micromolecule alcohol under the vacuum condition of-0.090 MPa, and maintaining for 1 h; b) continuously introducing propylene oxide into the reaction mixture for 1h under the stirring at 130 DEG CThe alkane is 3828 g; aging for 2h, adding N 2 Stripping, removing epoxy compound monomers and aldehyde compounds under the vacuum condition of-0.093 MPa, maintaining for 60min, filtering out a solid catalyst, cooling and discharging to prepare the soybean oil polyol.
Comparative example 1:
the synthesis method of the soybean oil polyalcohol comprises the following steps: adding 500g of epoxidized soybean oil, 40g of methanol, 30g of diethylene glycol, 0.5g of stannic chloride and 0.25g of isopropyl titanate into a high-pressure reaction kettle, fully replacing 10 times with nitrogen, and maintaining the reaction for 3 hours at 130 ℃ under stirring; after the reaction is finished, removing unreacted micromolecule alcohol under the vacuum condition of-0.090 MPa, maintaining for 1h, cooling and discharging to prepare the soybean oil polyol.
The prepared soybean oil polyalcohol has the following indexes of odor and aldehyde content:
| index (I) | Odor grade | Formaldehyde ppm | Acetaldehyde ppm | Propionaldehyde ppm | Acrolein ppm | Acetone ppm |
| Example 4 | 2.3 | Not detected out | 0.12 | 0.83 | Not detected out | Not detected out |
| Example 5 | 2.4 | Not detected out | 0.28 | 0.63 | Not detected out | Not detected out |
| Example 6 | 2.1 | 0.13 | Not detected out | 0.52 | Undetected | 0.13 |
| Comparative example 1 | 4.3 | 18.19 | 3.22 | 3.31 | 0.98 | 1.78 |
Polyurethane foams were prepared using the following components:
F3156D (produced by Wanhua chemical group Co., Ltd., starting with glycerin, EO and PO, hydroxyl value 56 mgKOH/g); f3135 (produced by Wanhua chemical group, Ltd., glycerin-initiated, EO and PO, hydroxyl value: 35 mgKOH/g); MDI (manufactured by Wanhua chemical group Co., Ltd.); silicone oil DC501, Y10366; catalyst a33, T9, T12.
The foam formulation and properties were as follows:
according to the application example of the invention, the foam prepared from the soybean oil polyol obtained by grafting and modifying the soybean oil by using the epoxy compound through the synthesis process disclosed by the invention has more excellent mechanical properties and very high practical value.
Claims (9)
1. The preparation method of the soybean oil polyol is characterized by comprising the following steps:
a) and ring-opening reaction: mixing epoxidized soybean oil, small molecular alcohol and a catalyst, and carrying out a ring-opening reaction at 100-180 ℃ for 1-5 h; removing unreacted micromolecule alcohol after the reaction is finished;
b) and polymerization modification: stirring the reaction mixture obtained in the step a), and continuously introducing an epoxy compound at 70-130 ℃ to perform polymerization reaction; curing, N 2 And stripping to remove epoxy compound monomers and aldehyde compounds to obtain the soybean oil polyol.
2. The preparation method of claim 1, wherein the small molecule alcohol in step a) is one or more of methanol, ethanol, ethylene glycol and diethylene glycol, and the addition amount is 10-20% of the mass of the epoxidized soybean oil;
preferably, the catalyst in step a) is a metallic tin and titanium supported activated carbon catalyst;
preferably, in the step a), the adding amount of the catalyst is 1-10% of the mass of the epoxidized soybean oil;
preferably, in the step a), after the reaction is completed, the unreacted small molecular alcohol is removed under the vacuum condition of-0.09 MPa to-0.095 MPa.
3. The method for preparing the catalyst according to claim 1 or 2, comprising the steps of:
1) and active carbon modification: refluxing and stirring a modifying reagent, coconut shell activated carbon and deionized water at 40-80 ℃; drying the water by distillation and drying;
2) and active carbon loading: adding the modified activated carbon prepared in the step 1), titanium salt, tin salt and water into a container, stirring and soaking for a period of time, and removing water to obtain the loaded activated carbon.
4. The preparation method according to any one of claims 1 to 3, wherein in the step 1), the modifying reagent is sulfuric acid or nitric acid, preferably, the modifying reagent is concentrated sulfuric acid or concentrated nitric acid, and the added amount of the modifying reagent is 1 to 10 percent of the mass of the activated carbon; the concentrated sulfuric acid or the concentrated nitric acid refers to sulfuric acid or nitric acid with mass fraction of more than 50%; preferably, in the step 1), the addition amount of the deionized water is 1-10 times of the mass of the modifying reagent.
5. The process according to any one of claims 1 to 4, wherein in step 2), the titanium salt is a phthalate selected from isobutyl titanate or isopropyl titanate; the tin salt is soluble salt of tin, and is selected from stannic chloride or sodium stannate; the total adding amount of the titanium salt and the tin salt is 1-10% of the mass of the activated carbon added in the step 1); the mass ratio of the titanium salt to the tin salt is 1: 0.5-3.
6. The process according to any one of claims 1 to 5, wherein the catalyst is used in the presence of N 2 Activation under an atmosphere, N 2 The flow rate is 100-120 mL/min; the activation temperature is 500-600 ℃; the activation time is 5-6 h.
7. The process according to any one of claims 1 to 6, wherein the catalyst has a specific surface area of 1000-1500m 2 /g, specific surface area of micropores 950- 2 Per g, the mesoporous specific surface area is 50-150m 2 Per g, average pore diameter of 0.8-1.5nm, pH1-3。
8. The process according to any one of claims 1 to 7, wherein the epoxy compound in step b) is one or more of ethylene oxide, propylene oxide and butylene oxide; the total addition of the epoxide is 4.4 to 12 times of the mass of the epoxidized soybean oil; preferably, in the step b), the epoxy compound monomer and the aldehyde compound are removed under the vacuum condition of-0.09 MPa to-0.095 MPa after the reaction is finished.
9. The soybean oil polyol produced by the production method according to any one of claims 1 to 8, comprising a structure of X having the general formula:
wherein m is 0-50, n is 0-30, and m + n is not less than 25;
the soybean oil polyol also comprises structures Y and Z, and the general formula is as follows:
wherein, a is 0-50, b is 0-30, a + b is not less than 10;
wherein c is 0-50, d is 0-30, and c + d is not less than 10;
in soybean oil polyalcohol, the proportion of the structure X is more than or equal to 95.0 (wt)%; the proportion of the structure Y is less than or equal to 4.0 (wt)%; the ratio of the structure Z is less than or equal to 1.0 (wt)%.
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| JP2006001865A (en) * | 2004-06-16 | 2006-01-05 | Asahi Denka Kogyo Kk | Hydroxyalkoxy compound derived from polymerized fats and oils |
| CN102731770A (en) * | 2012-06-28 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of soybean oil polyol |
| CN109369901A (en) * | 2018-09-29 | 2019-02-22 | 南京工业大学 | Vegetable oil polyurethane flexible foam polyol and preparation method and application thereof |
| CN110790916A (en) * | 2019-10-09 | 2020-02-14 | 万华化学集团股份有限公司 | Preparation method of low-odor polyether polyol |
| CN112876666A (en) * | 2021-01-14 | 2021-06-01 | 长华化学科技股份有限公司 | Low-aldehyde and low-odor polyether polyol and preparation method and application thereof |
| CN113908834A (en) * | 2021-08-11 | 2022-01-11 | 万华化学集团股份有限公司 | Preparation method of aldehyde-removing catalyst and refining method of polyether polyol |
| CN113929576A (en) * | 2021-10-15 | 2022-01-14 | 浙江嘉澳环保科技股份有限公司 | Preparation method of soybean oil polyalcohol |
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