KR101631606B1 - Preparing method for biopolyol from epoxidated-vegetable oil - Google Patents
Preparing method for biopolyol from epoxidated-vegetable oil Download PDFInfo
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- KR101631606B1 KR101631606B1 KR1020150038739A KR20150038739A KR101631606B1 KR 101631606 B1 KR101631606 B1 KR 101631606B1 KR 1020150038739 A KR1020150038739 A KR 1020150038739A KR 20150038739 A KR20150038739 A KR 20150038739A KR 101631606 B1 KR101631606 B1 KR 101631606B1
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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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
- C08G2230/00—Compositions for preparing biodegradable polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/16—Biodegradable polymers
Abstract
Description
The present invention relates to a process for preparing a bio-polyol by reacting an epoxidized vegetable oil with an alkali metal oxide catalyst or ZnCl 2 catalyst with a hydroxyl functional material.
The polyurethane is produced through a urethane reaction using a polyol compound having a hydroxyl group (-OH) and an isocyanate compound having an isocyanate group (-NCO) as raw materials. Until recently, the polyurethane industry used polyols obtained from petrochemicals as raw materials. However, due to environmental awareness and the demand for renewable biopolyols, the demand for waste cooking oil, milk, palm oil, flax oil, There is a growing interest in the development of a versatile eco-friendly polyol material. In general, petroleum-based polyols have advantages of low viscosity and processability and excellent physical properties of the produced polyurethane, whereas bio-polyols produced from natural oils have low usability compared to petroleum-based polyols and have excellent physical properties Is known to have a low problem. Despite these problems, development of biopolyols has been progressing steadily, and attempts to offset the disadvantages of biopolyols due to the development of additives and the like have continued.
The production method of the bio-polyol can largely be classified into a biological synthesis method and a chemical synthesis method. Large companies such as Cargill, Dupont, and AMD manufacture and sell bio-polyols by biological methods using vegetable oils. However, there is a problem that mass production is not easy due to the nature of biological methods. Organic synthesis is preferred over commercial biological synthesis.
The prior art for producing a bio-polyol by a chemical synthesis method is as follows.
A first ester exchange reaction using a vegetable oil, a polyhydric alcohol or a polyhydric amine, and a catalyst by the method disclosed in Patent Document 1 (Korean Patent Publication No. 10-0849123); 2) a second ester exchange reaction by adding a polyhydric alcohol; 3) an esterification reaction by adding a polybasic acid and a catalyst; And 4) adding a catalyst adsorbent and water, stirring and filtering to remove the catalyst; And a method for synthesizing a biodegradable polyol having a high functional group.
In the method disclosed in Patent Document 2 (Korean Patent Laid-Open Publication No. 10-2010-0099089), active oxygen is added to vegetable oil to prepare an epoxidized oil, and then methanol is added in an acidic solution of phosphoric acid to prepare a biodegradable polyol There is a way.
(1) a process of epoxidizing triglyceride of a vegetable oil, (2) a process of reacting the reaction product of maleic acid and a polyhydric alcohol with an epoxy resin prepared in 1) above under an acid catalyst in the same manner as described in Patent Document 3 (Korean Patent No. 10-1205322) And a step of reacting the cargo.
In the above conventional method, since a strong inorganic acid catalyst such as phosphoric acid or sulfuric acid is used in the process of preparing the bio-polyol from the epoxidized vegetable oil, if the acid catalyst is not completely removed after the completion of the reaction, it remains in the final product and causes another problem . In addition, when an inorganic acid catalyst is used to react the epoxidized vegetable oil and the hydroxyl functional substance, the inorganic acid catalyst has a high affinity with the prepared polyol and is not filtered due to affinity with water formed during neutralization A tendency is required to take an infinite amount of time. Such a method of producing a bio-polyol that is not easy to filtrate is unsuitable as a mass production method.
The present invention excludes the use of a strong inorganic acid catalyst used in the process of producing a biopolyol from epoxidized vegetable oil, while filtering the biopolyol produced even when reacting with a compound having a low molecular weight or a high molecular weight as a hydroxyl functional substance It is an object of the present invention to provide an improved production method of a bio-polyol which can be applied to a mass production process with ease.
In order to solve the above problems, in the present invention, when the epoxidized vegetable oil is reacted with the hydroxyl functional substance, the reaction is carried out in the presence of an alkali metal oxide catalyst or a biocatalyst which is carried out under a temperature of 50 ° C to 200 ° C under a ZnCl 2 catalyst And a method for producing the polyol.
Conventional methods require special equipment that does not cause acid corrosion by using inorganic acids such as sulfuric acid and phosphoric acid as a catalyst, and there has been a problem of environmental pollution due to generation of strong acid-containing wastewater. However, in the present invention, the use of a strong acid is excluded, thereby reducing the facility cost and the waste water treatment cost.
In addition, strong acid catalysts such as sulfuric acid and phosphoric acid have high affinity with hydroxyl functional materials, so that the produced bio-polyols are not easily filtered. However, in the present invention, by selectively using an alkali metal oxide catalyst or ZnCl 2 catalyst having no affinity with the produced polyol, the filtration process of the bio-polyol is simplified or there is no need for filtration. In particular, when an alkali metal oxide catalyst is used, bio-polyol produced by reacting an epoxidized vegetable oil with a hydroxyl-functional substance having a high molecular weight can be easily filtered. In addition, since ZnCl 2 does not affect physical properties such as transparency even if it remains in the production of polyurethane, it is also possible to omit the filtration step of the bio-polyol produced using the ZnCl 2 catalyst.
Accordingly, the present invention is useful as a method for mass production of bio-polyols for producing polyurethane or carbamate resins used as materials for construction sandwich panels, refrigerator insulation materials, LNG insulation materials, container insulation materials, spray insulation materials and double insulation pipes.
The present invention relates to a process for preparing bio-polyols by reacting epoxidized vegetable oils with hydroxyl functional materials.
Specifically, in the present invention, an alkali metal oxide catalyst or a ZnCl 2 catalyst is used as a catalyst for the reaction between the epoxidized vegetable oil and the hydroxyl functional substance, and preferably an alkali metal oxide catalyst is used. The alkali metal oxide catalyst may specifically be MgO, CaO or a mixture thereof. Since the CaO (calcium oxide) reacts with water and changes into a poorly soluble calcium hydroxide (Ca (OH) 2 ), the solid catalyst in the form of a solid Based catalyst) and can be easily separated after the reaction. Also, if ZnCl 2 catalyst is used, even if ZnCl 2 remains in the produced polyol, it can be used as a starting material for synthesis of polyurethane and the like, and thus the filtration process can be omitted because it has no effect on the physical properties.
The production method of the bio-polyol according to the present invention will be described in detail as follows.
The epoxidized vegetable oil used as a raw material in the present invention can be produced by converting part or all of the carbon-carbon double bond of the vegetable oil into an epoxide group. The vegetable oil has a structure in which various fatty acids are bound to triglycerides, and the fatty acid contains an unsaturated bond. Such vegetable oils may include at least one selected from the group consisting of soybean oil, palm oil, sunflower oil, rape oil, rapeseed oil, palm oil, jatropha oil and flax oil. In the examples of the present invention, examples using mainly soybean oil as the vegetable oil are specifically exemplified, but the vegetable oil in the present invention is not limited to soybean oil. In addition, the vegetable oil used in the present invention may be a new product, or the waste vegetable oil may be recycled. As described above, in the present invention, there is no particular restriction on the vegetable oil, and any oil may be used as long as it contains at least one carbon-carbon double bond so that an epoxide group can be introduced.
In addition, the reaction for epoxidizing the vegetable oil can be carried out by a method commonly known in the art. In order to facilitate understanding of the epoxidation reaction, Scheme 1 below briefly shows a method of epoxidizing soybean oil.
[Reaction Scheme 1]
According to the method (A) shown in Reaction Scheme 1, an epoxidized vegetable oil (A) can be prepared by reacting hydrogen peroxide (H 2 O 2 ) under the condition that an organic acid such as formic acid or acetic acid exists in a vegetable oil. According to the method (B) shown in the above Scheme 1, methanol and sodium hydroxide are added to the vegetable oil and reacted to form biodiesel. Hydrogen peroxide (H 2 O 2 ) is added to the biodiesel in the presence of an organic acid such as formic acid or acetic acid To produce an epoxidized vegetable oil (B).
As another raw material used in the present invention, the hydroxyl functional substance is a compound containing a hydroxyl group (-OH) in the molecular structure, and the epoxide group is subjected to a ring opening reaction. The hydroxyl functional material is specifically water; C 1 -C 6 aliphatic alcohols such as methanol and ethanol; Polyhydric alcohols having 2 to 15 hydroxyl groups such as 1,3-propanediol, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, pentaerythritol, dipentaerythritol, xylitol and sorbitol; C 2 -C 10 alcohol amines such as ethanolamine, diethanolamine and triethanolamine; May be used. Preferably, at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, pentaerythritol, ethanolamine, diethanolamine and triethanolamine can be used.
The reaction conditions between the epoxidized vegetable oil and the hydroxyl functional material for producing the bio-polyol according to the present invention will be described in more detail as follows.
As the reaction solvent, a conventional organic solvent may be used, or the reaction may be carried out using a hydroxyl functional substance without using a separate solvent. Typical organic solvents that can be used in accordance with necessity may include, for example, acetone, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, ethyl acetate, dichloromethane and the like
The amount of the hydroxyl functional substance used as the reactant is preferably 1 to 10 times by weight, preferably 1 to 5 times by weight, based on the weight of the epoxidized vegetable oil. When the amount of the hydroxyl functional material used is less than 1 part by weight, a polyol in which an epoxide group remains may be synthesized. If the hydroxyl functional material is used in an amount exceeding 10 times by weight, the reaction may proceed without using any solvent There is an economic loss, so use it within the above range.
The amount of the alkali metal oxide catalyst or ZnCl 2 catalyst used as the reaction catalyst is preferably in the range of 0.001 to 1 wt% relative to the weight of the epoxidized vegetable oil from the viewpoints of reactivity and economy.
The reaction temperature is in the range of 50 ° C to 200 ° C, and when the reaction is carried out for about 4 to 24 hours, the reaction can proceed almost quantitatively.
In order to further understand the process for preparing a biopolyol by reacting epoxidized vegetable oil and a hydroxyl functional material according to the present invention, epoxidized soybean oil is used in the following Reaction Schemes 2A and 2B to describe hydroxyl functionalities An example of a method for producing a polyol derived from soybean oil is illustrated.
[Reaction Scheme 2A]
[Reaction Scheme 2B]
Since the OH value of the bio-polyol prepared through the above-mentioned process is in the range of 80 to 250 mgKOH / g, it is possible to react with isocyanate to form a sandwich panel for construction, refrigerator insulation, LNG insulator, container insulation, spray insulation, Can be used as material. In particular, according to the present invention, since the bio-polyol produced can be easily filtered regardless of the molecular weight of the hydroxyl functional substance, it can be useful for the mass production of the bio-polyol.
Hereinafter, preferred embodiments and test examples of the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and should be construed in accordance with the technical meanings and concepts of the present invention.
The embodiments described herein are preferred embodiments of the present invention and are not intended to represent all of the technical ideas of the present invention, so that various equivalents and modifications may be substituted for them at the time of application of the present invention.
[Production Example] Production of epoxy soybean oil or biodiesel from soybean oil or waste soybean oil
Production Example 1. Preparation of epoxidized soybean oil (A) from soybean oil
217.7 g of soybean oil and 43.8 g of formic acid were added and stirred for 3 hours. 35% hydrogen peroxide (123.9 g) was added and stirred at room temperature for about 5 hours. After the reaction was completed, the oil layer and the water layer were separated using a centrifuge. 225 g of an epoxidized soybean oil (A) was obtained after moisture removal.
Yield 90%; 1 H NMR (CDCl 3 )? 5.11 (m, 1 H), 4.13 (m, 1 H), 3.97 1.34-1. 10 (m, 75H), 0.69 (m, 9H); Oxylan 6.8.
Production Example 2. Preparation of epoxidized soybean oil (A) from waste soybean oil
217.7 g of waste soybean oil and 43.8 g of formic acid were added and stirred for 3 hours. Then, 35% hydrogen peroxide (123.9 g) was added thereto and stirred at room temperature for about 5 hours. After completion of the reaction, the organic layer and the water layer were separated using a centrifugal separator. The separated organic layer was dried under reduced pressure to obtain 220 g of an epoxidized soybean oil (A).
Yield 88%; 1 H NMR (CDCl 3 )? 5.11 (m, 1 H), 4.13 (m, 1 H), 3.97 1.34-1. 10 (m, 75H), 0.69 (m, 9H); Oxirane 5.0.
Production Example 3. Preparation of epoxidized soybean oil (B) from soybean oil
500 g of methanol and 40 g of NaOH were added to 500 g of soybean oil and refluxed for 5 hours. The upper layer formed was separated to obtain 450 g of biodiesel (yield 90%). After adding 300 g of biodiesel and 172 g of formic acid, the mixture was stirred for 3 hours, 35% hydrogen peroxide (490 g) was added, and the mixture was stirred at room temperature for about 5 hours. After completion of the reaction, the organic layer and the water layer were separated using a centrifugal separator. The separated organic layer was dried under reduced pressure to obtain 270 g of epoxy soybean oil (B).
Yield 90%; 1 H NMR (300 MHz, CDCl 3) δ 3.60 (s, 3H), 3.59 (s, 3H), 3.55 (s, 3H), 2.34-2.10 (M, 2H), 1.51-1.38 (m, 2H), 1.30-1.20 (m, 22H), 0.88 (t, 3H).
Production Example 4. Preparation of epoxidized soybean oil (B) from waste soybean oil
To 500 g of methanol and 40 g of NaOH, 500 g of waste soybean oil was added and refluxed for 5 hours. The upper layer formed was separated to obtain 452 g of biodiesel (yield 92%). After adding 300 g of biodiesel and 172 g of formic acid, the mixture was stirred for 3 hours, 35% hydrogen peroxide (490 g) was added, and the mixture was stirred at room temperature for about 5 hours. After completion of the reaction, the organic layer and the water layer were separated using a centrifugal separator. The separated organic layer was dried under reduced pressure to obtain 275 g of epoxy soybean oil (B).
Yield 91%; 1 H NMR (300 MHz, CDCl 3) δ 3.60 (s, 3H), 3.59 (s, 3H), 3.55 (s, 3H), 2.34-2.10 (m, 2H), 1.51-1.38 (m, 2H), 1.30-1.20 (m, 22H), 0.88 (t, 3H).
EXAMPLES Preparation of polyols from epoxidized soybean oil
Example 1. Preparation of polyol 1 using CaO
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 1, 200 g of methanol and 0.1 g of CaO were added and refluxed for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 1.
Yield 100% (109.5 g); 1 H NMR (300 MHz, CDCl 3 )? 4.3 (m, 4H), 3.6 (s, 3H), 3.1 (m, 3H), 2.3 t, 3H); The hydroxyl group is 184.
Example 2 Preparation of Polyol 1 Using CaO
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 200 g of methanol and 0.1 g of CaO were added and refluxed for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 1.
Yield 100% (110.0 g); 1 H NMR (300 MHz, CDCl 3 )? 4.3 (m, 4H), 3.6 (s, 3H), 3.1 (m, 3H), 2.3 t, 3H); The hydroxyl value is 174.
Example 3. Preparation of environmentally friendly polyol 2 from soybean oil using CaO
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 1, 200 g of water and 0.1 g of CaO were placed and refluxed for 8 hours. The reaction solution was cooled to room temperature, filtered, and then distilled under reduced pressure to obtain polyol 2.
Yield 100% (105.9 g); 1 H NMR (300 MHz, CDCl 3 )? 4.2 (m, 4H), 3.3 (m, 3H), 2.4 (m, 3H), 1.7-1.1 (m, 64H), 0.8 (t, 3H); The hydroxyl group is 203.
Example 4. Preparation of polyol 2 using CaO
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 200 g of water and 0.1 g of CaO were added and refluxed for 8 hours. The reaction solution was cooled to room temperature, filtered, and then distilled under reduced pressure to obtain polyol 2.
Yield 100% (105.9 g); 1 H NMR (300 MHz, CDCl 3 )? 4.2 (m, 4H), 3.3 (m, 3H), 2.4 (m, 3H), 1.7-1.1 (m, 64H), 0.8 (t, 3H); The hydroxyl value is 192.
Example 5. Preparation of polyol 3 using CaO
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 100 g of ethylene glycol, and 0.1 g of CaO were added and reacted at 120 ° C for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 3.
Yield 100% (127.3 g); 1 H NMR (300 MHz, DMSO- d 6) δ 4.4 (m, 4H), 3.7 (m, 2H), 3.5 (m, 2H), 2.3 (m, 2H), 1.8-1.1 (m, 21H), 0.8 (m, 3 H).
Example 6. Preparation of polyol 4 using CaO
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 50 g of pentaerythritol and 0.1 g of CaO were placed and reacted at 120 ° C for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 4.
Yield 100% (146.6 g); 1 H NMR (300 MHz, DMSO- d 6) δ 4.4 (m, 4H), 3.6 (m, 1H), 3.3 (s, 6H), 3.1 (m, 1H), 2.4 (m, 2H), 1.8- 1.1 (m, 21H), 0.9 (m, 3H).
Example 7. Preparation of polyol 5 using CaO
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 3, 200 g of methanol and 0.1 g of CaO were placed and refluxed for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 5.
Yield 100% (114.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.6 (s, 3H), 3.3 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 127.
Example 8. Preparation of polyol 5 using CaO
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 200 g of methanol and 0.1 g of CaO were added and refluxed for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 5.
Yield 100% (114.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.6 (s, 3H), 3.3 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 115.
Example 9. Preparation of polyol 6 using CaO
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 3, 200 g of water and 0.1 g of CaO were added and refluxed for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 6.
Yield 100% (111.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.7 (s, 3H), 3.3 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 180.
Example 10. Preparation of environmentally friendly polyol 6 from waste soybean oil using CaO
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 200 g of water and 0.1 g of CaO were added and refluxed for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 6.
Yield 100% (111.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.7 (s, 3H), 3.3 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 176.
Example 11 Preparation of Polyol 7 Using CaO
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 100 g of ethylene glycol, and 0.1 g of CaO were added and reacted at 120 DEG C for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 7.
Yield 100% (120.4 g); 1 H NMR (300 MHz, DMSO- d 6) δ 3.7 (m, 2H), 3.6 9s, 3H), 3.1 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3 H).
Example 12. Preparation of polyol 8 using CaO
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 50 g of pentaerythritol and 0.1 g of CaO were placed and reacted at 120 ° C for 8 hours. The reaction solution was cooled to room temperature, filtered, and then distilled under reduced pressure to obtain polyol 8.
Yield 100% (146.5 g); 1 H NMR (300 MHz, DMSO- d 6) δ 3.6 (s, 3H), 3.3 (s, 6H), 3.1 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3 H).
Example 13. Preparation of polyol 1 using ZnCl 2
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 1, 200 g of methanol and 1 g of ZnCl 2 were added and refluxed for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 1.
Yield 100% (109.5 g); 1 H NMR (300 MHz, CDCl 3 )? 4.3 (m, 4H), 3.6 (s, 3H), 3.1 (m, 3H), 2.3 t, 3H); The hydroxyl value is 185.
Example 14. Preparation of polyol 1 using ZnCl 2
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 200 g of methanol and 1 g of ZnCl 2 were added and refluxed for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 1.
Yield 100% (110.0 g); 1 H NMR (300 MHz, CDCl 3 )? 4.3 (m, 4H), 3.6 (s, 3H), 3.1 (m, 3H), 2.3 t, 3H); The hydroxyl group is 171.
Example 15. Preparation of polyol 2 using ZnCl 2
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 1, 200 g of water and 1 g of ZnCl 2 were added and refluxed for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 2.
Yield 100% (105.9 g); 1 H NMR (300 MHz, CDCl 3 )? 4.2 (m, 4H), 3.3 (m, 3H), 2.4 (m, 3H), 1.7-1.1 (m, 64H), 0.8 (t, 3H); The hydroxyl value is 201.
Example 16. Preparation of polyol 2 using ZnCl 2
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 200 g of water and 1 g of ZnCl 2 were added and refluxed for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 2.
Yield 100% (105.9 g); 1 H NMR (300 MHz, CDCl 3 )? 4.2 (m, 4H), 3.3 (m, 3H), 2.4 (m, 3H), 1.7-1.1 (m, 64H), 0.8 (t, 3H); The hydroxyl group is 189.
Example 17. Preparation of polyol 3 using ZnCl 2
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 100 g of ethylene glycol, and 1 g of ZnCl 2 were added and reacted at 120 ° C for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 3.
Yield 100% (127.3 g); 1 H NMR (300 MHz, DMSO- d 6) δ 4.4 (m, 4H), 3.7 (m, 2H), 3.5 (m, 2H), 2.3 (m, 2H), 1.8-1.1 (m, 21H), 0.8 (m, 3 H).
Example 18. Preparation of polyol 4 using ZnCl 2
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 50 g of pentaerythritol and 1 g of ZnCl 2 were added and reacted at 120 ° C for 8 hours. The reaction solution was cooled to room temperature, filtered, and distilled under reduced pressure to obtain polyol 4.
Yield 100% (146.6 g); 1 H NMR (300 MHz, DMSO- d 6) δ 4.4 (m, 4H), 3.6 (m, 1H), 3.3 (s, 6H), 3.1 (m, 1H), 2.4 (m, 2H), 1.8- 1.1 (m, 21H), 0.9 (m, 3H).
Example 19. Preparation of polyol 5 using ZnCl 2
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 3, 200 g of methanol and 1 g of ZnCl 2 were added and refluxed for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 5.
Yield 100% (114.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.6 (s, 3H), 3.3 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 129.
Example 20. Preparation of polyol 5 using ZnCl 2
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 200 g of methanol and 1 g of ZnCl 2 were added and refluxed for 8 hours. The reaction solution was cooled and distilled under reduced pressure to obtain polyol 5.
Yield 100% (114.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.6 (s, 3H), 3.3 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl group is 119.
Example 21. Preparation of polyol 6 using ZnCl 2
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 3, 200 g of water and 1 g of ZnCl 2 were added and refluxed for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 6.
Yield 100% (111.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.7 (s, 3H), 3.3 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); Hydroxyl group 184
Example 22. Preparation of polyol 6 using ZnCl 2
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 200 g of water and 1 g of ZnCl 2 were added and refluxed for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 6.
Yield 100% (111.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.7 (s, 3H), 3.3 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 171
Example 23. Preparation of polyol 7 using ZnCl 2
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 100 g of ethylene glycol, and 1 g of ZnCl 2 were added and reacted at 120 ° C for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 7.
Yield 100% (120.4 g); 1 H NMR (300 MHz, DMSO- d 6) δ 3.7 (m, 2H), 3.6 9s, 3H), 3.1 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3 H).
Example 24. Preparation of polyol 8 using ZnCl 2
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 50 g of pentaerythritol and 1 g of ZnCl 2 were placed and reacted at 120 ° C for 8 hours. The reaction solution was cooled to room temperature and distilled under reduced pressure to obtain polyol 8.
Yield 100% (146.5 g); 1 H NMR (300 MHz, DMSO- d 6) δ 3.6 (s, 3H), 3.3 (s, 6H), 3.1 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3 H).
Comparative Example 1. Preparation of polyol 1 using sulfuric acid
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 1, 200 g of methanol and 0.5 g of sulfuric acid were added and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered and distilled under reduced pressure to obtain polyol 1.
Yield 99% (109.5 g); 1 H NMR (300 MHz, CDCl 3 )? 4.3 (m, 4H), 3.6 (s, 3H), 3.1 (m, 3H), 2.3 t, 3H); The hydroxyl group is 187.
COMPARATIVE EXAMPLE 2 Preparation of Polyol 1 Using Sulfuric Acid
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 200 g of methanol and 0.5 g of sulfuric acid were added and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered and distilled under reduced pressure to obtain polyol 1.
Yield 100% (110.0 g); 1 H NMR (300 MHz, CDCl 3 )? 4.3 (m, 4H), 3.6 (s, 3H), 3.1 (m, 3H), 2.3 t, 3H); The hydroxyl value is 175.
Comparative Example 3. Preparation of polyol 2 using sulfuric acid
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 1, 200 g of water and 0.5 g of sulfuric acid were placed and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction mixture was filtered under reduced pressure and then distilled under reduced pressure to obtain polyol 2.
Yield 100% (105.9 g); 1 H NMR (300 MHz, CDCl 3 )? 4.2 (m, 4H), 3.3 (m, 3H), 2.4 (m, 3H), 1.7-1.1 (m, 64H), 0.8 (t, 3H); The hydroxyl value is 200.
Comparative Example 4. Preparation of polyol 2 using sulfuric acid
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 2, 200 g of water and 0.5 g of sulfuric acid were placed and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction mixture was filtered under reduced pressure and then distilled under reduced pressure to obtain polyol 2.
Yield 100% (105.9 g); 1 H NMR (300 MHz, CDCl 3 )? 4.2 (m, 4H), 3.3 (m, 3H), 2.4 (m, 3H), 1.7-1.1 (m, 64H), 0.8 (t, 3H); The hydroxyl value is 186
Comparative Example 5. Preparation of polyol 3 using sulfuric acid
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 1, 100 g of ethylene glycol, and 0.5 g of sulfuric acid were added and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered and distilled under reduced pressure to obtain polyol 3.
Yield 100% (127.3 g); 1 H NMR (300 MHz, DMSO- d 6) δ 4.4 (m, 4H), 3.7 (m, 2H), 3.5 (m, 2H), 2.3 (m, 2H), 1.8-1.1 (m, 21H), 0.8 (m, 3 H).
Comparative Example 6. Preparation of polyol 4 using sulfuric acid
100 g of the epoxidized soybean oil (A) prepared in Preparation Example 1, 50 g of pentaerythritol and 0.5 g of sulfuric acid were added and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered and distilled under reduced pressure to obtain polyol 4.
Yield 100% (146.6 g); 1 H NMR (300 MHz, DMSO- d 6) δ 4.4 (m, 4H), 3.6 (m, 1H), 3.3 (s, 6H), 3.1 (m, 1H), 2.4 (m, 2H), 1.8- 1.1 (m, 21H), 0.9 (m, 3H).
Comparative Example 7. Preparation of polyol 5 using sulfuric acid
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 3, 200 g of methanol and 0.5 g of sulfuric acid were added and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered and distilled under reduced pressure to obtain polyol 5.
Yield 100% (114.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.6 (s, 3H), 3.3 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 127.
Comparative Example 8. Preparation of polyol 5 using sulfuric acid
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 200 g of methanol, and 0.5 g of sulfuric acid were placed and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered and distilled under reduced pressure to obtain polyol 5.
Yield 100% (114.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.6 (s, 3H), 3.3 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 110.
Comparative Example 9. Preparation of polyol 6 using sulfuric acid
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 3, 200 g of water and 0.5 g of sulfuric acid were placed and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered under reduced pressure and then distilled under reduced pressure to obtain polyol 6.
Yield 100% (111.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.7 (s, 3H), 3.3 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 188
Comparative Example 10. Preparation of polyol 6 using sulfuric acid
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 200 g of water and 0.5 g of sulfuric acid were placed and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered under reduced pressure and then distilled under reduced pressure to obtain polyol 6.
Yield 100% (111.8 g); 1 H NMR (300 MHz, CDCl 3 )? 3.7 (s, 3H), 3.3 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3H); The hydroxyl value is 166
Comparative Example 11. Preparation of polyol 7 using sulfuric acid
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 100 g of ethylene glycol, and 0.5 g of sulfuric acid were placed and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered and distilled under reduced pressure to obtain polyol 7.
Yield 100% (120.4 g); 1 H NMR (300 MHz, DMSO- d 6) δ 3.7 (m, 2H), 3.6 9s, 3H), 3.1 (m, 1H), 2.3 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3 H).
Comparative Example 12. Preparation of polyol 8 using sulfuric acid
100 g of the epoxidized soybean oil (B) prepared in Preparation Example 4, 50 g of pentaerythritol and 0.5 g of sulfuric acid were placed and refluxed for 8 hours. After cooling the reaction solution to room temperature, the pH was adjusted to 5 to 6 by adding a saturated solution of potassium hydroxide-methanol. The reaction solution was filtered and distilled under reduced pressure to obtain polyol 8.
Yield 100% (146.5 g); 1 H NMR (300 MHz, DMSO- d 6) δ 3.6 (s, 3H), 3.3 (s, 6H), 3.1 (m, 1H), 2.2 (m, 2H), 1.9-1.2 (m, 21H), 0.8 (m, 3 H).
[Experimental Example]
Experimental Example 1. Measurement of OH Value
The hydroxyl groups of the polyols prepared in Examples 1 to 24 and Comparative Examples 1 to 12 were calculated using the acetic anhydride-pyridine method (JISK 8004-1961).
[Experimental Method]
① Add the polyol synthesized in the Erlenmeyer flask and 5 mL of anhydrous acetic acid-pyridine mixture and stir for 2 hours in a water bath.
② Add 1 mL of distilled water and allow to react for 30 minutes under a water bath.
③ After standing at room temperature for 10 minutes, wash the inner wall of the cooler with 10 mL of acetone, add 3 ~ 4 drops of phenolphthalein indicator, and titrate with 0.5N NaOH standard solution.
④ The hydroxyl value was calculated by substituting into the following equation (1), and the results are summarized in the following Tables 1 to 3.
[Equation 1]
Wherein A is the volume (mL) of the 0.5 N NaOH used in the present experiment, and A is the volume (mL) of 0.5 N NaOH used in the blank (control) , AV is the acid value of the sample used in the experiment and f is the normal concentration of the titrant)
Experimental Example 2. Comparison of Filtration Possibilities
The following experiments were conducted to compare the filtration potentials of the polyols prepared in Examples 1 to 24 and Comparative Examples 1 to 12.
[Experimental Method]
CaO, ZnCl 2 or sulfuric acid was added to the epoxidized soybean oil (A), and the reaction solution was filtered. At this time, when the produced polyol was easily filtered, it was indicated as "", and when it was not easily filtered, it was indicated as" x ".
The following Tables 1 to 3 show the yield, hydroxyl value (OH value, mgKOH / g) of the polyol prepared by using CaO, ZnCl 2 , or sulfuric acid (H 2 SO 4 ) Respectively.
Possibility
(Production Example 1)
(Production Example 2)
(Production Example 1)
(Production Example 2)
(Production Example 2)
(Production Example 2)
(Production Example 3)
(Production Example 4)
(Production Example 3)
(Production Example 4)
(Production Example 4)
(Production Example 4)
Possibility
(Production Example 1)
(Production Example 2)
(Production Example 1)
(Production Example 2)
(Production Example 2)
(Production Example 2)
(Production Example 3)
(Production Example 4)
(Production Example 3)
(Production Example 4)
(Production Example 4)
(Production Example 4)
Possibility
(Production Example 1)
(Production Example 2)
(Production Example 1)
(Production Example 2)
(Production Example 1)
(Production Example 1)
(Production Example 3)
(Production Example 4)
(Production Example 3)
(Production Example 4)
(Production Example 4)
(Production Example 4)
From the results of Tables 1 to 3, it was confirmed that the production yield and hydroxyl value of the bio polyol were maintained regardless of the type of catalyst in the reaction of producing the bio polyol from epoxidized vegetal ally.
However, the possibility of filtration was significantly different depending on the type of catalyst.
When an alkali metal oxide catalyst was used, all the polyol-1 to polyol-8 were easily filtered. That is, the alkali metal oxide catalyst is useful as a method for mass production of polyols since the bio-polyol produced irrespective of the kind of the hydroxy-functional substance can be easily filtered.
When the polyol-1 to polyol-8 were prepared using the ZnCl 2 catalyst, the filtration was easy. In particular, although the ZnCl 2 catalyst remains in the bio-polyol, it is used as a starting material for synthesis of polyurethane and the like, and has no effect on physical properties such as transparency. Therefore, there is a convenient advantage in the process that the filtration process is not performed.
On the other hand, when a sulfuric acid (H 2 SO 4 ) catalyst was used, all bio-polyols were not easily filtered.
Claims (9)
Wherein the reaction is carried out at a temperature of from 50 DEG C to 200 DEG C under an alkali metal oxide catalyst selected from MgO, CaO, or a mixture thereof.
Wherein the amount of the alkali metal oxide catalyst used is in the range of 0.001 to 1 wt% relative to the weight of the epoxidized vegetable oil.
The hydroxyl functional material is selected from the group consisting of water; C 1 -C 6 aliphatic alcohols; Polyhydric alcohols having 2 to 15 hydroxyl groups; And C 2 to C 10 alcohol amines. The method for producing a bio-polyol according to claim 1,
Wherein the hydroxyl functional material is at least one selected from the group consisting of water, methanol, ethanol, ethylene glycol, pentaerythritol, ethanolamine, diethanolamine and triethanolamine.
Wherein the epoxidized vegetable oil is prepared by reacting vegetable oil with hydrogen peroxide (H 2 O 2 ) in the presence of an organic acid selected from formic acid and acetic acid.
Wherein the epoxidized vegetable oil is produced by reacting methanol and sodium hydroxide in a vegetable oil and then reacting hydrogen peroxide (H 2 O 2 ) in the presence of an organic acid selected from formic acid and acetic acid. Way.
Wherein the vegetable oil is at least one selected from the group consisting of soybean oil, palm oil, sunflower oil, rape oil, rapeseed oil, palm oil, jatropha oil and flax oil.
Wherein the vegetable oil is a new product or a waste vegetable oil.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018152608A1 (en) * | 2017-02-24 | 2018-08-30 | Vieceli Antonio Carlos | Polymeric depollutant foam composition, method for producing same and use thereof |
| KR20200065253A (en) | 2018-11-30 | 2020-06-09 | 주식회사 세호 | Low Toxic Polymeric MDI, Polyurethane Resin Comprising the Same and Method Thereof |
| EP4053111A1 (en) | 2021-03-01 | 2022-09-07 | Komagra Spólka Z O.O. | The method of producing epoxidised rapeseed oil and method of producing biopolyol using epoxidised rapeseed oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100849123B1 (en) | 2007-06-15 | 2008-07-30 | 한국포리올 주식회사 | Synthesis method of high functional polyol using the castor oil and polyol and polyurethane produced by that method |
| KR20100099089A (en) | 2010-08-23 | 2010-09-10 | 주식회사 사조해표 | Process for preparing biodegradable polyol using plant oil |
| KR101072674B1 (en) * | 2010-09-27 | 2011-10-11 | 삼성석유화학(주) | Process for the preparation of aliphatic alkylester |
| KR20110132336A (en) * | 2009-03-05 | 2011-12-07 | 아크조노벨코팅스인터내셔널비.브이. | Hydroxyl functional oil polyols and coating compositions prepared from hydroxyl functional oil polyols |
| KR101205322B1 (en) | 2011-09-20 | 2012-11-27 | 에이치플러스에코 주식회사 | Plant oil-based polyols and processes for their preparation |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100849123B1 (en) | 2007-06-15 | 2008-07-30 | 한국포리올 주식회사 | Synthesis method of high functional polyol using the castor oil and polyol and polyurethane produced by that method |
| KR20110132336A (en) * | 2009-03-05 | 2011-12-07 | 아크조노벨코팅스인터내셔널비.브이. | Hydroxyl functional oil polyols and coating compositions prepared from hydroxyl functional oil polyols |
| KR20100099089A (en) | 2010-08-23 | 2010-09-10 | 주식회사 사조해표 | Process for preparing biodegradable polyol using plant oil |
| KR101072674B1 (en) * | 2010-09-27 | 2011-10-11 | 삼성석유화학(주) | Process for the preparation of aliphatic alkylester |
| KR101205322B1 (en) | 2011-09-20 | 2012-11-27 | 에이치플러스에코 주식회사 | Plant oil-based polyols and processes for their preparation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018152608A1 (en) * | 2017-02-24 | 2018-08-30 | Vieceli Antonio Carlos | Polymeric depollutant foam composition, method for producing same and use thereof |
| KR20200065253A (en) | 2018-11-30 | 2020-06-09 | 주식회사 세호 | Low Toxic Polymeric MDI, Polyurethane Resin Comprising the Same and Method Thereof |
| EP4053111A1 (en) | 2021-03-01 | 2022-09-07 | Komagra Spólka Z O.O. | The method of producing epoxidised rapeseed oil and method of producing biopolyol using epoxidised rapeseed oil |
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