CN112662482A - Preparation method of thioglycerol modified castor oil-based polyol - Google Patents
Preparation method of thioglycerol modified castor oil-based polyol Download PDFInfo
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- CN112662482A CN112662482A CN202011523170.XA CN202011523170A CN112662482A CN 112662482 A CN112662482 A CN 112662482A CN 202011523170 A CN202011523170 A CN 202011523170A CN 112662482 A CN112662482 A CN 112662482A
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Abstract
The invention relates to a method for preparing castor oil-based polyol by using thioglycerol modified castor oil. The invention uses thioglycerol (3-mercapto-1, 2-propylene glycol) to modify castor oil through mercapto-alkene click reaction to prepare the bio-based polyol, and the hydroxyl value of the castor oil after the thioglycerol modification is increased from the original 60mg KOH/g to over 110mg KOH/g. The hydroxyl number of castor oil polyol modified by thioglycerol is obviously higher. Compared with the commercial petroleum-based polyol, the vegetable oil-based polyol prepared by the invention is more environment-friendly, and provides a new raw material for preparing the polyhydroxy high-crosslinking bio-based material.
Description
Technical Field
The invention relates to a preparation method of castor oil-based polyol, in particular to a preparation method of thioglycerol modified castor oil-based polyol.
Background
The polyols currently on the market are mainly produced from petrochemical resources and are widely used as important intermediates for the synthesis of industrial products such as polyester resins, alkyd resins, explosives, varnishes and the like. In order to achieve sustainable development in greenness, some renewable vegetable oils are used to replace petroleum resources. The natural castor oil contains 88 percent of ricinoleic acid, the molecules of the castor oil carry hydroxyl, the average hydroxyl functionality is 2.7, and the castor oil can be directly used for industrial production of bio-based polyol. However, the hydroxyl group of the castor oil side chain has low reactivity and is difficult to directly participate in the polymerization reaction. The hydroxyl value of the natural castor oil is not high, so that the hydroxyl number of the prepared castor oil-based polyol is limited, and the further preparation of the resin material with excellent mechanical properties is not facilitated.
The mercapto-alkene click reaction is a traditional method for modifying castor oil, and more primary carbon hydroxyl groups with high reactivity are introduced by beta-mercaptoethanol. However, beta-mercaptoethanol has high volatility and toxicity, and the number of hydroxyl groups on the molecule is small. The thioglycerol with similar structure contains one primary hydroxyl group and one secondary hydroxyl group, and has high reactivity with isocyanate and lower toxicity.
Disclosure of Invention
The invention aims to provide a preparation method of a thioglycerol modified castor oil-based polyol, which utilizes the addition of sulfydryl in the thioglycerol and unsaturated double bonds in castor oil through sulfydryl-alkene click reaction to introduce more hydroxyl groups on the basis of the original castor oil.
The technical scheme adopted by the invention is as follows:
the method comprises the following steps: and (3) photoreaction:
mixing 3-7 parts by weight of natural castor oil, 4-8 parts by weight of thioglycerol and 0.14-0.3 part by weight of photoinitiator 1173 in a 100ml three-necked bottle; adjusting the mechanical stirring speed to 200r/min, and then irradiating ultraviolet light for 6-8 hours at room temperature by using an ultraviolet lamp to form an organic phase product;
step two: separation and purification:
diluting the reaction product obtained in the step one by using 45-55 parts by weight of ethyl acetate, and washing by using 95-105 parts by weight of saturated NaCl solution; 5-8 times; the organic layer was washed with 15 to 18 parts by weight of anhydrous MgSO4Drying, and filtering under reduced pressure; and finally, removing the ethyl acetate by using a rotary evaporation and vacuum drying method at the temperature of 60 ℃ to obtain the faint yellow thioglycerol modified castor oil-based polyol.
The invention has the following advantages:
the invention takes thioglycerol, natural castor oil, a photoinitiator 1173 and the like as raw materials, and prepares polyhydroxy castor oil polyol through sulfydryl-alkene click reaction. The conversion rate of carbon-carbon double bonds in the reaction is high, the reaction can be carried out under ultraviolet illumination at room temperature, severe reaction conditions are not needed, and the separation and purification are convenient and simple. The preparation process uses the low-toxicity thioglycerol to replace the traditional mercaptoethanol, and is safer. The hydroxyl number of the modified castor oil is increased, the hydroxyl value of the modified castor oil is increased to more than 110mg KOH/g from about 60mg KOH/g, and the modified castor oil can be used as polyol to prepare green and environment-friendly high-crosslinking bio-based resin materials.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention relates to a preparation method of castor oil-based polyol by adding unsaturated double bonds of castor oil into thioglycerol through a sulfydryl-alkene click reaction. The method comprises the steps of taking thioglycerol, natural castor oil, a photoinitiator 1173 and the like as raw materials, preparing polyhydroxy castor oil polyol in one step through sulfydryl-alkene click reaction under the condition of ultraviolet irradiation, and obtaining a light yellow liquid polyol product after subsequent separation and purification of the product. The method is realized by the following steps:
the method comprises the following steps: and (3) photoreaction:
3 to 7 parts by weight of natural castor oil, 4 to 8 parts by weight of thioglycerol and 0.14 to 0.3 part by weight of photoinitiator 1173 are mixed in a 100ml three-necked flask. Adjusting the rotation speed of mechanical stirring to 200r/min, and then irradiating ultraviolet light for 6-8 hours at room temperature by using an ultraviolet lamp to form an organic phase product.
Step two: separation and purification:
diluting the reaction product obtained in the first step with 45-55 parts by weight of ethyl acetate, and washing with 95-105 parts by weight of saturated NaCl solution at least 5 times. The organic layer was washed with 15 to 18 parts by weight of anhydrous MgSO4After drying, filtration was carried out under reduced pressure. And finally, removing the ethyl acetate by using a rotary evaporation and vacuum drying method at the temperature of 60 ℃ to obtain the faint yellow thioglycerol modified castor oil-based polyol.
Example 1:
the method comprises the following steps: and (3) photoreaction:
4.8 parts by weight of natural castor oil, 6.25 parts by weight of thioglycerol, 0.21 part by weight of photoinitiator 1173 were mixed in a 100ml three-necked flask. Adjusting the mechanical stirring speed to 200r/min, and then irradiating ultraviolet light for 7 hours at room temperature by using an ultraviolet lamp to form an organic oil phase product.
Step two: separation and purification:
the reaction product obtained in the first step was diluted with 46 parts by weight of ethyl acetate and washed with 100 parts by weight of a saturated NaCl solution at least 5 times. The resulting organic layer was washed with 15 parts by weight of anhydrous MgSO4After drying, filtration was carried out under reduced pressure. And finally, removing the ethyl acetate by using a rotary evaporation and vacuum drying method at the temperature of 60 ℃ to obtain the faint yellow thioglycerol modified castor oil-based polyol.
Example 2:
the method comprises the following steps: and (3) photoreaction:
5.2 parts by weight of natural castor oil, 6.7 parts by weight of thioglycerol, 0.22 part by weight of photoinitiator 1173 were mixed in a 100ml three-necked flask. Adjusting the mechanical stirring speed to 200r/min, and then irradiating ultraviolet light for 7 hours at room temperature by using an ultraviolet lamp to form an organic oil phase product.
Step two: separation and purification:
the reaction product obtained in the first step was diluted with 50 parts by weight of ethyl acetate and washed with 100 parts by weight of a saturated NaCl solution at least 5 times. The resulting organic layer was treated with 16 parts by weight of anhydrous MgSO4After drying, filtration was carried out under reduced pressure. And finally, removing the ethyl acetate by using a rotary evaporation and vacuum drying method at the temperature of 60 ℃ to obtain the faint yellow thioglycerol modified castor oil-based polyol.
Example 3:
the method comprises the following steps: and (3) photoreaction:
6.1 parts by weight of natural castor oil, 7.0 parts by weight of thioglycerol, 0.25 parts by weight of photoinitiator 1173 were mixed in a 100ml three-necked flask. Adjusting the rotation speed of mechanical stirring to 200r/min, and then irradiating ultraviolet light for 7.5 hours at room temperature by using an ultraviolet lamp to form an organic oil phase product.
Step two: separation and purification:
the reaction product obtained in the first step was diluted with 53 parts by weight of ethyl acetate and washed with 100 parts by weight of a saturated NaCl solution at least 5 times. The resulting organic layer was washed with 17 parts by weight of anhydrous MgSO4After drying, filtration was carried out under reduced pressure. Finally, ethyl acetate is removed by rotary evaporation and vacuum drying at 60 ℃ to obtain the faint yellow thioglycerol modified castor oil-based polyol。
Example 4:
the method comprises the following steps: and (3) photoreaction:
5.5 parts by weight of natural castor oil, 6.8 parts by weight of thioglycerol, 0.25 part by weight of photoinitiator 1173 were mixed in a 100ml three-necked flask. Adjusting the rotation speed of mechanical stirring to 200r/min, and then irradiating ultraviolet light for 6.5 hours at room temperature by using an ultraviolet lamp to form an organic oil phase product.
Step two: separation and purification:
the reaction product obtained in the first step was diluted with 53 parts by weight of ethyl acetate and washed with 100 parts by weight of a saturated NaCl solution at least 5 times. The resulting organic layer was washed with 17 parts by weight of anhydrous MgSO4After drying, filtration was carried out under reduced pressure. And finally, removing the ethyl acetate by using a rotary evaporation and vacuum drying method at the temperature of 60 ℃ to obtain the faint yellow thioglycerol modified castor oil-based polyol.
The thioglycerol modified castor oil-based polyol can be obtained by the method. The method can avoid the use of high-toxicity beta mercaptoethanol, greatly improve the number of castor oil hydroxyl groups, and can be used for preparing high-crosslinking bio-based materials.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (4)
1. A preparation method of a thioglycerol modified castor oil-based polyol is characterized by comprising the following steps:
the method is realized by the following steps:
the method comprises the following steps: and (3) photoreaction:
mixing 3-7 parts by weight of natural castor oil, 4-8 parts by weight of thioglycerol and 0.14-0.3 part by weight of photoinitiator 1173 in a 100ml three-necked bottle; adjusting the mechanical stirring speed to 200r/min, and then irradiating ultraviolet light for 6-8 hours at room temperature by using an ultraviolet lamp to form an organic phase product;
step two: separation and purification:
diluting the reaction product obtained in the step one by using 45-55 parts by weight of ethyl acetate,washing with 95-105 parts by weight of saturated NaCl solution; 5-8 times; the organic layer was washed with 15 to 18 parts by weight of anhydrous MgSO4Drying, and filtering under reduced pressure; and finally, removing the ethyl acetate by using a rotary evaporation and vacuum drying method at the temperature of 60 ℃ to obtain the faint yellow thioglycerol modified castor oil-based polyol.
2. The method of preparing the thioglycerol-modified castor oil-based polyol of claim 1, wherein:
in the first step, the thioglycerol is polyhydroxy thiol compound thioglycerol (3-mercapto-1, 2-propanediol).
3. The method of preparing the thioglycerol-modified castor oil-based polyol of claim 1, wherein:
in the first step, the weight ratio of the natural castor oil to the thioglycerol is between 1:1 and 5: 6.
4. The method of preparing the thioglycerol-modified castor oil-based polyol of claim 1, wherein:
in the first step, the reaction temperature is 25 ℃, the ultraviolet irradiation wavelength is 340-360nm, and the reaction time is 7 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113264857A (en) * | 2021-05-17 | 2021-08-17 | 华南农业大学 | Epoxy vegetable oil-based polyol and preparation method thereof, epoxy vegetable oil-based hyperbranched polyurethane resin and application thereof |
| CN116285505A (en) * | 2022-12-19 | 2023-06-23 | 南宝树脂（佛山）有限公司 | Water-based treating agent suitable for high-elasticity EVA material and preparation method thereof |
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| CN105683245A (en) * | 2013-09-05 | 2016-06-15 | 科思创德国股份有限公司 | Cross-linking of polyether carbonate polyols containing double-bonds, by adding mercapto-compounds |
| CN107556452A (en) * | 2017-09-15 | 2018-01-09 | 华南农业大学 | A kind of castor oil-base hydrophilic chain extender and its preparation method and application |
| CN111269759A (en) * | 2018-12-04 | 2020-06-12 | 北京化工大学 | Method for preparing castor oil-based polyols with different hydroxyl values |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105683245A (en) * | 2013-09-05 | 2016-06-15 | 科思创德国股份有限公司 | Cross-linking of polyether carbonate polyols containing double-bonds, by adding mercapto-compounds |
| CN105367790A (en) * | 2015-12-07 | 2016-03-02 | 江西科技师范大学 | Preparation method of castor-oil base branched polybasic cyclic carbonate and non-isocyanate polyurethane thereof |
| CN107556452A (en) * | 2017-09-15 | 2018-01-09 | 华南农业大学 | A kind of castor oil-base hydrophilic chain extender and its preparation method and application |
| CN111269759A (en) * | 2018-12-04 | 2020-06-12 | 北京化工大学 | Method for preparing castor oil-based polyols with different hydroxyl values |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113264857A (en) * | 2021-05-17 | 2021-08-17 | 华南农业大学 | Epoxy vegetable oil-based polyol and preparation method thereof, epoxy vegetable oil-based hyperbranched polyurethane resin and application thereof |
| CN116285505A (en) * | 2022-12-19 | 2023-06-23 | 南宝树脂（佛山）有限公司 | Water-based treating agent suitable for high-elasticity EVA material and preparation method thereof |
| CN116285505B (en) * | 2022-12-19 | 2023-10-20 | 南宝树脂（佛山）有限公司 | Water-based treating agent suitable for high-elasticity EVA material and preparation method thereof |
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