CN110407774B - High-functionality castor oil based epoxy resin and preparation method thereof - Google Patents
High-functionality castor oil based epoxy resin and preparation method thereof Download PDFInfo
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- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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Abstract
The invention provides a castor oil based epoxy resin with high functionality and a preparation method thereof, belonging to the field of organic synthesis. The invention provides castor oil based epoxy resin with high functionality, which has high epoxy value, does not contain carbon-carbon double bonds in a molecular structure, has good weather resistance, and can improve the crosslinking density of the epoxy resin and the flexibility of a cured product when being doped into bisphenol A type epoxy resin for use. The data of the examples show that the incorporation of the high functionality castor oil based epoxy resin provided by the present invention can significantly improve the tensile strength, elongation at break and impact strength of the cured E-51 epoxy resin.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to high-functionality castor oil-based epoxy resin and a preparation method thereof.
Background
Castor Oil (CO) is a triglyceride of natural fatty acids, the main component of which is ricinoleic acid, accounting for about 90%, and the second component is oleic acid, linoleic acid, which is the only vegetable oil containing hydroxyl groups in nature. CO is nondrying oil, and has an iodine value of 80-90 mgI/g, a saponification value of 170-190 mgKOH/g, and a hydroxyl value of 156-160 mgKOH/g.
The epoxy resin is an organic compound containing two or more than two epoxy groups in molecules, the molecular structure of the epoxy resin is characterized in that active epoxy groups are contained in a molecular chain, and the epoxy resin and various curing agents can generate cross-linking reaction to form insoluble high polymers with a three-dimensional network structure due to the active epoxy groups contained in the molecular structure. The cured epoxy resin has good physical and chemical properties, excellent bonding strength, good dielectric property, small deformation shrinkage, good product dimensional stability, high hardness, good flexibility and stability to alkali and most solvents, and is widely applied to various departments of national defense and national economy for casting, impregnation, laminating materials, adhesives, coatings and the like. However, the epoxy resin in the prior art has the problem of low functionality.
Disclosure of Invention
In view of the above, the present invention aims to provide a castor oil based epoxy resin with high functionality and a preparation method thereof. The epoxy resin provided by the invention has high functionality.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-functionality castor oil based epoxy resin, which has a structure shown as a formula I:
the invention also provides a preparation method of the high-functionality castor oil based epoxy resin, which comprises the following steps:
mixing castor oil, hydrogen peroxide, acetic acid, an aromatic hydrocarbon solvent and a first acidic catalyst to perform a first epoxidation reaction to obtain epoxidized castor oil;
mixing the epoxidized castor oil, allyl alcohol and a Lewis acid catalyst to perform a first ring-opening reaction to obtain allyloxy castor oil-based polyol;
sequentially carrying out a second ring-opening reaction and a ring-closing reaction on the allyloxy castor oil-based polyol, epoxy chloropropane and sodium hydroxide to obtain allyloxy castor oil-based polyglycidyl ether;
mixing the allyloxy castor oil-based polyglycidyl ether, hydrogen peroxide, acetic acid, an aromatic hydrocarbon solvent and a second acidic catalyst for a second epoxidation reaction to obtain the high-functionality castor oil-based epoxy resin.
Preferably, the first acidic catalyst and the second acidic catalyst are independently sulfuric acid, phosphoric acid, phosphotungstic heteropoly acid, HZSM-5 molecular sieve, and strong acid cation exchange resin.
Preferably, the temperature of the first epoxidation reaction and the temperature of the second epoxidation reaction are independently 40-80 ℃, and the time is independently 3-8 h.
Preferably, the molar ratio of the castor oil to the hydrogen peroxide to the acetic acid is 1: 3-5: 2-4.
Preferably, the molar ratio of the allyl alcohol to the epoxy group in the epoxidized castor oil is 5-30: 1.
Preferably, the temperature of the first ring-opening reaction is 50-90 ℃ and the time is 1-5 h.
Preferably, the molar ratio of the epoxy chloropropane to the hydroxyl in the allyloxy castor oil-based polyol is 1-1.5: 1.
Preferably, the temperature of the second ring-opening reaction is 40-80 ℃ and the time is 1-5 h.
Preferably, the ring-closure reaction is carried out in the presence of a ring-closure catalyst and solid alkali, the temperature of the ring-closure reaction is 30-80 ℃, and the time is 2-6 hours.
Preferably, the molar ratio of the allyloxy castor oil-based polyglycidyl ether to the hydrogen peroxide to the acetic acid is 1: 2-5: 2-4.
The invention provides a high-functionality castor oil based epoxy resin, which has a structure shown as a formula I:
the invention provides castor oil based epoxy resin with high functionality, which has high epoxy value, does not contain carbon-carbon double bonds in a molecular structure, has good weather resistance, and can improve the crosslinking density of the epoxy resin and the flexibility of a cured product when being doped into bisphenol A type epoxy resin for use. The data of the examples show that the incorporation of the high functionality castor oil based epoxy resin provided by the present invention can significantly improve the tensile strength, elongation at break and impact strength of the cured E-51 epoxy resin.
Drawings
FIG. 1 is an infrared spectrum of a high functionality castor oil based epoxy resin prepared by the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the castor oil-based epoxy resin with high functionality prepared by the invention.
Detailed Description
The invention provides a high-functionality castor oil based epoxy resin, which has a structure shown as a formula I:
the invention also provides a preparation method of the high-functionality castor oil based epoxy resin, which comprises the following steps:
mixing castor oil, hydrogen peroxide, acetic acid, an aromatic hydrocarbon solvent and a first acidic catalyst to perform a first epoxidation reaction to obtain epoxidized castor oil;
mixing the epoxidized castor oil, allyl alcohol and a Lewis acid catalyst to perform a first ring-opening reaction to obtain allyloxy castor oil-based polyol;
sequentially carrying out a second ring-opening reaction and a ring-closing reaction on the allyloxy castor oil-based polyol and epoxy chloropropane to obtain allyloxy castor oil-based polyglycidyl ether;
mixing the allyloxy castor oil-based polyglycidyl ether, hydrogen peroxide, acetic acid, an aromatic hydrocarbon solvent and a second acidic catalyst for a second epoxidation reaction to obtain the high-functionality castor oil-based epoxy resin.
According to the invention, castor oil, hydrogen peroxide, acetic acid, an aromatic solvent and a first acidic catalyst are mixed for a first epoxidation reaction to obtain epoxidized castor oil.
In the present invention, the first acidic catalyst is preferably sulfuric acid, phosphoric acid, phosphotungstic heteropoly acid, HZSM-5 molecular sieve or a strongly acidic cation exchange resin. In the present invention, the amount of the first acid catalyst is preferably 1% to 10%, more preferably 7.5% by mass of castor oil.
In the invention, the temperature of the first epoxidation reaction is preferably 40-80 ℃, and the time is preferably 3-8 h.
In the invention, the molar ratio of the castor oil to the hydrogen peroxide to the acetic acid is preferably 1: 3-5: 2-4.
In the present invention, the aromatic hydrocarbon solvent is preferably toluene or xylene, and the amount of the aromatic hydrocarbon solvent is preferably 50% by mass of castor oil.
After the first epoxidation reaction is finished, the first acidic catalyst is preferably removed from the obtained first epoxidation reaction product by filtration, the first epoxidation reaction product is washed to be neutral by water, and then low-boiling-point substances such as an aromatic hydrocarbon solvent and the like are removed by reduced pressure distillation to obtain the epoxidized castor oil.
After obtaining the epoxidized castor oil, mixing the epoxidized castor oil, allyl alcohol and a Lewis acid catalyst to perform a first ring-opening reaction to obtain the allyloxy castor oil-based polyol.
In the invention, the molar ratio of the allyl alcohol to the epoxy group in the epoxidized castor oil is preferably 5-30: 1.
In the invention, the temperature of the first ring-opening reaction is preferably 50-90 ℃, and the time is preferably 1-5 h.
In the present invention, the lewis acid catalyst is preferably boron trifluoride diethyl etherate or tin tetrachloride. In the present invention, the amount of the lewis acid catalyst is preferably 0.1% to 1%, more preferably 0.5% by mass of the epoxidized castor oil.
After the first ring-opening reaction is finished, the obtained first ring-opening reaction product is preferably washed by water to remove the Lewis acid catalyst, and then is distilled under reduced pressure to obtain the allyloxy castor oil-based polyol.
After the allyloxy castor oil-based polyol is obtained, the allyloxy castor oil-based polyol and epoxy chloropropane are subjected to a second ring-opening reaction and a ring-closing reaction in sequence to obtain the allyloxy castor oil-based polyglycidyl ether.
In the invention, the molar ratio of the epichlorohydrin to hydroxyl in the allyloxy castor oil-based polyol is preferably 1-1.5: 1. In the invention, the epichlorohydrin is preferably dropwise added into the allyloxy castor oil-based polyol, and the dropwise adding time is preferably 1-4 h.
In the invention, the temperature of the second ring-opening reaction is preferably 40-80 ℃, more preferably 60 ℃, and the time is preferably 1-5 h.
In the present invention, the second ring-opening reaction is preferably performed under the conditions of an aromatic hydrocarbon solvent, which is preferably used in an amount of 50% by mass of the allyloxy castor oil-based polyol, and a lewis acid catalyst, which is preferably used in an amount of 0.1% to 1% by mass, more preferably 0.4% by mass of the allyloxy castor oil-based polyol. The types of the aromatic hydrocarbon solvent and the Lewis acid catalyst in the present invention are preferably the same as those in the above scheme, and are not described herein again.
In the invention, the ring-closure reaction is preferably carried out under the conditions of a ring-closure catalyst and solid alkali, the temperature of the ring-closure reaction is preferably 30-80 ℃, more preferably 50 ℃, and the time is preferably 2-6 h, more preferably 4 h. In the invention, the ring-closure catalyst is preferably a quaternary ammonium salt type phase transfer catalyst, more preferably tetramethylammonium chloride, tetrabutylammonium bromide or triethylbenzylammonium chloride, and the dosage of the ring-closure catalyst is preferably 0.1-1% of the mass of the allyloxy castor oil-based polyol. In the invention, the solid base is preferably NaOH or KOH, and the molar ratio of the allyloxy castor oil-based polyol to the solid base is preferably 1: 0.5-1.5.
After the ring-closure reaction is finished, the obtained ring-closure reaction product is preferably filtered, washed by water and subjected to reduced pressure distillation to remove the solvent, so that the allyloxy castor oil polyglycidyl ether is obtained. The present invention is not particularly limited to the specific operations of filtration, washing with water and distillation under reduced pressure, and the operation method known to those skilled in the art can be adopted.
After the allyloxy castor oil-based polyglycidyl ether is obtained, the allyloxy castor oil-based polyglycidyl ether, hydrogen peroxide, acetic acid, an aromatic hydrocarbon solvent and a second acidic catalyst are mixed for a second epoxidation reaction, and the high-functionality castor oil-based epoxy resin is obtained.
In the invention, the preferred molar ratio of the allyloxy castor oil polyglycidyl ether to hydrogen peroxide is 1: 2-5; the preferred molar ratio of the allyloxy castor oil polyglycidyl ether to the acetic acid is 1: 2-4.
In the present invention, the kind of the second acidic catalyst is preferably the same as that of the first acidic catalyst, and thus, the description thereof is omitted. In the invention, the amount of the second acidic catalyst is preferably 1-10% of the mass of allyloxy castor oil polyglycidyl ether.
In the present invention, the kind of the aromatic hydrocarbon solvent is preferably the same as the above scheme, and will not be described herein, and the amount of the aromatic hydrocarbon solvent is preferably 50% of the mass of the allyloxy castor oil polyglycidyl ether.
In the present invention, the temperature and time of the second epoxidation reaction are preferably identical to those of the first epoxidation reaction, and will not be described herein.
After the second epoxidation reaction is completed, the second epoxidation reaction product is preferably filtered to remove the second acidic catalyst, washed to be neutral, and then subjected to reduced pressure distillation to remove low-boiling-point substances such as an aromatic hydrocarbon solvent, so as to obtain the high-functionality castor oil-based epoxy resin.
The invention also provides the application of the high-functionality castor oil-based epoxy resin in the technical scheme in the field of epoxy resin, and the application is not particularly limited by the invention, and the scheme known by the technical personnel in the field can be adopted.
In order to further illustrate the present invention, the high functionality castor oil based epoxy resin and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The raw materials of castor oil, allyl alcohol, Epichlorohydrin (ECH) and boron trifluoride diethyl etherate (BF) in the examples3-Et2O), tetrabutylammonium bromide, E-51 bisphenol A epoxy resin and diethylenetriamine are all provided by industrial grade, New remote science and technology Limited, Anhui; sodium hydroxide, 30% hydrogen peroxide, acetic acid and toluene are all analytically pure and are produced by Nanjing chemical reagent GmbH; the strong acid cation exchange resin model 732 is industrial grade and is supplied by Chinaba biotechnology, Inc.
The hydroxyl value of the allyloxy castor oil-based polyol is detected by a phthalic anhydride method, and the hydroxyl value of the high-functionality castor oil-based epoxy resin is detected by a hydrochloric acid-acetone method.
Example 1
Adding castor oil, acetic acid, 732 type strong acid cation exchange resin and a solvent toluene into a four-neck flask provided with a mechanical stirrer with mechanical seal, a reflux condenser and a thermometer, wherein the molar ratio of the castor oil to the hydrogen peroxide to the acetic acid is 1:3.5:3, the dosage of the strong acid cation exchange resin is 7.5 percent of the mass of the castor oil, and the dosage of the toluene is 50 percent of the mass of the castor oil, slowly dripping 30 percent of hydrogen peroxide at 60 ℃ under the stirring condition, keeping the temperature for 5 hours after the addition is finished, then filtering, washing with water, and distilling under reduced pressure to remove the toluene to prepare the epoxidized castor oil, wherein the epoxy value is 0.20eq/100 g.
Example 2
Epoxidized castor oil, allyl alcohol and BF prepared in example 13-Et2O is introduced into a four-neck flask equipped with a mechanical stirrer with mechanical seal, reflux condenser and thermometer, n (epoxy group): n (allyl alcohol): 1:20, BF3-Et2The O dosage is 0.5 percent of the mass of the epoxidized castor oil, the reaction is carried out for 2 hours at the temperature of 60 ℃, the catalyst is removed by washing after the reaction is finished, then the excessive allyl alcohol is removed by distillation, the allyloxy castor oil-based polyol is obtained, and the measured hydroxyl value is 214.12 mgKOH/g.
Example 3
The allyloxy castor oil-based polyol from example 2, BF3-Et2O and toluene solvent were charged into a four-necked flask equipped with a mechanical stirrer with mechanical seal, reflux condenser and thermometer, BF3-Et2The dosage of O is 0.4 percent of the mass of allyloxy castor oil-based polyol, the dosage of toluene is 50 percent of the mass of allyloxy castor oil-based polyol, ECH is slowly dripped under the condition of 60 ℃ and stirring, n (R-OH) n (ECH) is 1:1.2, 2 hours are added, and the reaction is kept for 5 hours; and then adding tetrabutylammonium bromide catalyst into the ring-opening reaction product, wherein the adding amount is 0.4 percent of the mass of the allyloxy castor oil-based polyol, then adding solid sodium hydroxide in batches for ring-closing reaction, wherein n (R-OH) is (n), (NaOH) is (1: 1.1), controlling the reaction temperature at 80 ℃, adding the sodium hydroxide for 4 hours, keeping the temperature for reaction for 4 hours, and after the reaction is finished, filtering, washing and distilling the ring-closing product under reduced pressure to remove low-boiling-point substances such as toluene and the like to prepare the allyloxy castor oil-based polyglycidyl ether, wherein the epoxy value is 0.17eq/100 g.
Example 4
The allyloxy castor oil-based epoxy resin with high functionality is prepared by adding the allyloxy castor oil-based polyglycidyl ether prepared in the example 3, acetic acid, 732 type strong acid cation exchange resin and solvent toluene into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, wherein the molar ratio of the allyloxy castor oil-based polyglycidyl ether to the hydrogen peroxide to the acetic acid is 1:3.5:3, the dosage of the cation exchange resin is 7.5% of the mass of the allyloxy castor oil-based polyglycidyl ether, the dosage of the toluene is 50% of the mass of the allyloxy castor oil-based polyglycidyl ether, 30% of the hydrogen peroxide is slowly dripped at 60 ℃ under the stirring condition, after 2h addition, the reaction is carried out for 5h under the heat preservation condition, then filtering, washing, and carrying out reduced pressure distillation to remove low-boiling substances such as toluene and the like, and the.
Fig. 1 is an infrared spectrogram of the high-functionality castor oil-based epoxy resin prepared by the invention, fig. 2 is a nuclear magnetic hydrogen spectrogram of the high-functionality castor oil-based epoxy resin prepared by the invention, and fig. 1-2 show that the high-functionality castor oil-based epoxy resin with the structure shown in formula I is prepared by the invention.
Example 5
The allyloxy castor oil-based epoxy resin with high functionality is prepared by adding the allyloxy castor oil-based polyglycidyl ether prepared in the example 3, acetic acid, 732 type strong acid cation exchange resin and solvent toluene into a four-neck flask provided with a mechanical stirrer with a mechanical seal, a reflux condenser and a thermometer, wherein the molar ratio of the allyloxy castor oil-based polyglycidyl ether to the hydrogen peroxide to the acetic acid is 1:3.5:3, the using amount of the strong acid cation exchange resin is 7.5% of the mass of the allyloxy castor oil-based polyglycidyl ether, the using amount of the toluene is 50% of the mass of the allyloxy castor oil-based polyglycidyl ether, 30% of the hydrogen peroxide is slowly dripped at 80 ℃ under the stirring condition, after 2h addition, the reaction is carried out for 3h under the heat preservation condition, then low-boiling substances such as the toluene and the like are removed through filtration, water washing and reduced pressure distillation.
Example 6
A suitable amount of the high-functionality castor oil-based epoxy resin prepared in example 5 was incorporated into E-51 epoxy resin and then cured with the addition of the theoretically required amount of diethylenetriamine under the curing conditions: the curing performance data measured after curing for 3h at 60 ℃ are shown in Table 1, and it can be seen from Table 1 that the tensile strength, elongation at break and impact strength of the cured E-51 epoxy resin are remarkably improved by the incorporation of the high-functionality castor oil-based epoxy resin.
TABLE 1 Performance results after incorporation of high functionality castor oil based epoxy resins
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The castor oil based epoxy resin is characterized by having a structure shown as a formula I:
2. the method for preparing the castor oil-based epoxy resin according to claim 1, comprising the steps of:
mixing castor oil, hydrogen peroxide, acetic acid, an aromatic hydrocarbon solvent and a first acidic catalyst to perform a first epoxidation reaction to obtain epoxidized castor oil;
mixing the epoxidized castor oil, allyl alcohol and a Lewis acid catalyst to perform a first ring-opening reaction to obtain allyloxy castor oil-based polyol;
sequentially carrying out a second ring-opening reaction and a ring-closing reaction on the allyloxy castor oil-based polyol and epoxy chloropropane to obtain allyloxy castor oil-based polyglycidyl ether;
and mixing the allyloxy castor oil-based polyglycidyl ether, hydrogen peroxide, acetic acid, an aromatic hydrocarbon solvent and a second acidic catalyst for a second epoxidation reaction to obtain the castor oil-based epoxy resin.
3. The method of claim 2, wherein the first and second acidic catalysts are independently sulfuric acid, phosphoric acid, phosphotungstic heteropoly acid, HZSM-5 molecular sieve, strongly acidic cation exchange resin.
4. The method according to claim 2, wherein the first epoxidation reaction and the second epoxidation reaction are independently carried out at a temperature of 40 to 80 ℃ for 3 to 8 hours.
5. The preparation method of claim 2, wherein the molar ratio of the castor oil to the hydrogen peroxide to the acetic acid is 1: 3-5: 2-4.
6. The method according to claim 2, wherein the molar ratio of the allyl alcohol to the epoxy group in the epoxidized castor oil is 5 to 30: 1.
7. The preparation method according to claim 2, wherein the temperature of the first ring-opening reaction is 50-90 ℃ and the time is 1-5 h.
8. The preparation method according to claim 2, wherein the molar ratio of the epichlorohydrin to the hydroxyl groups in the allyloxy castor oil-based polyol is 1-1.5: 1.
9. The preparation method according to claim 2, wherein the temperature of the second ring-opening reaction is 40-80 ℃ and the time is 1-5 h.
10. The preparation method according to claim 2, wherein the ring-closing reaction is carried out in the presence of a ring-closing catalyst and solid alkali, the temperature of the ring-closing reaction is 30-80 ℃, and the time is 2-6 h; the ring-closing catalyst is a quaternary ammonium salt phase transfer catalyst.
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| EP1406885B1 (en) * | 2001-07-05 | 2006-01-18 | Dow Global Technologies Inc. | Process for manufacturing an a-dihydroxy derivative and epoxy resins prepared therefrom |
| CN108299341A (en) * | 2018-01-04 | 2018-07-20 | 南京林业大学 | A kind of castor oil-base epoxy resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1406885B1 (en) * | 2001-07-05 | 2006-01-18 | Dow Global Technologies Inc. | Process for manufacturing an a-dihydroxy derivative and epoxy resins prepared therefrom |
| CN108299341A (en) * | 2018-01-04 | 2018-07-20 | 南京林业大学 | A kind of castor oil-base epoxy resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Synthesis and properties of castor oil based plasticizers;Qinghe Fu et al.,;《RSC Adv.》;20190329;第9卷;第10049-10057页 * |
| 蓖麻油缩水甘油醚合成工艺研究;王芳 等;《林产化学与工业》;20150831;第35卷(第4期);第112-116页 * |
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