CN112961458A - Tung oil based epoxy flexibilizer and preparation method thereof - Google Patents
Tung oil based epoxy flexibilizer and preparation method thereof Download PDFInfo
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- CN112961458A CN112961458A CN202110104068.4A CN202110104068A CN112961458A CN 112961458 A CN112961458 A CN 112961458A CN 202110104068 A CN202110104068 A CN 202110104068A CN 112961458 A CN112961458 A CN 112961458A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
- C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
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Abstract
A tung oil based epoxy flexibilizer and a preparation method thereof are disclosed, wherein the preparation steps comprise mixing tung oil and glycerol according to a molar ratio of 2:1, adding a catalyst KOH with the mass of 0.5-2 wt.% of the tung oil, reacting for 3-4 h at 180 ℃ under the protection of nitrogen to obtain a mixture of tung oil diglyceride and glycerol, and then separating liquid to obtain light yellow tung oil diglyceride; mixing tung oil diglycidylester and saturated cyclic anhydride according to the molar ratio of 1: 1-1: 4, adding a catalyst with the mass of 0.5-2 wt.% of tung oil monoglyceride, and reacting for 3-6 h at 120-150 ℃ under the protection of nitrogen to synthesize the tung oil based epoxy flexibilizer containing one carboxyl group and two molecular chains containing conjugated double bonds. The prepared tung oil-based epoxy toughening agent has excellent compatibility with epoxy resin, avoids the problem of material transparency reduction and the like caused by phase separation, and can ensure that the epoxy resin has very high elongation at break and toughness and can also keep very high strength and modulus by adding a small amount of the tung oil-based epoxy toughening agent.
Description
Technical Field
The invention belongs to the field of epoxy resin, and particularly relates to a tung oil-based epoxy flexibilizer and a preparation method thereof.
Background
The epoxy resin as thermosetting resin can react with amine, acid anhydride and other curing agent to produce three-dimensional network cross-linking structure. The epoxy resin composition has the advantages of excellent thermal stability, mechanical property, insulativity, high adhesion, molding processability and the like, and is widely applied to the fields of coatings, electronics and electrics, adhesives, composite materials, civil engineering and the like. However, the cured product has a high cross-linked network structure, large internal stress, brittleness and poor impact resistance, and is easy to damage when directly used, thereby causing serious dangerous accidents and economic losses, so the toughening design of the cured product is very important. The epoxy tougheners currently used are mainly based on petroleum-based rubber elastomers, interpenetrating network polymers, flexible curing agents, thermoplastic resins, hyperbranched polymers, thermotropic liquid crystal polymers and core-shell particles. These methods have more or less some problems, for example, poor compatibility and reduced transparency occur when the hydantoin type epoxy resin is toughened with liquid butyl rubber; the inorganic nano particles or the nano particles with the core-shell structure and the organic elastic nano particles are used for toughening, so that the processing difficulty is high, the uniform dispersion is difficult, and the toughening purpose cannot be achieved. In addition, the large amount of the petroleum-based epoxy flexibilizer is not in line with the concept of sustainable development, and simultaneously faces the problems of environmental pollution and the like.
Disclosure of Invention
The technical problem to be solved is as follows: the invention discloses a tung oil-based epoxy flexibilizer and a preparation method thereof, aiming at solving the defects of high rigidity, brittle quality and the like of epoxy resin and meeting the sustainable green development requirement. The addition of a very small amount of the tung oil based epoxy toughener can make the epoxy resin have very high elongation at break and toughness, and can also keep very high strength and modulus.
The technical scheme is as follows: a tung oil based epoxy flexibilizer has the following chemical structure:
wherein R is1Is composed of
R2Is composed of
Or, R1Is that
R2Is composed of
The tung oil-based epoxy toughening agent is one or a mixture of two of the above molecular structures.
The preparation method of the tung oil-based epoxy toughening agent comprises the following steps: step 1, mixing tung oil and glycerol according to a molar ratio of 2:1, adding a catalyst KOH with the mass of 0.5-2 wt.% of the tung oil, reacting for 3-4 h at 180 ℃ under the protection of nitrogen to obtain a mixture of tung oil diglyceride and glycerol, and separating liquid to obtain light yellow tung oil diglyceride; and 2, mixing the tung oil diglyceride and saturated cyclic anhydride according to the molar ratio of 1: 1-1: 4, adding a catalyst with the mass of 0.5-2 wt.% of the tung oil monoglyceride, and reacting for 3-6 h at 120-150 ℃ under the protection of nitrogen to synthesize the tung oil based epoxy flexibilizer containing one carboxyl group and two molecular chains containing conjugated double bonds.
In the step 2, the saturated cyclic acid anhydride is at least one of phthalic anhydride, succinic anhydride, glutaric anhydride, 1, 2-cyclohexanedicarboxylic anhydride, 2-dimethylsuccinic anhydride, 2-dimethylglutaric anhydride, 3-dimethylglutaric anhydride, 3-methylglutaric anhydride, 3-hydroxyphthalic anhydride, 1, 8-naphthalic anhydride, 4-nitro-1, 8-naphthalic anhydride, 2- (triphenylphosphoridene) succinic anhydride and 2-phenylpentanoic anhydride.
In the step 2, the catalyst is at least one of triphenylphosphine, p-toluenesulfonic acid, benzyltrimethylammonium chloride and benzyltriethylammonium chloride; the content of the catalyst is 0.5-1 wt% of the mass of the tung oil diglyceride.
And 2, the molar ratio of the tung oil diglycol to the saturated cyclic anhydride is 1: 1.
Has the advantages that: the epoxy toughening agent is prepared by taking tung oil as a raw material, and cheap and renewable raw materials are used for replacing petrochemical resources. Secondly, the epoxy resin can have very high elongation at break and toughness by adding a small amount of the tung oil-based epoxy flexibilizer, and the epoxy resin can also keep very high strength and modulus. The prepared tung oil-based epoxy flexibilizer has excellent compatibility with epoxy resin, and the problem of material transparency reduction caused by phase separation is avoided. Fourthly, the tung oil based epoxy flexibilizer has simple preparation process and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an infrared spectrum of raw tung oil;
FIG. 2 is an infrared spectrum of the tung oil-based epoxy toughener synthesized in example 1, showing 1713cm-1Characteristic peak of carboxyl group;
FIG. 3 is a stress-strain curve of a cured product of modified epoxy resin E51 obtained in example 4.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1
The method comprises the following steps: 100g of tung oil, 34g of glycerol and 0.05g of potassium hydroxide are added into a 250mL four-neck flask provided with a stirring device, nitrogen protection is introduced, and the mixture reacts for 3 hours at 180 ℃. And after the reaction is finished, cooling to room temperature for liquid separation to obtain the tung oil monoglyceride.
Step two: and (3) taking 61.1g of the diglycol tung oil prepared in the step one and 10g of succinic anhydride, adding p-toluenesulfonic acid which is 0.5 wt% of the weight of the diglycol tung oil into a 250mL four-neck flask, and reacting at 130 ℃ for 3 hours under the protection of nitrogen to prepare the faint yellow tung oil-based epoxy flexibilizer.
Step three: weighing 2.5g of the tung oil-based epoxy flexibilizer prepared in the step two, placing 100g of epoxy resin in a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3h to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
Example 2
The reaction procedure is the same as in example 1 except that the amount of the tung oil based epoxy toughener used to modify the epoxy resin is 5 g.
Example 3
The reaction procedure is the same as in example 1 except that the amount of the tung oil based epoxy toughener used to modify the epoxy resin is 7.5 g.
Example 4
The reaction procedure is the same as in example 1 except that the amount of the tung oil based epoxy toughener used to modify the epoxy resin is 10 g.
Example 5
The method comprises the following steps: 61.1g of diethylene glycol tung oil and 11.4g of glutaric anhydride, adding 0.5 wt.% of triphenylphosphine in the mass of the diethylene glycol tung oil into a 250mL four-neck flask, protecting with nitrogen, and reacting at 130 ℃ for 3 hours to obtain the faint yellow tung oil-based epoxy flexibilizer.
Step two: and (3) weighing 10g of the tung oil-based epoxy flexibilizer prepared in the step one and 100g of epoxy resin in a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3h to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
Example 6
The method comprises the following steps: 61.1g of tung oil diglycol and 14.8g of terephthalic anhydride, adding 0.5 wt.% of benzyltrimethylammonium chloride based on the mass of the tung oil diglycol into a 250mL four-neck flask, and reacting for 3 hours at 130 ℃ under the protection of nitrogen to prepare the faint yellow tung oil-based epoxy flexibilizer.
Step two: and (3) weighing 10g of the tung oil-based epoxy flexibilizer prepared in the step one and 100g of epoxy resin in a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3h to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
Example 7
The method comprises the following steps: 61.1g of tung oil diglycol and 15.4g of 1, 2-cyclohexane dicarboxylic anhydride, 0.5 wt.% of benzyltriethylammonium chloride based on the mass of the tung oil diglycol is added into a 250mL four-neck flask, and the mixture is reacted for 3 hours at 130 ℃ under the protection of nitrogen to prepare the faint yellow tung oil-based epoxy flexibilizer.
Step two: and (3) weighing 10g of the tung oil-based epoxy flexibilizer prepared in the step two and 100g of epoxy resin in a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3h to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
Comparative example 1
Weighing 7.5g of epoxidized soybean oil and 100g of epoxy resin in a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3 hours to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
Comparative example 2
Weighing 20g of random carboxyl nitrile rubber and 100g of epoxy resin in a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3h to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
Comparative example 3
Preparing random carboxyl tung nitrile rubber according to CN201811531525.2 patent, weighing 35g of random carboxyl tung nitrile rubber and 100g of epoxy resin in a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3h to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
Comparative example 4
A random carboxyl tung nitrile rubber epoxy flexibilizer is prepared according to the patent CN 201811531525.2. Weighing 45g of random carboxyl nitrile rubber and 100g of epoxy resin in a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3h to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
Comparative example 5
Preparing the polar carboxylated tung oil epoxy flexibilizer according to a patent of CN201910540079. Weighing 30g of polar carboxylated tung oil and 100g of epoxy resin into a 250mL four-neck flask, heating to 130 ℃ under the protection of nitrogen, and continuing to react for 3 hours to obtain the modified epoxy resin.
10g of the resulting modified epoxy resin was added to 5g D400 and cured at room temperature.
TABLE 1 mechanical Properties of cured modified epoxy resins
| Curing System (toughening agent content) | Tensile strength MPa | Elongation at break% | Modulus of elasticity MPa | Toughness (MJ/m)3) |
| Example 1 (2.5%) | 52.6 | 9.1 | 2794 | 2.2 |
| Example 2 (5%) | 45.9 | 30.3 | 2565 | 7.7 |
| Example 3 (7.5%) | 35.4 | 90.1 | 2223 | 19.7 |
| Example 4 (10%) | 28.9 | 115.0 | 1993 | 23.9 |
| Example 5 (10%) | 26.5 | 121.0 | 1875 | 24.5 |
| Example 6 (10%) | 37.4 | 100.5 | 2453 | 27.2 |
| Example 7 (10%) | 27.2 | 119.2 | 2001 | 26.1 |
| Comparative example 1 (7.5%) | 34.7 | 24.2 | 2244 | 5.8 |
| Comparative example 2 (20%) | 28.0 | 15.0 | 1988 | 2.3 |
| Comparative example 3 (35%) | 27.5 | 33.5 | 1651 | 7.6 |
| Comparative example 4 (45%) | 17.3 | 100.0 | 354 | 13.5 |
| Comparative example 5 (30%) | 37.8 | 22.3 | 1925 | 6.6 |
It can be seen from the table that the elongation at break and toughness of the epoxy resin can be improved by only adding a small amount of tung oil-based epoxy toughening agent, and higher strength and modulus can be maintained, and the toughening effect of the epoxy resin is superior to that of commercially available epoxy soybean oil and random carboxyl nitrile rubber and also superior to that of the tung oil-based epoxy toughening agent (CN201811531525.2, CN201910540079.X) of the previous patent application.
Claims (6)
1. A tung oil based epoxy flexibilizer is characterized in that the chemical structure is as follows:
wherein R is1Is composed of
R2Is composed of
Or, R1Is that
R2Is composed of
2. A tung oil based epoxy flexibilizer according to claim 1 characterized by being one or a mixture of both of the above molecular structures.
3. A method of making the tung oil-based epoxy toughener of claim 1, characterized by the steps of:
step 1, mixing tung oil and glycerol according to a molar ratio of 2:1, adding a catalyst KOH with the mass of 0.5-2 wt.% of the tung oil, reacting for 3-4 h at 180 ℃ under the protection of nitrogen to obtain a mixture of tung oil diglyceride and glycerol, and separating liquid to obtain light yellow tung oil diglyceride;
and 2, mixing the tung oil diglyceride and saturated cyclic anhydride according to the molar ratio of 1: 1-1: 4, adding a catalyst with the mass of 0.5-2 wt.% of the tung oil monoglyceride, and reacting for 3-6 h at 120-150 ℃ under the protection of nitrogen to synthesize the tung oil based epoxy flexibilizer containing one carboxyl group and two molecular chains containing conjugated double bonds.
4. The method of preparing a tung oil-based epoxy toughener as recited in claim 3, wherein the saturated cyclic anhydride in step 2 is at least one of phthalic anhydride, succinic anhydride, glutaric anhydride, 1, 2-cyclohexanedicarboxylic anhydride, 2-dimethylsuccinic anhydride, 2-dimethylglutaric anhydride, 3-dimethylglutaric anhydride, 3-methylglutaric anhydride, 3-hydroxyphthalic anhydride, 1, 8-naphthalic anhydride, 4-nitro-1, 8-naphthalic anhydride, 2- (triphenylphosphoridene) succinic anhydride, 2-phenylpentanoic anhydride.
5. The method for preparing the tung oil-based epoxy toughener as claimed in claim 3, wherein the catalyst in step 2 is at least one of triphenylphosphine, p-toluenesulfonic acid, benzyltrimethylammonium chloride and benzyltriethylammonium chloride; the content of the catalyst is 0.5-1 wt% of the mass of the tung oil diglyceride.
6. The method of preparing the tung oil-based epoxy toughener of claim 3, wherein the molar ratio of the tung oil diglycolate to the saturated cyclic anhydride of step 2 is 1: 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115895544A (en) * | 2022-12-29 | 2023-04-04 | 中国林业科学研究院林产化学工业研究所 | High-toughness military shelter structural adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360246A (en) * | 2013-07-11 | 2013-10-23 | 中南林业科技大学 | Method for preparing eleostearic acid monoglycerides from tung oil |
| CN105980604A (en) * | 2013-12-10 | 2016-09-28 | 路博润公司 | Organic salts of glyceride-cyclic carboxylic acid anhydride adducts as corrosion inhibitors |
| CN106519199A (en) * | 2016-11-14 | 2017-03-22 | 南京林业大学 | Preparation method of modified tung oil alkyd resin |
| CN110256654A (en) * | 2019-06-21 | 2019-09-20 | 中国林业科学研究院林产化学工业研究所 | A kind of flexible epoxy resin of tung oil base and preparation method thereof |
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- 2021-01-26 CN CN202110104068.4A patent/CN112961458A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360246A (en) * | 2013-07-11 | 2013-10-23 | 中南林业科技大学 | Method for preparing eleostearic acid monoglycerides from tung oil |
| CN105980604A (en) * | 2013-12-10 | 2016-09-28 | 路博润公司 | Organic salts of glyceride-cyclic carboxylic acid anhydride adducts as corrosion inhibitors |
| CN106519199A (en) * | 2016-11-14 | 2017-03-22 | 南京林业大学 | Preparation method of modified tung oil alkyd resin |
| CN110256654A (en) * | 2019-06-21 | 2019-09-20 | 中国林业科学研究院林产化学工业研究所 | A kind of flexible epoxy resin of tung oil base and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115895544A (en) * | 2022-12-29 | 2023-04-04 | 中国林业科学研究院林产化学工业研究所 | High-toughness military shelter structural adhesive and preparation method thereof |
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