CN112920061A - Preparation method of amino cardanol curing agent - Google Patents
Preparation method of amino cardanol curing agent Download PDFInfo
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- CN112920061A CN112920061A CN202110097674.8A CN202110097674A CN112920061A CN 112920061 A CN112920061 A CN 112920061A CN 202110097674 A CN202110097674 A CN 202110097674A CN 112920061 A CN112920061 A CN 112920061A
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- cardanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- 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
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
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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
- 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
- C08G59/40—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 curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The application relates to the technical field of fine chemical engineering, and particularly discloses a preparation method of an amino cardanol curing agent. The preparation method of the amino cardanol curing agent takes cardanol, peracetic acid and plant regenerative polyamine as raw materials and adopts a two-step method to prepare the amino cardanol curing agent, and the plant regenerative polyamine is pentanediamine. According to the preparation method, cardanol and plant renewable polyamine which are bio-based renewable resources are used as raw materials, harm to health of workers and environment in the preparation process is reduced, and the prepared curing agent has good curing performance.
Description
Technical Field
The application relates to the technical field of fine chemical engineering, in particular to a preparation method of an amino cardanol curing agent.
Background
Curing agents, also known as hardeners, curing agents or setting agents, are a class of substances or mixtures that enhance or control the curing reaction. The resin curing is carried out by adding a curing (crosslinking) agent to a thermosetting resin through chemical reactions such as condensation, ring closure, addition or catalysis to cause irreversible change of the thermosetting resin. The curing agent is an indispensable additive, and the curing agent is required to be added when the epoxy resin is used as an adhesive, a coating and a casting material, otherwise, the epoxy resin cannot be cured. The variety of the curing agent has great influence on the mechanical property, heat resistance, water resistance, corrosion resistance and the like of the cured product.
Commonly used curing agents are aliphatic amines, alicyclic amines, aromatic amines, acid anhydrides, polyamides, and the like. In the related technology, in the preparation process of the curing agent, a large amount of toxic and harmful substances such as formaldehyde, diamine and the like are used, and the solid raw materials need to be put into a reaction system in batches by operators for reaction, so that the harm is brought to the health of the operators, and the environmental pollution is also caused.
Disclosure of Invention
In order to reduce harm to health of workers and environment in the preparation process of the curing agent and enable the prepared curing agent to have good curing performance, the application provides a preparation method of the amino cardanol curing agent.
The preparation method of the amino cardanol curing agent is characterized in that cardanol, peracetic acid and plant regenerative polyamine are used as raw materials, the amino cardanol curing agent is prepared by a two-step method, the plant regenerative polyamine is pentanediamine, and the reaction equation is as follows:
S1：
S2：
by adopting the technical scheme, the amino cardanol curing agent is prepared by taking cardanol, peracetic acid and plant regenerative polyamine as raw materials, the raw materials do not contain toxic and harmful substances, harm to health of workers in the preparation process of the curing agent is reduced, the environment is protected, and the prepared amino cardanol curing agent has good curing performance and good corrosion resistance and chemical resistance. Meanwhile, impurities do not need to be removed after the reaction, the steps are simple, and the method is suitable for industrial production.
Preferably, the step of S1 is: adding cardanol into a solvent, adding a catalyst, heating and stirring, adding peroxyacetic acid while stirring, and carrying out heat preservation reaction to obtain the epoxidized cardanol.
By adopting the technical scheme, cardanol reacts with peroxyacetic acid under the action of a catalyst, and carbon-carbon double bonds are epoxidized to generate epoxidized cardanol. The cardanol and the peroxyacetic acid are used as raw materials, the raw materials are easy to purchase, the cardanol is refined from natural cashew nut shell oil, the environment-friendly performance is outstanding, and the cardanol is used for replacing phenol to manufacture an epoxy curing agent, so that the environment is protected.
Preferably, the step of S2 is: adding epoxy cardanol into a solvent, heating and dissolving, adding plant regenerative polyamine, heating for reaction, and distilling under reduced pressure to remove the solvent and acetic acid to obtain the amino cardanol.
By adopting the technical scheme, the epoxidized cardanol reacts with plant regenerative polyamine at high temperature to generate the amino cardanol. The raw materials used in the whole preparation process are environment-friendly raw materials, do not contain carcinogens, reduce the use of fossil raw materials and are beneficial to protecting the environment.
Preferably, the solvent is any one of xylene and aromatic hydrocarbon solvent # 100.
By adopting the technical scheme, the raw materials in the preparation method have good solubility in the solvent, and the solvent does not react with the raw materials chemically and is used as a reaction medium, so that the reaction is mild, and the temperature is easy to control.
Preferably, the catalyst is phosphotungstic heteropoly acid.
By adopting the technical scheme, phosphotungstic heteropoly acid, namely dodecaphosphotungstic acid, is solid strong acid, has better catalytic performance when added into a reaction system, promotes the forward reaction of cardanol and peroxyacetic acid, improves the reaction rate and promotes the formation of epoxidized cardanol.
Preferably, the temperature of the S1 is set to be 50-60 ℃ during heating and stirring, and after the peracetic acid is added, the reaction is kept for 8-12 h.
By adopting the technical scheme, at the reaction temperature, the cardanol reacts with peroxyacetic acid under the action of the catalyst, and epoxidation is performed to generate the epoxidized cardanol, so that the forward progress of the reaction is promoted, the reaction rate is increased, and the yield is increased.
Preferably, the plant regenerable polyamine may also be methylpentamethylene diamine.
By adopting the technical scheme, the methyl pentanediamine and the pentanediamine are plant regenerative polyamine, and the amino cardanol curing agent is prepared by using the methyl pentanediamine and the pentanediamine as raw materials to react, so that the use of fossil raw materials is reduced, the environment is protected, and resources are saved.
Preferably, in S2, the heating and dissolving temperature is set to 70-80 ℃, after the plant regenerative polyamine is added, the temperature is raised to 110 ℃ and the reaction is carried out for 3-5 h.
By adopting the technical scheme, under the temperature range, the epoxidized cardanol and the plant regenerative polyamine fully react to generate the amino cardanol, so that the reaction rate is improved.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, cardanol, peracetic acid and plant regenerative polyamine are used as raw materials to prepare the amino cardanol curing agent, the raw materials do not contain toxic and harmful substances, the environment is protected, meanwhile, the use of petrochemical raw materials is reduced, energy is saved, and harm to the health of workers and the environment in the curing agent preparation process is reduced;
2. the preparation method does not need to remove impurities, has simple steps and safe and controllable conditions, and is suitable for industrial production;
3. according to the preparation method, phosphotungstic heteropoly acid is used as a catalyst, so that the forward progress of the reaction of cardanol and peroxyacetic acid is promoted, the reaction rate is improved, and the formation of epoxidized cardanol is promoted.
Detailed Description
The present application will be described in further detail with reference to examples.
The phosphotungstic heteropoly acid in the embodiment of the application is obtained from Shanghai Hualan chemical science and technology limited;
xylene is collected from Wuxi Yongyou, chemical Co Ltd;
aromatic hydrocarbon solvent No. 100 was obtained from chemical company of Jinan Huahao, Ji;
cardanol is collected from Jiangsu saint Lun chemical technology Co., Ltd;
pentanediamine was obtained from Shanghai shellfish chemical Co., Ltd;
the methyl pentanediamine is obtained from Dalian Sun oil additives Co.
Examples
Example 1: a preparation method of an amino cardanol curing agent comprises the following steps:
s1, adding 30.2g of cardanol into 40g of dimethylbenzene, adding 1g of phosphotungstic heteropoly acid, heating to 50 ℃, stirring for 5min, adding 7.6g of peroxyacetic acid while stirring, and carrying out heat preservation reaction for 8h to obtain the epoxidized cardanol, wherein the reaction equation is as follows:
s2, adding epoxy cardanol into 40g of dimethylbenzene, heating to 70 ℃ for dissolution, adding 8.8g of pentamethylene diamine, heating to 100 ℃, reacting for 3 hours, and removing dimethylbenzene and acetic acid through reduced pressure distillation to obtain amino cardanol, wherein the reaction equation is as follows:
example 2: a preparation method of an amino cardanol curing agent comprises the following steps:
s1, adding 30.2g of cardanol into 40g of aromatic hydrocarbon solvent 100#, adding 1g of phosphotungstic heteropoly acid, heating to 50 ℃, stirring for 5min, adding 7.6g of peroxyacetic acid while stirring, and carrying out heat preservation reaction for 8h to obtain the epoxidized cardanol, wherein the reaction equation is as follows:
s2, adding epoxy cardanol into 40g of aromatic hydrocarbon solvent 100#, heating to 70 ℃ for dissolving, adding 8.8g of pentamethylene diamine, heating to 100 ℃, reacting for 3 hours, and removing xylene and acetic acid through reduced pressure distillation to obtain amino cardanol, wherein the reaction equation is as follows:
example 3: a preparation method of an amino cardanol curing agent comprises the following steps:
s1, adding 30.2g of cardanol into 40g of dimethylbenzene, adding 1g of phosphotungstic heteropoly acid, heating to 55 ℃, stirring for 5min, adding 7.6g of peroxyacetic acid while stirring, and carrying out heat preservation reaction for 10h to obtain the epoxidized cardanol, wherein the reaction equation is as follows:
s2, adding epoxy cardanol into 40g of xylene, heating to 75 ℃ to dissolve, adding 8.8g of pentamethylene diamine, heating to 105 ℃, reacting for 4 hours, and removing xylene and acetic acid through reduced pressure distillation to obtain amino cardanol, wherein the reaction equation is as follows:
example 4: a preparation method of an amino cardanol curing agent comprises the following steps:
s1, adding 30.2g of cardanol into 40g of dimethylbenzene, adding 1g of phosphotungstic heteropoly acid, heating to 60 ℃, stirring for 5min, adding 7.6g of peroxyacetic acid while stirring, and carrying out heat preservation reaction for 12h to obtain the epoxidized cardanol, wherein the reaction equation is as follows:
s2, adding epoxy cardanol into 40g of dimethylbenzene, heating to 80 ℃ for dissolution, adding 8.8g of pentamethylene diamine, heating to 110 ℃, reacting for 5 hours, and removing dimethylbenzene and acetic acid through reduced pressure distillation to obtain amino cardanol, wherein the reaction equation is as follows:
example 5: a preparation method of an amino cardanol curing agent comprises the following steps:
s1, adding 30.2g of cardanol into 40g of dimethylbenzene, adding 1g of phosphotungstic heteropoly acid, heating to 50 ℃, stirring for 5min, adding 7.6g of peroxyacetic acid while stirring, and carrying out heat preservation reaction for 8h to obtain the epoxidized cardanol, wherein the reaction equation is as follows:
s2, adding epoxy cardanol into 40g of dimethylbenzene, heating to 70 ℃ for dissolution, adding 10.2g of methyl pentanediamine, heating to 100 ℃, reacting for 3 hours, and removing dimethylbenzene and acetic acid through reduced pressure distillation to obtain amino cardanol, wherein the reaction equation is as follows:
comparative example
Comparative example 1: a curing agent is a 593 epoxy resin curing agent which is obtained from Wuxi Yehao chemical Co.
Comparative example 2: a curing agent was different from example 1 in that the temperature during heating and stirring in S1 in the production process of the curing agent was set to 40 ℃.
Comparative example 3: a curing agent was different from example 1 in that the temperature during heating and stirring in S1 in the production process of the curing agent was set to 70 ℃.
Comparative example 4: a curing agent was different from example 1 in that the reaction temperature was set to 90 ℃ after addition of pentamethylenediamine in S2 during the preparation of the curing agent.
Comparative example 5: a curing agent was different from example 1 in that the reaction temperature was set to 120 ℃ after addition of pentamethylenediamine in S2 during the preparation of the curing agent.
Performance test
The curing agents prepared in examples 1-5 and comparative examples 1-5 were respectively used as test objects, epoxy resin and the prepared curing agent were mixed according to a weight ratio of 3:1, and the mixture was uniformly coated on a tin plate to form a film, the specification of the tin plate was 120mm by 50mm by 0.20mm, the film thickness was 40 μm, the molding time and the curing time of the curing agent were recorded, the adhesion of the curing agent was tested according to the paint film circling test in GB/T1720-.
As can be seen from the test data in table 1: the amino cardanol curing agent prepared by the preparation method of the embodiment 1-5 has good adhesion and short forming and curing time, wherein the embodiment 3 is the optimal embodiment.
As can be seen from the combination of example 3 and comparative example 1, and table 1, the amino cardanol curing agent prepared by using the preparation method of example 3 of the present application has no significant difference in molding time, curing time and adhesion grade compared with the epoxy curing agent commercially available in comparative example 1. The application shows that when cardanol and plant renewable polyamine are used as raw materials to synthesize the amino cardanol curing agent, the prepared amino cardanol curing agent has good curing performance while harm to health of workers and environment in the preparation process is reduced, and the performance of the amino cardanol curing agent is not obviously reduced compared with that of a commercially available curing agent.
As can be seen from the combination of examples 1, 3, 4 and comparative examples 2 to 5 and table 1, in the preparation process of the amino cardanol, the stirring temperature is preferably set to 50 to 60 ℃ in S1, and the reaction temperature of the epoxidized cardanol and the plant renewable polyamine is preferably set to 110 ℃ in S2, and the prepared amino cardanol curing agent is molded and cured more rapidly in the temperature range.
Table 1 results of performance testing
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The preparation method of the amino cardanol curing agent is characterized in that cardanol, peroxyacetic acid and plant regenerative polyamine are used as raw materials and prepared by a two-step method, wherein the plant regenerative polyamine is pentanediamine, and the reaction equation is as follows:
S1：
S2：
2. the method for preparing the amino cardanol curing agent according to claim 1, wherein the step of S1 is: adding cardanol into a solvent, adding a catalyst, heating and stirring, adding peroxyacetic acid while stirring, and carrying out heat preservation reaction to obtain the epoxidized cardanol.
3. The method for preparing the amino cardanol curing agent according to claim 1, wherein the step of S2 is: adding epoxy cardanol into a solvent, heating and dissolving, adding plant regenerative polyamine, heating for reaction, and distilling under reduced pressure to remove the solvent and acetic acid to obtain the amino cardanol.
4. The method for preparing amino cardanol curing agent according to any one of claims 2 to 3, wherein said solvent is any one of xylene and aromatic hydrocarbon solvent # 100.
5. The preparation method of the amino cardanol curing agent according to claim 2, wherein the catalyst is phosphotungstic heteropoly acid.
6. The preparation method of the amino cardanol curing agent according to claim 5, wherein the temperature during heating and stirring in S1 is set to 50-60 ℃, and after peracetic acid is added, the reaction is kept for 8-12 h.
7. The method for preparing amino cardanol curing agent according to claim 3, wherein said plant regenerative polyamine may also be methylpentamethylene diamine.
8. The method for preparing amino cardanol curing agent according to claim 7, wherein the temperature for heating and dissolving in S2 is set to 70-80 ℃, after adding the plant regenerative polyamine, the temperature is raised to 100-110 ℃, and the reaction is carried out for 3-5 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011037959A (en) * | 2009-08-08 | 2011-02-24 | Daicel Chemical Industries Ltd | Method for producing epoxidized polyene resin |
| CN105601887A (en) * | 2015-12-31 | 2016-05-25 | 上海美东生物材料股份有限公司 | Alicyclic amine curing agent and preparing method thereof |
| CN111808252A (en) * | 2020-07-31 | 2020-10-23 | 浙江万盛股份有限公司 | Preparation method of N-P synergistic cardanol-based flame-retardant curing agent |
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2021
- 2021-01-25 CN CN202110097674.8A patent/CN112920061B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011037959A (en) * | 2009-08-08 | 2011-02-24 | Daicel Chemical Industries Ltd | Method for producing epoxidized polyene resin |
| CN105601887A (en) * | 2015-12-31 | 2016-05-25 | 上海美东生物材料股份有限公司 | Alicyclic amine curing agent and preparing method thereof |
| CN111808252A (en) * | 2020-07-31 | 2020-10-23 | 浙江万盛股份有限公司 | Preparation method of N-P synergistic cardanol-based flame-retardant curing agent |
Non-Patent Citations (1)
| Title |
|---|
| 刘小英: ""氨基腰果酚的合成、表征与特性的研究"", 《林 产 化 学 与 工 业》 * |
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