CN107189357B - Epoxy resin system and preparation method thereof - Google Patents
Epoxy resin system and preparation method thereof Download PDFInfo
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- CN107189357B CN107189357B CN201710561789.1A CN201710561789A CN107189357B CN 107189357 B CN107189357 B CN 107189357B CN 201710561789 A CN201710561789 A CN 201710561789A CN 107189357 B CN107189357 B CN 107189357B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an epoxy resin system which comprises the following components in parts by weight: 100 parts of epoxy resin, 10-70 parts of curing agent, 1-20 parts of accelerator and 0.1-10 parts of coating agent. The viscosity change of the epoxy resin system prepared by the invention is less than 150% after the epoxy resin system is placed for 1 hour at 50 ℃ and 1 bar; the curing time at 50 ℃ and 50bar is 10-30 seconds.
Description
Technical Field
The invention relates to the technical field of chemical materials, and particularly relates to an epoxy resin system and a preparation method thereof.
Background
Since the advent of the epoxy resin, due to its excellent physical and chemical properties and simple molding process, it has been widely used in various industries, and is currently the most widely used thermosetting resin with optimal properties in the industry. In recent years, with the rapid development of industries such as wind power generation, automobiles, aerospace and the like, the status of the reinforced fiber/epoxy resin composite material is increasingly important.
At present, large-scale fiber reinforced epoxy resin composite materials are mostly manufactured by Vacuum Assisted Resin Transfer Molding (VARTM), Resin Transfer Molding (RTM) and Reaction Injection Molding (RIM), wherein the RTM process is favored due to the advantages of short molding period, good production environment and the like because of closed mold molding, however, the RTM process generally has the following two problems that ⑴ resin is not ideal for soaking fibers, common RTM is not pressurized, only gravity or vacuum pumping is used for limiting the amount of liquid resin soaked into a fiber layer, so that the molding time is long, the void ratio of products is high, resin flow is unbalanced in ⑵ large-size or complex-structure molds, prediction and control cannot be carried out, the application of the process in the aspect of complex structural part molding is limited, therefore, the speed of soaking the resin into the fiber material is accelerated by adding high pressure, and the problems are overcome, and CN102675827 provides an epoxy resin-based carbon fiber composite material manufactured by using a high-pressure resin transfer molding rapid prototyping process (HP-ATM).
In order to meet the requirements of high pressure resin transfer molding rapid prototyping processes, the resin needs to be cured rapidly. However, in the preparation processes of raw material mixing and the like, the resin needs to be stabilized, and particularly, an aliphatic amine curing agent system which can be cured at room temperature or slightly above room temperature is difficult to ensure that the preparation time of raw material mixing and the like is sufficient, and the resin can be cured at high speed during molding; if a suitable accelerator is added, its cure rate can be increased, but too fast a cure rate can result in too short a time available for mixing of the raw materials.
Therefore, in the high-pressure resin transfer molding process, an on-line mixing process is generally adopted, i.e., epoxy resin and curing agent are respectively metered and injected into a mixing chamber, and after being mixed in the mixing chamber, the epoxy resin and the curing agent are injected into a cavity at high pressure. The process needs to precisely control the flow rates of the epoxy resin and the curing agent, and the device cost is high; even if a precise flow rate control device is used, when the addition amount of the curing agent is small, the flow rate is generally difficult to be precisely controlled, so that the deviation of the epoxy resin/curing agent ratio and the design value is caused, and the product quality is influenced; finally, short mixing times result in uneven mixing and can also affect product quality.
Disclosure of Invention
In view of the technical problems of the background art, the present invention provides an epoxy resin system that is curable at room temperature or slightly above room temperature, is stable for a long time at normal pressure, and is rapidly cured at high pressure. Therefore, the raw materials can be premixed under normal pressure, online mixing is not needed, the manufacturing cost is reduced, and the product quality is improved.
The invention provides an epoxy resin system which comprises the following components in parts by weight: 100 parts of epoxy resin, 10-70 parts of curing agent, 1-20 parts of accelerator and 0.1-10 parts of coating agent.
The epoxy resin system has over 90 wt% of the promoter dispersed in the coating agent phase under 1bar pressure. The epoxy resin system can also contain one or more of a diluent, a defoaming agent, a coupling agent and an antioxidant.
The epoxy resin is one of bisphenol A epoxy resin, bisphenol F epoxy resin, p-aminophenol epoxy resin, o-cresol epoxy resin, phenol aldehyde epoxy resin and polyfunctional epoxy resin, and bisphenol A epoxy resin is preferred.
Preferably, the curing agent comprises one of aliphatic polyamine curing agents.
Preferably, the accelerator is phenol or one of derivatives.
Preferably, the coating agent is selected from polysuccinate glyceride or polyhexamate glyceride.
Preferably, the coating agent is dispersed in the epoxy resin phase as a dispersed phase, the dispersed phase of the coating agent having an average diameter of 100 μm or less.
Preferably, the coating agent is not crosslinked, and the number average molecular weight is 5000-25000 g/mol.
A preparation method of an epoxy resin system comprises the following steps: s1: and (3) uniformly mixing the accelerant and the coating agent, and cooling. S2: pulverizing the mixture obtained in S1 into particles with diameter of less than 100 μm by a pulverizer; s3: and (3) mixing the particles prepared by the step S2 with epoxy resin and a curing agent to obtain an epoxy resin system.
Further, the mixing temperature of the S1 is 80-100 ℃, and the mixing temperature of the S3 is 20-30 ℃.
The invention provides an epoxy resin system for preparing a fiber reinforced epoxy composite material, which comprises the following steps: 1) placing the fiber cloth prefabricated part into a mold cavity; 2) closing the mould, vacuumizing by a vacuum pump, injecting the epoxy resin system prepared by the invention into the cavity at high pressure of 30-80bar, and curing and molding the epoxy resin at high pressure. The fiber cloth is one or more of glass fiber cloth, carbon fiber cloth and the like, and carbon fiber cloth is preferred.
Compared with the prior art, the invention has the beneficial effects that:
1. the epoxy resin system of the invention is at normal temperature and normal pressure, and the accelerant is coated by the coating agent, so the accelerant can not play a role in accelerating the curing of the epoxy resin, the properties of the raw materials are stable, and the raw materials in the system can be fully mixed and stored for a long time; the viscosity change of the epoxy resin system is less than 150% after the epoxy resin system is placed at 50 ℃ and 1bar for 1 hour;
2. when the epoxy resin system is applied to a high-pressure resin transfer molding rapid forming process, the coating agent is broken under a high-pressure condition, and the epoxy curing accelerator coated in the coating agent is released, so that the curing rate of the epoxy resin is increased, and the effect of rapid curing is achieved; the curing time of the epoxy resin system of the invention is 10-30 seconds at 50 ℃ and 50 bar.
3. When the epoxy resin system is applied to the high-pressure resin transfer molding rapid forming process, online mixing is not needed, the equipment cost is reduced, and the popularization of the high-pressure resin transfer molding rapid forming process is facilitated.
Detailed Description
The present invention is directed to an epoxy resin system, and the invention is further illustrated with reference to the following specific examples.
The detection items and the test methods thereof in the embodiments:
1. viscosity change (%): after the raw materials were thoroughly mixed using a mixer, the initial viscosity of the sample at 1bar at 50 ℃ was measured using a rotational viscometer. Thereafter, the sample was left at 50 ℃ for 1 hour at 1bar, the viscosity was measured again with a rotary viscometer, and the change in viscosity of the sample during the leaving was calculated as follows:
sample viscosity after 1 hour (%)/initial viscosity x 100%
2. Curing time: the measurement was carried out by using a high-pressure type differential scanning calorimeter of DSC204HP, manufactured by Netzsch company. And (3) under 1bar or 50bar, heating to 50 ℃ at a heating rate of 10 ℃/min, and then measuring the isothermal solidification curve of the sample as a time zero point. The peak time of the curing peak was twice as long as the curing time at 50 ℃ and 50 bar.
3. Number average molecular weight: using chloroform as mobile phase, and measuring with gel chromatography (GPC).
4. Particle size: the sample size was measured using light scattering. The number average of the diameters was taken as the average diameter of the sample.
Raw materials used in examples and comparative examples:
epoxy resin: bisphenol a type epoxy resin;
curing agent: g1: diethylenetriamine; g2: menthane diamine.
Accelerator (b): c1: phenol; c2: p-chlorophenol.
Coating agent: b1: the poly (glycerol succinate) is prepared by the following method: dehydrating and polycondensing equimolar succinic acid and glycerol at 160 ℃ for a certain time under the protection of nitrogen, and cooling to obtain a colorless transparent solid. Samples with number average molecular weights of 5000, 10000, 15000, 20000, 25000g/mol were prepared, respectively. (error in number average molecular weight is less than. + -. 10%)
B2: the polyglycerol adipate is prepared by the following method: dehydrating and polycondensing equimolar adipic acid and glycerol at 160 ℃ for a certain time under the protection of nitrogen, and cooling to obtain a colorless transparent solid. Samples with number average molecular weights of 5000, 10000, 15000, 20000, 25000g/mol were prepared, respectively. (error in number average molecular weight is less than. + -. 10%)
Comparative examples 1 to 4
Epoxy resin, curing agent and accelerator were mixed uniformly at 25 ℃ with a mixer according to the formulation in table 1 to obtain an epoxy resin system. Of these, comparative examples 1 and 2 did not use an accelerator.
The viscosity change (50 ℃ C., 1bar, standing for 1 hour), curing time (50 ℃ C., 50bar) were measured and the results are shown in Table 1.
TABLE 1
And (4) conclusion: the epoxy systems of comparative examples 1 and 2, although having a very slow change in viscosity at 50 ℃ and 1bar, have a curing speed at 50 ℃ and 50bar that is too slow to be suitable for high pressure resin transfer molding rapid prototyping processes. Comparative examples 3 and 4 had too rapid a viscosity change at 1bar at 50 ℃ to be premixed.
Examples 1 to 8
The accelerator and the coating agent were mixed uniformly at 80 ℃ in a mixer according to the formulation shown in Table 2, and then cooled. The mixture of the accelerator and the coating agent is pulverized into particles having a diameter of 100 μm or less using a pulverizer. Then, the above-mentioned accelerator, coating agent, epoxy resin and curing agent were mixed uniformly at 20 ℃ in the proportions shown in Table 1 to obtain an epoxy resin system.
The viscosity change (50 ℃ C., 1bar, standing for 1 hour), the curing time (50 ℃ C., 50bar) were measured and the results are shown in Table 2.
TABLE 2 compositions and test results of examples 1-8
Examples 9 to 12
The accelerator and the coating agent were mixed uniformly at 90 ℃ in a mixer according to the formulation shown in Table 3, and then cooled. The mixture of the accelerator and the coating agent is pulverized into particles having a diameter of 100 μm or less using a pulverizer. Then, the above-mentioned accelerator, coating agent, epoxy resin and curing agent were mixed uniformly at 25 ℃ in the proportions shown in Table 1 to obtain an epoxy resin system. Only the coating agent was replaced with the coating agent shown in table 3.
The viscosity change (50 ℃ C., 1bar, standing for 1 hour), the curing time (50 ℃ C., 50bar) were measured and the results are shown in Table 3.
TABLE 3 compositions and test results for examples 9-12
Examples 13 to 15
A portion of the accelerator (the accelerator mixed with the coating agent described in the table) and the coating agent were mixed uniformly at 100 ℃ in a mixer according to the raw materials and the mixing ratio of example 11, and then cooled. The mixture of the accelerator and the coating agent is pulverized into particles having a diameter of 100 μm or less using a pulverizer.
Then, the mixed particles of the accelerator and the coating agent, the remaining accelerator, the epoxy resin, and the curing agent were uniformly mixed at 30 ℃ in the ratio of example 11 to obtain an epoxy resin system. The viscosity change (50 ℃, 1bar, 1 hour of standing), the curing time (50 ℃, 1bar and 50bar) were tested and the results are given in Table 4.
TABLE 4 compositions and test results of examples 13-15
And (4) conclusion: the viscosity change of the epoxy resin system prepared by the invention is less than 150% after the epoxy resin system is placed for 1 hour at 50 ℃ and 1 bar; the curing time at 50 ℃ and 50bar is 10-30 seconds.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. An epoxy resin system is characterized by comprising the following components in parts by weight: 100 parts of epoxy resin, 10-70 parts of curing agent, 1-20 parts of accelerator and 0.1-10 parts of coating agent; the coating agent is not crosslinked, and the number average molecular weight is 5000-25000 g/mol; the coating agent is poly-glycerol succinate or poly-glycerol adipate; the epoxy resin system is prepared by uniformly mixing an accelerator and a coating agent in advance to prepare a mixture, crushing the mixture into particles with the particle size of less than 100 microns, and then mixing the particles with epoxy resin and a curing agent; wherein the mixing of the accelerator and the coating agent is carried out at a pressure of 1bar and a temperature of 80-100 ℃, and more than 90% by weight of the accelerator is dispersed in the coating agent phase in the mixture of the accelerator and the coating agent.
2. An epoxy resin system according to claim 1, wherein said curing agent comprises one of aliphatic polyamine type curing agents.
3. The epoxy resin system of claim 1, wherein the accelerator is one of phenol and a derivative thereof.
4. The epoxy system of claim 1, wherein the coating agent is dispersed in the epoxy phase as a dispersed phase, the dispersed phase of the coating agent having an average diameter of less than 100 microns.
5. The method of claim 1, comprising the steps of: s1: uniformly mixing the accelerator and the coating agent, and cooling, wherein the mixing temperature in the step S1 is 80-100 ℃, and the mixing pressure is 1 bar; s2: pulverizing the mixture obtained in S1 into particles with diameter of less than 100 μm by a pulverizer; s3: and (3) mixing the particles prepared in the step S2 with epoxy resin and a curing agent, wherein the mixing temperature in the step S3 is 20-30 ℃, and thus an epoxy resin system is obtained.
6. Use of an epoxy resin system according to any one of claims 1 to 4 for the preparation of a fibre-reinforced epoxy composite.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710561789.1A CN107189357B (en) | 2017-07-11 | 2017-07-11 | Epoxy resin system and preparation method thereof |
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| CN201710561789.1A CN107189357B (en) | 2017-07-11 | 2017-07-11 | Epoxy resin system and preparation method thereof |
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| CN107189357B true CN107189357B (en) | 2020-06-02 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295824A (en) * | 2011-07-08 | 2011-12-28 | 蓝星(北京)化工机械有限公司 | One-part high-performance epoxy resin composition for pultrusion |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295824A (en) * | 2011-07-08 | 2011-12-28 | 蓝星(北京)化工机械有限公司 | One-part high-performance epoxy resin composition for pultrusion |
Non-Patent Citations (2)
| Title |
|---|
| Development of poly(glycerol adipate) nanoparticles loaded with non-steroidal anti-inflammatory drugs;Abdul Wahab et al.;《Journal of Microencapsulation》;20120706;第29卷(第5期);第497–504页 * |
| Synthesis and Characterization of Poly(glycerol-succinic acid) Dendrimers;Michael A. Carnahan et al.;《Macromolecules》;20010929;第34卷(第22期);第7648-7655页 * |
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