CN112079993A - Preparation method of epoxy resin latent curing agent - Google Patents
Preparation method of epoxy resin latent curing agent Download PDFInfo
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- CN112079993A CN112079993A CN202011000859.4A CN202011000859A CN112079993A CN 112079993 A CN112079993 A CN 112079993A CN 202011000859 A CN202011000859 A CN 202011000859A CN 112079993 A CN112079993 A CN 112079993A
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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
- C08G59/44—Amides
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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
- C08G59/188—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 using encapsulated compounds
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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)
Abstract
The invention discloses a preparation method of an epoxy resin latent curing agent, and relates to a preparation method of an epoxy resin latent curing agent. The invention aims to solve the problem that the epoxy resin latent curing agent prepared by the existing method is poor in stability. According to the invention, xanthan gum is added into the water phase formed by the dispersing agent, the emulsifying agent and the deionized water, so that the water phase thickening effect is achieved, the coating of the oil phase thickening agent on the water phase is improved, and the room temperature stability of the prepared epoxy resin latent curing agent is further improved. The invention is used for preparing the latent curing agent of the epoxy resin.
Description
Technical Field
The invention relates to a preparation method of an epoxy resin latent curing agent.
Background
The epoxy resin is a typical thermosetting resin, a molecular chain contains more than two epoxy groups, the epoxy resin is viscous liquid at normal temperature, and the epoxy resin and a curing agent are cured and crosslinked to form a three-dimensional network type macromolecular structure. Epoxy resin has excellent mechanical and physical properties, good chemical stability, low molding shrinkage and good dimensional stability, and therefore, the epoxy resin has been widely used in the fields of electronic packaging, construction, aerospace, automobiles and the like. In industrial production, the epoxy resin and the curing agent are required to be stored separately, and then are prepared again when being used, and are uniformly stirred and cured, so that the efficiency of producing epoxy resin products is greatly reduced, and the use of the epoxy resin is limited. If the epoxy resin prepreg is prepared for the next production of epoxy resin, the production speed can be greatly improved, and the quality of the prepreg can determine the performance of the product to a great extent. Generally, epoxy resin prepregs have a short storage life at room temperature and need to be stored at low temperature, which increases the difficulty and cost of transportation. If a curing agent with low curing activity is used, the curing temperature of the curing agent and epoxy resin is too high, and the problems of large curing internal stress, long forming period, high energy consumption, high manufacturing cost and the like exist. Therefore, the latent curing agent for curing the epoxy resin at the medium and low temperature needs to have proper activity, good latent period and excellent comprehensive performance. Therefore, the microcapsule technology can be applied to the preparation of latent curing agents to coat curing agent molecules with high activity, so as to greatly prolong the room-temperature storage period of a system and realize the rapid curing of epoxy resin at medium and low temperature.
Patent CN111004370A discloses a preparation method of latent epoxy resin curing agent, in which the oil phase thickener is added into the oil phase, so as to improve the stability of the oil phase droplets, but the oil phase thickener has poor coating effect on the water phase, which is not good for the stability. At home and abroad, a plurality of methods for preparing microcapsule curing agents exist, wherein chemical methods such as an interfacial polymerization method are common methods for preparing microcapsules, but the interfacial polymerization method has the defects of long reaction time, complex equipment, high cost of required raw materials and the like.
Disclosure of Invention
The invention provides a preparation method of an epoxy resin latent curing agent, aiming at solving the problem of poor stability of the epoxy resin latent curing agent prepared by the existing method.
The preparation method of the latent epoxy resin curing agent comprises the following steps:
firstly, dissolving a dispersing agent, an emulsifying agent and xanthan gum in deionized water in a container provided with an electric stirrer, and mechanically stirring to obtain a water phase; the dispersing agent is polyvinyl pyrrolidone, styrene-maleic anhydride copolymer or polyvinyl acetal; the emulsifier is triton;
secondly, adding a wall material, a core material and an oil phase thickener into the volatile solvent, and performing ultrasonic dispersion to obtain an oil phase; the wall material is a styrene-methyl methacrylate copolymer or a styrene-divinylbenzene copolymer; the core material is polyamide;
thirdly, dropwise adding the water phase into the oil phase to form a water-in-oil emulsion, and continuously dropwise adding the water phase until the phase inversion of the emulsion occurs to form an oil-in-water emulsion; the mass ratio of the water phase to the oil phase is (2-4) to 1;
and fourthly, stirring and emulsifying for 20-60 min, raising the reaction temperature to 30-35 ℃, stirring for 3-5 h, transferring to a water bath with the temperature of 35-45 ℃, heating to form microcapsule precipitate, then carrying out suction filtration, placing the precipitate after suction filtration in a vacuum drying oven, and drying to obtain the latent epoxy resin curing agent.
The invention has the advantages that:
according to the invention, xanthan gum is added into the water phase formed by the dispersing agent, the emulsifying agent and the deionized water, so that the water phase thickening effect is achieved, the coating of the oil phase thickening agent on the water phase is improved, and the room temperature stability of the prepared epoxy resin latent curing agent is further improved.
Detailed Description
The first embodiment is as follows: the preparation method of the latent epoxy resin curing agent of the embodiment comprises the following steps:
firstly, dissolving a dispersing agent, an emulsifying agent and xanthan gum in deionized water in a container provided with an electric stirrer, and mechanically stirring to obtain a water phase; the dispersing agent is polyvinyl pyrrolidone, styrene-maleic anhydride copolymer or polyvinyl acetal; the emulsifier is triton;
secondly, adding a wall material, a core material and an oil phase thickener into the volatile solvent, and performing ultrasonic dispersion to obtain an oil phase; the wall material is a styrene-methyl methacrylate copolymer or a styrene-divinylbenzene copolymer; the core material is polyamide;
thirdly, dropwise adding the water phase into the oil phase to form a water-in-oil emulsion, and continuously dropwise adding the water phase until the phase inversion of the emulsion occurs to form an oil-in-water emulsion; the mass ratio of the water phase to the oil phase is (2-4) to 1;
and fourthly, stirring and emulsifying for 20-60 min, raising the reaction temperature to 30-35 ℃, stirring for 3-5 h, transferring to a water bath with the temperature of 35-45 ℃, heating to form microcapsule precipitate, then carrying out suction filtration, placing the precipitate after suction filtration in a vacuum drying oven, and drying to obtain the latent epoxy resin curing agent.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, 15-25 parts by weight of dispersing agent, 15-25 parts by weight of emulsifier, 30-40 parts by weight of xanthan gum and 1000-1500 parts by weight of deionized water are used. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, by weight, 20 parts of dispersing agent, 20 parts of emulsifying agent, 35 parts of xanthan gum and 1000 parts of deionized water are used. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: and step two, the oil phase thickening agent is petroleum fat, polydistearate or polyamide. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and the volatile solvent in the second step is dichloromethane, trichloromethane or acetone. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the second step, the wall material is 25-55 parts by weight, the core material is 50-100 parts by weight, the oil phase thickener is 50-100 parts by weight, and the volatile solvent is 100-1000 parts by weight. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: in the second step, the wall material is 40 parts, the core material is 80 parts, the oil phase thickener is 80 parts, and the volatile solvent is 600 parts by weight. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: in the second step, the wall material is 50 parts, the core material is 100 parts, the oil phase thickener is 50 parts, and the volatile solvent is 800 parts by weight. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: in the second step, the wall material is 30 parts, the core material is 100 parts, the oil phase thickener is 60 parts, and the volatile solvent is 1000 parts by weight. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and step three, the mass ratio of the water phase to the oil phase is 3: 1. The other is the same as one of the first to ninth embodiments.
The beneficial effects of the present invention are demonstrated by the following examples:
the preparation method of the epoxy resin latent curing agent comprises the following steps:
firstly, dissolving a dispersing agent, an emulsifying agent and xanthan gum in deionized water in a container provided with an electric stirrer, and mechanically stirring to obtain a water phase; the dispersing agent is styrene-maleic anhydride copolymer; the emulsifier is triton; according to the weight parts, the dispersing agent is 20 parts, the emulsifier is 20 parts, the xanthan gum is 35 parts, and the deionized water is 1000 parts;
secondly, adding a wall material, a core material and an oil phase thickener into the volatile solvent, and performing ultrasonic dispersion to obtain an oil phase; the wall material is a styrene-methyl methacrylate copolymer or a styrene-divinylbenzene copolymer; the core material is polyamide; the oil phase thickener is petroleum grease; the volatile solvent is trichloromethane; the oil phase thickening agent comprises, by weight, 40 parts of wall materials, 80 parts of core materials, 80 parts of oil phase thickening agents and 600 parts of volatile solvents;
thirdly, dropwise adding the water phase into the oil phase to form a water-in-oil emulsion, and continuously dropwise adding the water phase until the phase inversion of the emulsion occurs to form an oil-in-water emulsion; the mass ratio of the water phase to the oil phase is 3: 1;
and fourthly, stirring and emulsifying for 20-60 min, raising the reaction temperature to 30-35 ℃, stirring for 3-5 h, transferring to a water bath with the temperature of 35-45 ℃, heating to form microcapsule precipitate, then carrying out suction filtration, placing the precipitate after suction filtration in a vacuum drying oven, and drying to obtain the latent epoxy resin curing agent.
1 part of epoxy resin latent curing agent and 10 parts of epoxy resin E-51 are mixed, the mixture is cured for 30min at 120 ℃, and the prepared prepreg has a normal-temperature storage period of more than 4 months.
Claims (10)
1. A preparation method of an epoxy resin latent curing agent is characterized in that the preparation method of the epoxy resin latent curing agent is carried out according to the following steps:
firstly, dissolving a dispersing agent, an emulsifying agent and xanthan gum in deionized water in a container provided with an electric stirrer, and mechanically stirring to obtain a water phase; the dispersing agent is polyvinyl pyrrolidone, styrene-maleic anhydride copolymer or polyvinyl acetal; the emulsifier is triton;
secondly, adding a wall material, a core material and an oil phase thickener into the volatile solvent, and performing ultrasonic dispersion to obtain an oil phase; the wall material is a styrene-methyl methacrylate copolymer or a styrene-divinylbenzene copolymer; the core material is polyamide;
thirdly, dropwise adding the water phase into the oil phase to form a water-in-oil emulsion, and continuously dropwise adding the water phase until the phase inversion of the emulsion occurs to form an oil-in-water emulsion; the mass ratio of the water phase to the oil phase is (2-4) to 1;
and fourthly, stirring and emulsifying for 20-60 min, raising the reaction temperature to 30-35 ℃, stirring for 3-5 h, transferring to a water bath with the temperature of 35-45 ℃, heating to form microcapsule precipitate, then carrying out suction filtration, placing the precipitate after suction filtration in a vacuum drying oven, and drying to obtain the latent epoxy resin curing agent.
2. The method of claim 1, wherein in the first step, the amount of the dispersant is 15 to 25 parts, the amount of the emulsifier is 15 to 25 parts, the amount of the xanthan gum is 30 to 40 parts, and the amount of the deionized water is 1000 to 1500 parts by weight.
3. The method according to claim 1, wherein in the first step, the amount of the dispersant is 20 parts, the amount of the emulsifier is 20 parts, the amount of the xanthan gum is 35 parts, and the amount of the deionized water is 1000 parts.
4. The method of claim 1, wherein the oil phase thickener in step two is selected from petroleum resin, poly-bis-stearate, and polyamide.
5. The method of claim 1, wherein the volatile solvent in step two is dichloromethane, chloroform or acetone.
6. The method for preparing a latent epoxy resin curing agent according to claim 1, wherein in the second step, the amount of the wall material is 25 to 55 parts by weight, the amount of the core material is 50 to 100 parts by weight, the amount of the oil phase thickener is 50 to 100 parts by weight, and the amount of the volatile solvent is 100 to 1000 parts by weight.
7. The method according to claim 1, wherein in the second step, the amount of the wall material is 40 parts, the amount of the core material is 80 parts, the amount of the oil phase thickener is 80 parts, and the amount of the volatile solvent is 600 parts by weight.
8. The method according to claim 1, wherein in the second step, the amount of the wall material is 50 parts, the amount of the core material is 100 parts, the amount of the oil phase thickener is 50 parts, and the amount of the volatile solvent is 800 parts.
9. The method according to claim 1, wherein in the second step, the amount of the wall material is 30 parts, the amount of the core material is 100 parts, the amount of the oil phase thickener is 60 parts, and the amount of the volatile solvent is 1000 parts.
10. The method according to claim 1, wherein the mass ratio of the water phase to the oil phase in step three is 3: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011000859.4A CN112079993A (en) | 2020-09-22 | 2020-09-22 | Preparation method of epoxy resin latent curing agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011000859.4A CN112079993A (en) | 2020-09-22 | 2020-09-22 | Preparation method of epoxy resin latent curing agent |
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| CN112079993A true CN112079993A (en) | 2020-12-15 |
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| CN202011000859.4A Pending CN112079993A (en) | 2020-09-22 | 2020-09-22 | Preparation method of epoxy resin latent curing agent |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107292A (en) * | 1974-04-01 | 1978-08-15 | Akzona Incorporated | Stable water dispersions of encapsulated parathion |
| JPH01313550A (en) * | 1988-06-13 | 1989-12-19 | Maruzen Petrochem Co Ltd | Aqueous emulsion of phenolic resin |
| WO1998026865A1 (en) * | 1996-12-17 | 1998-06-25 | Chemcolloids Limited | Encapsulation |
| US20050161843A1 (en) * | 2004-01-23 | 2005-07-28 | Yongcai Wang | Process of producing microcapsules and product thereof |
| US20050208144A1 (en) * | 2000-06-12 | 2005-09-22 | Yutaka Igari | Microcapsule suspension liquid and process for production thereof |
| CN102423673A (en) * | 2011-07-28 | 2012-04-25 | 西北工业大学 | Latent microcapsule curing agent initiating thermosetting epoxy resin curing at medium temperature and preparation method of adhesive thereof |
| CN107875985A (en) * | 2017-12-18 | 2018-04-06 | 北京工业大学 | A kind of preparation method of resting form micro capsule curing agent |
| CN111004370A (en) * | 2019-12-20 | 2020-04-14 | 肇庆市海特复合材料技术研究院 | Preparation method of epoxy resin latent curing agent |
-
2020
- 2020-09-22 CN CN202011000859.4A patent/CN112079993A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4107292A (en) * | 1974-04-01 | 1978-08-15 | Akzona Incorporated | Stable water dispersions of encapsulated parathion |
| JPH01313550A (en) * | 1988-06-13 | 1989-12-19 | Maruzen Petrochem Co Ltd | Aqueous emulsion of phenolic resin |
| WO1998026865A1 (en) * | 1996-12-17 | 1998-06-25 | Chemcolloids Limited | Encapsulation |
| US20050208144A1 (en) * | 2000-06-12 | 2005-09-22 | Yutaka Igari | Microcapsule suspension liquid and process for production thereof |
| US20050161843A1 (en) * | 2004-01-23 | 2005-07-28 | Yongcai Wang | Process of producing microcapsules and product thereof |
| CN102423673A (en) * | 2011-07-28 | 2012-04-25 | 西北工业大学 | Latent microcapsule curing agent initiating thermosetting epoxy resin curing at medium temperature and preparation method of adhesive thereof |
| CN107875985A (en) * | 2017-12-18 | 2018-04-06 | 北京工业大学 | A kind of preparation method of resting form micro capsule curing agent |
| CN111004370A (en) * | 2019-12-20 | 2020-04-14 | 肇庆市海特复合材料技术研究院 | Preparation method of epoxy resin latent curing agent |
Non-Patent Citations (1)
| Title |
|---|
| 吴赞敏等: "热敏变色整理剂的研制", 《纺织学报》 * |
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Application publication date: 20201215 |