CN113024839A - Water-based epoxy resin emulsion and preparation method and application thereof - Google Patents
Water-based epoxy resin emulsion and preparation method and application thereof Download PDFInfo
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- CN113024839A CN113024839A CN202110265677.8A CN202110265677A CN113024839A CN 113024839 A CN113024839 A CN 113024839A CN 202110265677 A CN202110265677 A CN 202110265677A CN 113024839 A CN113024839 A CN 113024839A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/02—Polyglycidyl ethers of bis-phenols
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention relates to a water-based epoxy resin emulsion and a preparation method and application thereof, and solves the technical problems that the existing water-based carbon fiber sizing agent cannot form uniform and stable emulsion and has unsatisfactory effect when used as a carbon fiber sizing agent. The invention also provides a preparation method and application thereof. The invention can be used in the field of preparation of carbon fiber sizing agents.
Description
Technical Field
The invention relates to an epoxy resin emulsion, a preparation method and application thereof, in particular to a water-based epoxy resin emulsion, a preparation method and application thereof.
Background
Carbon fiber reinforced resin matrix composites are usually prepared by bundling, protecting and enhancing the functional group content on the surface of carbon fibers by a sizing method, and carbon fiber sizing agents mainly comprise a solvent sizing agent and a water-based sizing agent. The solvent sizing agent usually needs a large amount of flammable and volatile organic solvent, environmental pollution and solvent waste can be caused in the production and use processes, and the solvent is easy to volatilize in the sizing process, so that resin remains on the guide roller, and subsequent passing fibers can be damaged. The water-based sizing agent takes water as a solvent, and has the advantages of no toxicity, no smell, safe use, small environmental pollution and low production cost.
The water-based carbon fiber sizing agent is mainly an emulsion type sizing agent, namely a water-based epoxy resin emulsion. The method for preparing the water-based epoxy mainly comprises a mechanical method, an additional emulsifier method and a chemical modification method. The chemical modification method is widely adopted because the prepared emulsion has the best performance, but the epoxy resin obtained by the chemical modification method has certain hydrophilicity and cannot spontaneously form a uniform and stable emulsion, so that high-energy-consumption high-shear equipment is required for preparation in the emulsification process, the emulsion preparation is complicated, and the preparation cost and the energy consumption are increased.
Disclosure of Invention
The invention provides a water-based epoxy resin emulsion with extremely small emulsion particle size, excellent stability and better performance of the prepared carbon fiber material, a preparation method and application thereof, aiming at the technical problems that the existing water-based carbon fiber sizing agent can not form uniform and stable emulsion and has unsatisfactory effect when being used as a carbon fiber sizing agent.
The invention provides a water-based epoxy resin emulsion which comprises four components, namely modified epoxy resin, bisphenol A epoxy resin, cosurfactant and water according to the system, and the components are as follows according to the parts by mass: 1-10 parts, 2-10 parts, 5-50 parts and 100-400 parts.
Preferably, the modified epoxy resin is a single-end-capped epoxy resin obtained by reacting a secondary amine diol with an epoxy resin.
Preferably, the secondary diol amine is one of diethanolamine, diisopropanolamine or dibutanolamine.
Preferably, the modified epoxy resin is any one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a helical cyclic acetal structure type epoxy resin, and the like.
Preferably, the bisphenol a type epoxy resin is any one or more of E51, E44, E20, and the like.
Preferably, the cosurfactant is any one or more of short-chain alcohols such as ethanol and propanol.
The invention also provides a preparation method of the water-based epoxy resin emulsion, which comprises the following steps: (1) preparing modified epoxy resin: sequentially mixing epoxy resin and diol secondary amine according to the mass ratio of 6: (1-3) adding the mixture into a three-neck flask, adding ethanol as a solvent, and mechanically stirring at the stirring speed of 300-600 r/min; reacting the system at 70-80 ℃, pouring the system into a beaker after reacting for 2-4h, and removing ethanol in an oven to prepare modified epoxy resin; (2) and (3) activation: mixing the modified epoxy resin prepared in the step (1), bisphenol A type epoxy resin and cosurfactant according to the mass ratio of (1-10): (2-10): (5-50) stirring, mixing and dissolving at the temperature of 40-60 ℃, at the stirring speed of 100-200r/min and for 5-10min to obtain an activated resin system; (3) emulsification: and (3) directly adding 100-400 parts by mass of deionized water into the activated resin system obtained in the step (2), and then adding acetic acid with the molar ratio of the acetic acid to the epoxy groups in the modified resin being 1-2 for neutralization reaction to obtain the waterborne epoxy resin emulsion.
The invention also provides application of the water-based epoxy resin emulsion as a carbon fiber sizing agent.
Preferably, the application of the water-based epoxy resin emulsion provided by the invention as a carbon fiber sizing agent is characterized by comprising the following steps:
(1) preparing a sizing agent: preparing a sizing agent according to the formula of claim 1, wherein the solid content of the sizing agent is 0.5-3%;
(2) sizing and drying: : and placing the prepared sizing agent into a sizing tank, and soaking carbon fibers which are not sized through the sizing tank to finish sizing. And drying the sized carbon fibers by blowing at normal temperature, and rolling to obtain the dried sized carbon fibers.
Preferably, in the step (1), the solid content of the sizing agent is 1-2%; in the step (2), the sizing time is 10-45 s; drying for 3-5 min; the carbon fiber which is not sized is T800 carbon fiber; the sizing amount of the sized carbon fiber is controlled to be 0.5-1.0 wt%.
The invention has the following beneficial effects:
the cosurfactant is added into a system of modified epoxy resin, epoxy resin and water, and the emulsification process provides high-shear spontaneous emulsion without high-speed stirring by utilizing the functions of increasing the entropy of the system and reducing the free energy, and the prepared emulsion is a thermodynamically stable system, so that the demixing and the sedimentation cannot occur. Specifically, the present invention has the following advantages:
1) and modifying the epoxy resin by using secondary diol amine. The reaction mechanism is clear, the process is simple, and side reactions can be avoided;
2) emulsion is spontaneously formed in an emulsification process system without high-speed stirring, the operation is simple and convenient, and the energy consumption is low;
3) the prepared water-based epoxy resin has excellent emulsifying property, stable system thermodynamics, average grain diameter less than 10nm and excellent performance.
Drawings
FIG. 1 is a structural diagram of an epoxy resin containing a helical cyclic acetal structure modified by diethanolamine in the present invention;
FIG. 2 is a chart of particle size analysis of the aqueous epoxy resin emulsion prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of unsized T800 carbon fibers;
FIG. 4 is a scanning electron microscope image of the surface of T800 carbon fiber after sizing by the sizing agent in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
The particle size of the emulsions in the examples below was measured using a laser particle sizer.
The mechanical stability of the emulsion was measured as follows: respectively measuring 10mL of the emulsion in each group of examples, placing the emulsion in a 15mL centrifuge tube, placing the centrifuge tube in a desktop centrifuge, setting the rotating speed to 3000r/min, setting the centrifugation time to 30min, and observing emulsion breaking and layering conditions of the emulsion in the centrifuge tube. If the bottom of the centrifugal tube has sediment or the demulsification condition occurs, the mechanical stability of the emulsion is considered to be poor, otherwise, the mechanical stability of the emulsion is considered to be good.
The material storage stability was tested as follows: placing the emulsion in a closed container, and observing whether the emulsion has obvious layering phenomenon or whether the viscosity of the system has obvious change after the emulsion is placed for a period of time under the natural environment condition. If there was significant delamination or viscosity change, indicating poor storage stability of the emulsion, the number of days the emulsion was allowed to stand was recorded. The emulsion is considered to be excellent in storage stability if the emulsion does not delaminate after standing for 6 months and the change in viscosity of the system is not significant.
Interlaminar shear strength testing was as follows: the interlaminar shear strength of the unidirectional composites was tested by a universal material testing machine (model 1121, Instron) in accordance with the GB/T3375 standard. The selected matrix resin is E51 type bisphenol A type epoxy resin.
Example 1
1) Sequentially adding 20mL of absolute ethyl alcohol and 12g of epoxy resin containing a spiral cyclic acetal structure into a three-neck flask, weighing 2g of diethanolamine, dripping the diethanolamine into a reaction system, raising the temperature to 80 ℃, reacting for several hours, clarifying the solution, and standing to remove the ethanol to obtain the diethanolamine modified epoxy resin containing the spiral cyclic acetal structure;
2) weighing 0.5g of the surfactant obtained in the step 1) and 2.0g of 2.0g E51 epoxy resin, weighing 20g of absolute ethyl alcohol, and mixing and dissolving at 50 ℃;
3) adding 100mL of deionized water into the solution in the step 2), adding 0.1g of acetic acid for neutralization, and obtaining the aqueous epoxy resin emulsion after the neutralization reaction is completed.
4) Preparing a sizing agent: preparing a sizing agent from the aqueous epoxy resin emulsion, and enabling the solid content of the sizing agent to be 2%;
5) sizing and drying: placing the prepared sizing agent in a sizing tank, and soaking carbon fibers which are not sized in the sizing tank to finish sizing; drying the sized carbon fibers by normal-temperature air blowing, and rolling to obtain dried sized carbon fibers; the sizing time is 30 s; drying for 4 min; the carbon fiber which is not sized is T800 carbon fiber; the sizing amount of the sized carbon fiber is controlled to be 0.8 wt%.
Example 2
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: 1) the epoxy resin used in (1) is E51.
Example 3
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: the amount of ethanol used was 12 g.
The aqueous epoxy resin emulsion system of this example was unstable and the precipitation increased with the increase of the standing time.
Example 4
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: the amount of ethanol used was 45 g.
Example 5
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: the amount of ethanol used was 90 g.
The aqueous epoxy resin emulsion of this example was transparent at the initial stage, and was cloudy and separated with standing time, and finally phase separated.
Comparative example 6
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: 2) the amount of the co-surfactant used in (1) is 0.
The aqueous epoxy resin emulsion of this example did not form a stable and uniform emulsion.
Example 7
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: 2) the amount of the co-surfactant used in (1) was 60g.
The average particle size of the aqueous epoxy resin emulsion of this example was 108nm, and the emulsion was allowed to stand and separate.
Example 8
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: 2) the co-surfactant used in (1) is propanol.
Example 9
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: 3) the amount of deionized water used in (1) was 50 g.
Example 10
The aqueous epoxy resin emulsion in this example differs from the aqueous epoxy resin emulsion in example 1 in that: 3) the amount of deionized water used in (1) was 200 g.
Example 11
The procedure was as in example 1 except for the following steps.
4) Preparing a sizing agent: preparing a sizing agent from the aqueous epoxy resin emulsion, and enabling the solid content of the sizing agent to be 0.5%;
5) sizing and drying: placing the prepared sizing agent in a sizing tank, and soaking carbon fibers which are not sized in the sizing tank to finish sizing; drying the sized carbon fibers by normal-temperature air blowing, and rolling to obtain dried sized carbon fibers; the sizing time is 10 s; drying for 3 min; the sizing amount of the sized carbon fiber is controlled to be 0.5 wt%.
Example 12
The procedure was as in example 1 except for the following steps.
4) Preparing a sizing agent: preparing a sizing agent from the aqueous epoxy resin emulsion, and enabling the solid content of the sizing agent to be 3%;
5) sizing and drying: placing the prepared sizing agent in a sizing tank, and soaking carbon fibers which are not sized in the sizing tank to finish sizing; drying the sized carbon fibers by normal-temperature air blowing, and rolling to obtain dried sized carbon fibers; the solid content of the sizing agent is 2 percent; the sizing time is 45 s; drying for 5 min; the sizing amount of the sized carbon fiber is controlled to be 1.0 wt%.
TABLE 1 physical Properties and interlaminar shear Strength of some examples
However, the above description is only exemplary of the present invention, and the scope of the present invention should not be limited thereby, and the replacement of the equivalent components or the equivalent changes and modifications made according to the protection scope of the present invention should be covered by the claims of the present invention.
Claims (10)
1. The water-based epoxy resin emulsion is characterized by comprising, by mass, 1-10 parts of modified epoxy resin, 2-10 parts of bisphenol A type epoxy resin, 5-50 parts of cosurfactant and 100 parts of water.
2. The aqueous epoxy resin emulsion according to claim 1, wherein the modified epoxy resin is a mono-blocked epoxy resin obtained by reacting a secondary amine of a diol with an epoxy resin.
3. The aqueous epoxy resin emulsion of claim 2 wherein the secondary amine diol is one of diethanolamine, diisopropanolamine or dibutanolamine.
4. The aqueous epoxy resin emulsion according to claim 1, wherein the modified epoxy resin is any one of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a helical cyclic acetal structure type epoxy resin, and the like.
5. The aqueous epoxy resin emulsion according to claim 4, wherein the bisphenol A type epoxy resin is any one or more of E51, E44, E20, and the like.
6. The aqueous epoxy resin emulsion according to claim 1, wherein the cosurfactant is any one or more of short chain alcohols such as ethanol and propanol.
7. The method for preparing an aqueous epoxy resin emulsion according to claim 1, comprising the steps of:
(1) preparing modified epoxy resin: sequentially mixing epoxy resin and diol secondary amine according to the mass ratio of 6: (1-3) adding the mixture into a three-neck flask, adding ethanol as a solvent, and mechanically stirring at the stirring speed of 300-600 r/min; reacting the system at 70-80 ℃, pouring the system into a beaker after reacting for 2-4h, and removing ethanol in an oven to prepare modified epoxy resin;
(2) and (3) activation: mixing the modified epoxy resin prepared in the step (1), bisphenol A type epoxy resin and cosurfactant according to the mass ratio of (1-10): (2-10): (5-50) stirring, mixing and dissolving at the temperature of 40-60 ℃, at the stirring speed of 100-200r/min and for 5-10min to obtain an activated resin system;
(3) emulsification: and (3) directly adding 100-400 parts by mass of deionized water into the activated resin system obtained in the step (2), and then adding acetic acid with the molar ratio of the acetic acid to the epoxy groups in the modified resin being 1-2 for neutralization reaction to obtain the waterborne epoxy resin emulsion.
8. Use of the aqueous epoxy resin emulsion of claim 1 as a carbon fiber sizing agent.
9. The use of the aqueous epoxy resin emulsion as a carbon fiber sizing agent according to claim 8, characterized by comprising the steps of:
(1) preparing a sizing agent: preparing a sizing agent from the aqueous epoxy resin emulsion, and enabling the solid content of the sizing agent to be 0.5-3%;
(2) sizing and drying: placing the prepared sizing agent in a sizing tank, and soaking carbon fibers which are not sized in the sizing tank to finish sizing; and drying the sized carbon fibers by blowing at normal temperature, and rolling to obtain the dried sized carbon fibers.
10. The method of application according to claim 9, characterized in that: in the step (1), the solid content of the sizing agent is 1-2%; in the step (2), the sizing time is 10-45 s; drying for 3-5 min; the carbon fiber which is not sized is T800 carbon fiber; the sizing amount of the sized carbon fiber is controlled to be 0.5-1.0 wt%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005213687A (en) * | 2004-01-30 | 2005-08-11 | Toray Ind Inc | Method for producing carbon fiber bundle |
| CN104420204A (en) * | 2013-09-10 | 2015-03-18 | 济南大学 | Carbon fiber water-soluble epoxy resin sizing agent |
| CN105862427A (en) * | 2016-04-29 | 2016-08-17 | 中简科技股份有限公司 | Preparation method of modified epoxy resin emulsion |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005213687A (en) * | 2004-01-30 | 2005-08-11 | Toray Ind Inc | Method for producing carbon fiber bundle |
| CN104420204A (en) * | 2013-09-10 | 2015-03-18 | 济南大学 | Carbon fiber water-soluble epoxy resin sizing agent |
| CN105862427A (en) * | 2016-04-29 | 2016-08-17 | 中简科技股份有限公司 | Preparation method of modified epoxy resin emulsion |
Non-Patent Citations (1)
| Title |
|---|
| 高艳等: "碳纤维用耐高温型环氧树脂上浆剂的制备及性能研究", 《高科技纤维与应用》 * |
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