CN104448245A - Preparation method of hyper-branched epoxy emulsion - Google Patents
Preparation method of hyper-branched epoxy emulsion Download PDFInfo
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- CN104448245A CN104448245A CN201410784716.5A CN201410784716A CN104448245A CN 104448245 A CN104448245 A CN 104448245A CN 201410784716 A CN201410784716 A CN 201410784716A CN 104448245 A CN104448245 A CN 104448245A
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Abstract
The invention relates to the technical field of epoxy emulsion, and particularly relates to a preparation method of hyper-branched epoxy emulsion. The preparation method comprises the following steps: allowing polyamine to react with epoxy resin to synthesize hyper-branched epoxy resin; allowing the hyper-branched epoxy resin to react with hydrophilic polyether under the effect of a catalyst to obtain modified hydrophilic hyper-branched epoxy resin; and adding deionized water into the modified hydrophilic hyper-branched epoxy resin, shearing and stirring to prepare the hyper-branched epoxy emulsion. The method disclosed by the invention is used for preparing the stable hyper-branched epoxy emulsion by preparing hydrophilic polyether modified hyper-branched epoxy resin and then emulsifying the hydrophilic polyether modified hyper-branched epoxy resin; the prepared stable hyper-branched epoxy emulsion can be used as a carbon fiber sizing agent and a wetting agent for glass fibers and basalt fibers and can provide excellent collection property and splitting property of fiber bundles and wettability of epoxy resin; the fibers sized by using the epoxy emulsion can be used for preparing a composite material which is high in inter-laminar shear strength and resistant to high temperature.
Description
Technical field
The present invention relates to epoxy emulsion preparing technical field, be specifically related to a kind of preparation method of hyperbranched type epoxy emulsion.
Background technology
A main application of the contour performance fibers of carbon fiber, glass fibre, basalt fibre is the matrix material material preparing fiber-reinforced resin, in order to improve the performance of fiber-reinforced resin, usually in the contour performance fiber production process of carbon fiber, glass fibre and basalt fibre, need to process fiber surface, as the sizing agent used in carbon fiber production, the treating compound used in glass fibre or basalt fibre are produced.
Main component in the treating compound of carbon fiber sizing agent and glass fibre is all resin emulsion, nano level resin layer is formed at fiber surface by sizing technique, resin layer will improve wear resistance, convergency, expanding, the static resistance of fiber, regulate flexural resilience and straight elevator degree, reduce the frictional coefficient of carbon fiber, reducing the generating capacity of processed and applied process lousiness, adapting in later stage composite material shaping process weaving the technique such as laying, winding to the demand of fibre property.On the other hand, the resin layer of fiber surface, can improve and regulate and control the matrix resin consistency of carbon fiber in matrix material preparation process and wetting property, by the curing reaction in matrix material later stage, between fiber and polymeric matrix, form good composite material interface, improve fiber and the cohesiveness of matrix resin and the interlaminar shear strength (ILSS) of fibre reinforced composites.In view of the performance of resin emulsion on high-performance fiber and matrix material thereof all has remarkably influenced, therefore to the stability of resin emulsion, the film-forming properties of resin, the thermotolerance of resin, reactive behavior etc. all require strictly.
Epoxy emulsion applies maximum resin emulsions in carbon fiber sizing agent and glass fiber infiltration agent.Current epoxy emulsion preparation method uses surfactant emulsifies epoxy resin usually, resin emulsion prepared by this method, and the large and wider distribution of emulsion particle diameter, can affect the distribution uniformity of resin at fiber surface; The migration of tensio-active agent also can make stability of emulsion destroy, and tensio-active agent does not have reactive behavior, can have influence on the interlaminar shear strength of matrix material yet.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of hyperbranched type epoxy emulsion, the hyperbranched type epoxy emulsion prepared by this preparation method can be used as the treating compound of carbon fiber sizing agent, glass fibre and basalt fibre, can provide the convergency of fibrous bundle excellence, fibrillation and the wetting property with epoxy resin.
In order to achieve the above object, the technical solution used in the present invention is:
A preparation method for hyperbranched type epoxy emulsion, comprises the steps:
Polyamine and epoxy resin are reacted, synthesis of super branched type epoxy resin;
Described hyperbranched type epoxy resin, under the effect of catalyzer, is reacted into Hydrophilicrto polyether the hyperbranched type epoxy resin obtaining hydrophilic modifying;
In the over-expense chemistry epoxy resin of described hydrophilic modifying, add deionized water, by shear agitation, be prepared into hyperbranched type epoxy emulsion.
Further, describedly polyamine and epoxy resin to be reacted, synthesis of super branched type epoxy resin, comprises the steps:
Determine in polyamine reactive hydrogen molar weight to be a, determine that the molar weight of the epoxide group of epoxy resin is b, in a:b value be 1 ~ 30 ratio polyamine and epoxy resin once or are in batches put in reactor, be warming up to 40 ~ 120 DEG C of reaction 1-8 hour, obtain hyperbranched type epoxy resin or hyperbranched type epoxy resin solution.
Further, describedly polyamine and epoxy resin to be reacted, synthesis of super branched type epoxy resin, also comprises the steps:
Described, polyamine and epoxy resin once or are in batches put into after in reactor, according to reaction system viscosity, add solvent to reduce reaction system viscosity.
Further, described hyperbranched type epoxy resin, under the effect of catalyzer, is reacted into Hydrophilicrto polyether the hyperbranched type epoxy resin obtaining hydrophilic modifying, comprises the steps:
Solvent is used to be dissolved by described hyperbranched type epoxy resin;
Hydrophilicrto polyether and catalyzer is added, stirring reaction 4-12 hour, temperature of reaction 0 ~ 80 DEG C in the chemical epoxy resin of described over-expense upon dissolution; The add-on of described Hydrophilicrto polyether is the 5-40% of described hyperbranched type epoxy resin quality, and the add-on of described catalyzer is the 0.01%-0.5% of described Hydrophilicrto polyether weight;
Add deionized water termination reaction, by underpressure distillation, remove the solvent in solution, obtain the hyperbranched type epoxy resin of hydrophilic modifying.
Further, add deionized water in the described chemistry of the over-expense at described hydrophilic modifying epoxy resin, comprise the steps:
In the hyperbranched type epoxy resin of described hydrophilic modifying, once or in batches add deionized water, the add-on of described deionized water is 1-5 times of the hyperbranched type weight epoxy of described hydrophilic modifying.
Further, described polyamine is one or more in quadrol, propylene diamine, N, N-dimethylated propyl diethylenetriamine, diethylene triamine, diethylenetriamine, triethylene tetramine, season penta tetramine.
Further, described epoxy resin is one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, diglycidyl ether type epoxy resin.
Further, described catalyzer is the one in boron trifluoride diethyl etherate, aluminum chloride, iron trichloride.
Further, described Hydrophilicrto polyether is one or more in polyoxyethylene glycol, polyoxyethylene glycol monoether, polyoxyethylene glycol monoesters class.
Further, described solvent is the one in methylene dichloride, trichloromethane, acetone, glycol dimethyl ether, ethylene glycol dibutyl ether.
Compared with prior art, the beneficial effect that the technical solution used in the present invention produces is as follows:
The present invention is by a kind of hydrophilic polyether modified hyperbranched type epoxy resin of preparation, stable hyperbranched type epoxy emulsion is prepared into through emulsification, can use as the treating compound of carbon fiber sizing agent, glass fibre and basalt fibre, the convergency of fibrous bundle excellence, fibrillation and the wetting property with epoxy resin can be provided, use the fiber of this epoxy emulsion starching to can be used for preparing high interlayer shear and high-temperature resistant composite material.
Accompanying drawing explanation
The process flow sheet of the preparation method of the hyperbranched type epoxy emulsion that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is described in detail.
As shown in Figure 1, the embodiment of the present invention provides a kind of preparation method of hyperbranched type epoxy emulsion, comprises the steps:
Step 110: polyamine and epoxy resin are reacted, synthesis of super branched type epoxy resin;
Particularly, described step 110 comprises the steps:
Determine in polyamine reactive hydrogen molar weight to be a, determine that the molar weight of the epoxide group of epoxy resin is b, in a:b value be 1 ~ 30 ratio polyamine and epoxy resin once or are in batches put in reactor, be warming up to 40 ~ 120 DEG C of reaction 1-8 hour, obtain hyperbranched type epoxy resin or hyperbranched type epoxy resin solution.Described polyamine is one or more in quadrol, propylene diamine, N, N-dimethylated propyl diethylenetriamine, diethylene triamine, diethylenetriamine, triethylene tetramine, season penta tetramine; Described epoxy resin is one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, diglycidyl ether type epoxy resin;
Described step 110 also comprises the steps:
Described, polyamine and epoxy resin once or are in batches put into after in reactor, if reaction system viscosity is large, solvent can be added to reduce reaction system viscosity; Described solvent is the one in methylene dichloride, trichloromethane, acetone, glycol dimethyl ether, ethylene glycol dibutyl ether.
Step 120: described hyperbranched type epoxy resin, under the effect of catalyzer, is reacted into Hydrophilicrto polyether the hyperbranched type epoxy resin obtaining hydrophilic modifying;
Particularly, described step 120 comprises the steps:
Step 1201: use solvent to be dissolved by described hyperbranched type epoxy resin; Described solvent is the one in methylene dichloride, trichloromethane, acetone, glycol dimethyl ether, ethylene glycol dibutyl ether;
Step 1202: add Hydrophilicrto polyether and catalyzer, stirring reaction 4-12 hour in the chemical epoxy resin of described over-expense upon dissolution, temperature of reaction 0 ~ 80 DEG C; The add-on of described Hydrophilicrto polyether is the 5-40% of described hyperbranched type epoxy resin quality, and the add-on of described catalyzer is the 0.01%-0.5% of described Hydrophilicrto polyether weight; Described catalyzer is the one in boron trifluoride diethyl etherate, aluminum chloride, iron trichloride; Described Hydrophilicrto polyether is one or more in polyoxyethylene glycol, polyoxyethylene glycol monoether, polyoxyethylene glycol monoesters class;
Step 1203: add deionized water termination reaction, by underpressure distillation, removes the solvent in solution, obtains the hyperbranched type epoxy resin of hydrophilic modifying.
Step 130: add deionized water in the over-expense chemistry epoxy resin of described hydrophilic modifying, by shear agitation, be prepared into hyperbranched type epoxy emulsion;
Particularly, in the hyperbranched type epoxy resin of described hydrophilic modifying, once or in batches add deionized water, the add-on of described deionized water is 1-5 times of the hyperbranched type weight epoxy of described hydrophilic modifying.
Embodiment 1:
The present embodiment provides a kind of preparation method of hyperbranched type epoxy resin latex, comprises the steps:
(1) by 1 mole of diethylenetriamine, 10 moles of bisphenol A type epoxy E51 and 5 mole ethylene glycol dibutyl ethers join in there-necked flask, be warming up to 80 DEG C, react after 2 hours, add 10 moles of propylene diamine and continue reaction 4 hours, and then drop into 40 moles of bisphenol A type epoxy E51 resins continuation reaction 4 hours, obtain hyperbranched type epoxy resin solution;
(2) after the hyperbranched type epoxy resin solution of preparation being cooled to 40 DEG C, add the PEG2000 resin (molecular-weight average is 2000 polyethyleneglycol resins) of prepared hyperbranched type epoxy resin quality 20% and the boron trifluoride ether solution of 0.2%, keep 40 DEG C and stir after 2 hours, add the deionized water of system weight 30%, go out solvent ethylene glycol dibutyl ether by underpressure distillation, obtain the hyperbranched type epoxy resin of hydrophilic modifying;
(3) the hyperbranched type epoxy resin of hydrophilic modifying is warmed up to 60 DEG C, the deionized water and stirring adding 50% of the hyperbranched type epoxy resin quality of hydrophilic modifying evenly after, be cooled to 40 DEG C, and then add in mixed system hydrophilic modifying hyperbranched type epoxy resin quality the deionized water of 1 times after stir or high-shear emulsifying prepare hyperbranched type epoxy emulsion.
Embodiment 2:
(1) by 1 mole of propylene diamine, 5 moles of polyetheramine D230,25 moles of bisphenol A type epoxy E44 are disposable to be joined in there-necked flask, is warming up to 100 DEG C, reacts after 3 hours, obtain hyperbranched type epoxy resin;
(2) after the hyperbranched type epoxy resin of preparation being cooled to 40 DEG C, after adding the acetone stirring and dissolving of prepared hyperbranched type epoxy resin quality 30%, continue the boron trifluoride ether solution of the PEG4000 (molecular-weight average is 4000 polyethyleneglycol resins) and 0.2% adding prepared hyperbranched type epoxy resin quality 15%, keep 40 DEG C and stir after 2 hours, add the deionized water of system weight 30%, go out solvent ethylene glycol dibutyl ether by underpressure distillation, obtain the hyperbranched type epoxy resin of hydrophilic modifying;
(3) the hyperbranched type epoxy resin of hydrophilic modifying is warmed up to 60 DEG C, the deionized water and stirring adding 50% of the hyperbranched type epoxy resin quality of hydrophilic modifying evenly after, be cooled to 40 DEG C, and then add in mixed system hydrophilic modifying hyperbranched type epoxy resin quality the deionized water of 1 times after stir or high-shear emulsifying prepare hyperbranched type epoxy emulsion.
Embodiment 3:
(1) by 1 mole season penta tetramine, 8 moles of bisphenol A type epoxy E51 and 5 mole ethylene glycol dibutyl ethers join in there-necked flask, be warming up to 80 DEG C, react after 2 hours, add 10 moles of dimethylene triamines and continue reaction 2 hours, and then drop into 40 moles of bisphenol A type epoxy E51 resins continuation reaction 2 hours, obtain hyperbranched type epoxy resin solution;
(2) after the hyperbranched type epoxy resin solution of preparation being cooled to 40 DEG C, add the boron trifluoride ether solution of the PEG10000 (molecular-weight average is 10000 polyethyleneglycol resins) and 0.2% of prepared hyperbranched type epoxy resin quality 15%, keep 40 DEG C and stir after 2 hours, add the deionized water of system weight 30%, go out solvent ethylene glycol dibutyl ether by underpressure distillation, obtain the hyperbranched type epoxy resin of hydrophilic modifying;
(3) the hyperbranched type epoxy resin of hydrophilic modifying is warmed up to 60 DEG C, the deionized water and stirring adding 50% of the hyperbranched type epoxy resin quality of hydrophilic modifying evenly after, be cooled to 40 DEG C, and then add in mixed system hydrophilic modifying hyperbranched type epoxy resin quality the deionized water of 1.5 times after stir or high-shear emulsifying prepare hyperbranched type epoxy emulsion.
The present invention compared with prior art, at least has the following advantages:
(1) the present invention first synthesizes a kind of stable hyperbranched type epoxy resin, and ordinary epoxy resin of comparing, hyperbranched type epoxy resin has tree structure, and resin viscosity is low, and active function groups is many, can provide higher mechanical property after hardening.
(2) the present invention is by a kind of hydrophilic polyether modified hyperbranched type epoxy resin of preparation, stable hyperbranched type epoxy emulsion is prepared into through emulsification, can use as the treating compound of carbon fiber sizing agent, glass fibre and basalt fibre, the convergency of fibrous bundle excellence, fibrillation and the wetting property with epoxy resin can be provided, use the fiber of this emulsion starching to can be used for preparing high interlayer shear and high-temperature resistant composite material.
The above is most preferred embodiment of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for hyperbranched type epoxy emulsion, is characterized in that, comprise the steps:
Polyamine and epoxy resin are reacted, synthesis of super branched type epoxy resin;
Described hyperbranched type epoxy resin, under the effect of catalyzer, is reacted into Hydrophilicrto polyether the hyperbranched type epoxy resin obtaining hydrophilic modifying;
In the over-expense chemistry epoxy resin of described hydrophilic modifying, add deionized water, by shear agitation, be prepared into hyperbranched type epoxy emulsion.
2. preparation method as claimed in claim 1, is characterized in that, describedly polyamine and epoxy resin is reacted, and synthesis of super branched type epoxy resin, comprises the steps:
Determine in polyamine reactive hydrogen molar weight to be a, determine that the molar weight of the epoxide group of epoxy resin is b, in a:b value be 1 ~ 30 ratio polyamine and epoxy resin once or are in batches put in reactor, be warming up to 40 ~ 120 DEG C of reaction 1-8 hour, obtain hyperbranched type epoxy resin or hyperbranched type epoxy resin solution.
3. preparation method as claimed in claim 2, is characterized in that, describedly polyamine and epoxy resin is reacted, and synthesis of super branched type epoxy resin, also comprises the steps:
Described, polyamine and epoxy resin once or are in batches put into after in reactor, according to reaction system viscosity, add solvent to reduce reaction system viscosity.
4. preparation method as claimed in claim 1, it is characterized in that, described hyperbranched type epoxy resin, under the effect of catalyzer, is reacted into Hydrophilicrto polyether the hyperbranched type epoxy resin obtaining hydrophilic modifying, comprises the steps:
Solvent is used to be dissolved by described hyperbranched type epoxy resin;
Hydrophilicrto polyether and catalyzer is added, stirring reaction 4-12 hour, temperature of reaction 0 ~ 80 DEG C in the chemical epoxy resin of described over-expense upon dissolution; The add-on of described Hydrophilicrto polyether is the 5-40% of described hyperbranched type epoxy resin quality, and the add-on of described catalyzer is the 0.01%-0.5% of described Hydrophilicrto polyether weight;
Add deionized water termination reaction, by underpressure distillation, remove the solvent in solution, obtain the hyperbranched type epoxy resin of hydrophilic modifying.
5. preparation method as claimed in claim 1, is characterized in that, adds deionized water, comprise the steps: in the described chemistry of the over-expense at described hydrophilic modifying epoxy resin
In the hyperbranched type epoxy resin of described hydrophilic modifying, once or in batches add deionized water, the add-on of described deionized water is 1-5 times of the hyperbranched type weight epoxy of described hydrophilic modifying.
6. preparation method as claimed in claim 1, is characterized in that, described polyamine be quadrol, propylene diamine, N, N-dimethylated propyl diethylenetriamine, diethylene triamine, diethylenetriamine, triethylene tetramine, season penta tetramine, one or more in polyether polyamine.
7. preparation method as claimed in claim 1, is characterized in that, described epoxy resin is one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, diglycidyl ether type epoxy resin.
8. preparation method as claimed in claim 1, it is characterized in that, described catalyzer is the one in boron trifluoride diethyl etherate, aluminum chloride, iron trichloride.
9. preparation method as claimed in claim 1, is characterized in that, described Hydrophilicrto polyether is one or more in polyoxyethylene glycol, polyoxyethylene glycol monoether, polyoxyethylene glycol monoesters class.
10. the preparation method as described in claim 3 or 4, is characterized in that, described solvent is the one in methylene dichloride, trichloromethane, acetone, glycol dimethyl ether, ethylene glycol dibutyl ether.
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Cited By (9)
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| CN106633086A (en) * | 2016-12-28 | 2017-05-10 | 北京光华纺织集团有限公司 | Preparation method for polyamide-modified epoxy resin emulsion |
| CN106637984A (en) * | 2016-12-28 | 2017-05-10 | 北京光华纺织集团有限公司 | Preparation method of polyamide-modified epoxy carbon fiber |
| CN108239883A (en) * | 2017-12-27 | 2018-07-03 | 北京光华纺织集团有限公司 | A kind of preparation method of the carbon fiber sizing agent of doped graphene |
| CN109251305A (en) * | 2018-07-10 | 2019-01-22 | 吉林乾仁新材料有限公司 | Two hydrophilic cationic epoxide resin type high-performance fiber sizing agent of self assembly self-emulsifying/size/film forming agent and preparation method thereof |
| CN110128034A (en) * | 2019-02-12 | 2019-08-16 | 吉林化工学院 | It nano-oxide fabricated in situ and is applied in polyester-type carbon fiber sizing agent and basalt fibre/glass fiber infiltration agent |
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| CN112812614A (en) * | 2021-01-12 | 2021-05-18 | 上海涂固安高科技有限公司 | Putty applied to low-surface treatment of steel material and preparation method thereof |
| CN114395130A (en) * | 2022-01-24 | 2022-04-26 | 常州大学 | Emulsifier for preparing low-viscosity water-based epoxy emulsion, preparation method thereof and water-based epoxy emulsion containing emulsifier |
| CN114622293A (en) * | 2021-12-07 | 2022-06-14 | 嘉兴逸鹏化纤有限公司 | Production process for spinning fine denier yarn on iBox 32-head equipment |
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| CN106633086A (en) * | 2016-12-28 | 2017-05-10 | 北京光华纺织集团有限公司 | Preparation method for polyamide-modified epoxy resin emulsion |
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| CN108239883A (en) * | 2017-12-27 | 2018-07-03 | 北京光华纺织集团有限公司 | A kind of preparation method of the carbon fiber sizing agent of doped graphene |
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| CN110128034A (en) * | 2019-02-12 | 2019-08-16 | 吉林化工学院 | It nano-oxide fabricated in situ and is applied in polyester-type carbon fiber sizing agent and basalt fibre/glass fiber infiltration agent |
| CN112779783A (en) * | 2021-01-04 | 2021-05-11 | 江苏先诺新材料科技有限公司 | Preparation method of polyimide mesh fabric |
| CN112779783B (en) * | 2021-01-04 | 2023-04-07 | 江苏先诺新材料科技有限公司 | Preparation method of polyimide mesh fabric |
| CN112812614A (en) * | 2021-01-12 | 2021-05-18 | 上海涂固安高科技有限公司 | Putty applied to low-surface treatment of steel material and preparation method thereof |
| CN114622293A (en) * | 2021-12-07 | 2022-06-14 | 嘉兴逸鹏化纤有限公司 | Production process for spinning fine denier yarn on iBox 32-head equipment |
| CN114395130A (en) * | 2022-01-24 | 2022-04-26 | 常州大学 | Emulsifier for preparing low-viscosity water-based epoxy emulsion, preparation method thereof and water-based epoxy emulsion containing emulsifier |
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