CN104448245B - A kind of preparation method of hyperbranched type epoxy emulsion - Google Patents
A kind of preparation method of hyperbranched type epoxy emulsion Download PDFInfo
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- CN104448245B CN104448245B CN201410784716.5A CN201410784716A CN104448245B CN 104448245 B CN104448245 B CN 104448245B CN 201410784716 A CN201410784716 A CN 201410784716A CN 104448245 B CN104448245 B CN 104448245B
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Abstract
The present invention relates to epoxy emulsion preparing technical fields, and in particular to a kind of preparation method of hyperbranched type epoxy emulsion.The preparation method, includes the following steps：Polyamine is reacted with epoxy resin, synthesis of super branched type epoxy resin；The hyperbranched type epoxy resin under the effect of the catalyst, reacts into Hydrophilicrto polyether and obtains the hyperbranched type epoxy resin of hydrophilic modifying；Deionized water is added in the over-expense chemistry epoxy resin of the hydrophilic modifying, by shear agitation, is prepared into hyperbranched type epoxy emulsion.The present invention is by preparing a kind of hydrophilic polyether modified hyperbranched type epoxy resin, stable hyperbranched type epoxy emulsion is prepared into through emulsification, it can be used as the size of carbon fiber sizing agent, glass fibre and basalt fibre, the excellent convergence of fibre bundle, fibrillation and the wellability with epoxy resin are capable of providing, can be used for preparing high interlayer shear and high-temperature resistant composite material using the fiber of the epoxy emulsion starching.
Description
Technical field
The present invention relates to epoxy emulsion preparing technical fields, and in particular to a kind of preparation side of hyperbranched type epoxy emulsion
Method.
Background technology
The main application of one of the high performance fibers such as carbon fiber, glass fibre, basalt fibre is to prepare fiber reinforcement tree
The composite material material of fat, it is usually fine in carbon fiber, glass fibre and basalt in order to improve the performance of fiber-reinforced resin
It ties up in contour performance fiber production process, needs to handle fiber surface, the sizing agent used in being produced such as carbon fiber,
The size used in glass fibre or basalt fibre production.
Main component in the size of carbon fiber sizing agent and glass fibre is all resin emulsion, is existed by sizing technique
Fiber surface forms nanometer stage resin layers, and wearability, convergence, expanding, the antistatic property that resin layer will improve fiber are adjusted
Flexural resilience and straight elevator degree reduce the friction coefficient of carbon fiber, reduce the occurrence quantity of processed and applied process lousiness, adapt to the later stage
To demand of the techniques to fibre property such as braiding laying, windings in composite material shaping process.On the other hand, the tree of fiber surface
Lipid layer can be improved and regulate and control matrix resin compatibility and wetting property of the carbon fiber in composite material preparation process, pass through
The curing reaction in composite material later stage forms good composite material interface between fiber and polymeric matrix, improves fine
Dimension and the caking property of matrix resin and the interlaminar shear strength (ILSS) of fibre reinforced composites.In view of resin emulsion is to high property
The performance of energy fiber and its composite material, which all has, to be significantly affected, therefore to the stability of resin emulsion, the film forming of resin, tree
Heat resistance, reactivity of fat etc. require strictly.
Epoxy emulsion is that most resin emulsions is applied in carbon fiber sizing agent and glass fiber infiltration agent.Epoxy at present
The resin emulsion that emulsion preparation method is prepared usually using surfactant emulsifies epoxy resin, this method, emulsion particle diameter are big
And wider distribution, distribution uniformity of the resin in fiber surface can be influenced；The migration of surfactant can also make stability of emulsion
It destroys, surfactant does not have reactivity, influences whether the interlaminar shear strength of composite material yet.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of hyperbranched type epoxy emulsion, are prepared by the preparation method
The hyperbranched type epoxy emulsion gone out can be used as the size of carbon fiber sizing agent, glass fibre and basalt fibre, energy
Enough provide fibre bundle excellent convergence, fibrillation and the wellability with epoxy resin.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of hyperbranched type epoxy emulsion, includes the following steps：
Polyamine is reacted with epoxy resin, synthesis of super branched type epoxy resin；
The hyperbranched type epoxy resin under the effect of the catalyst, reacts into Hydrophilicrto polyether and obtains hydrophilic modifying
Hyperbranched type epoxy resin；
Deionized water is added in the over-expense chemistry epoxy resin of the hydrophilic modifying, by shear agitation, is prepared into super
Branching type epoxy emulsion.
Further, it is described to react polyamine with epoxy resin, synthesis of super branched type epoxy resin, including walking as follows
Suddenly：
Determine in polyamine can reactive hydrogen mole be a, the mole for determining the epoxy group of epoxy resin is b, by a:b
The ratio being worth for 1~30 once or in batches puts into polyamine and epoxy resin in reaction kettle, is warming up to 40~120 DEG C of reactions
1-8 hours, obtain hyperbranched type epoxy resin or hyperbranched type epoxy resin solution.
Further, described to react polyamine with epoxy resin, synthesis of super branched type epoxy resin further includes following step
Suddenly：
Described that polyamine and epoxy resin is primary or after put into reaction kettle in batches, according to reaction system viscosity,
Solvent is added in reduce reaction system viscosity.
Further, the hyperbranched type epoxy resin under the effect of the catalyst, is reacted into Hydrophilicrto polyether and is obtained
The hyperbranched type epoxy resin of hydrophilic modifying, includes the following steps：
The hyperbranched type epoxy resin is dissolved using solvent；
Hydrophilicrto polyether and catalyst are added in the over-expense chemistry epoxy resin upon dissolution, it is small to be stirred to react 4-12
When, 0~80 DEG C of reaction temperature；The addition of the Hydrophilicrto polyether is the 5-40% of the hyperbranched type ring oxygen resin quality,
The addition of the catalyst is the 0.01%-0.5% of the Hydrophilicrto polyether weight；
It adds in deionized water and terminates reaction, by vacuum distillation, remove the solvent in solution, obtain the over-expense of hydrophilic modifying
Change type epoxy resin.
Further, it is described to add in deionized water in the over-expense chemistry epoxy resin of the hydrophilic modifying, including as follows
Step：
It is primary or deionized water, the deionized water is added portionwise into the hyperbranched type epoxy resin of the hydrophilic modifying
1-5 times of hyperbranched type weight epoxy for the hydrophilic modifying of addition.
Further, the polyamine be ethylenediamine, propane diamine, N, it is N- dimethylated propyl diethylenetriamines, diethylene triamine, two sub-
It is one or more in ethyl triamine, triethylene tetramine, season penta tetramine.
Further, the epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic epoxy tree
It is one or more in fat, diglycidyl ether type epoxy resin.
Further, the catalyst is one kind in boron trifluoride ether, alchlor, ferric trichloride.
Further, the Hydrophilicrto polyether is one kind in polyethylene glycol, polyethylene glycol monoether, polyethyleneglycol esters
It is or a variety of.
Further, the solvent is dichloromethane, in chloroform, acetone, glycol dimethyl ether, butyl cellosolve
One kind.
Compared with prior art, what the technical solution adopted by the present invention generated has the beneficial effect that：
The present invention is prepared into stable by preparing a kind of hydrophilic polyether modified hyperbranched type epoxy resin through emulsification
Hyperbranched type epoxy emulsion can use, Neng Gouti as the size of carbon fiber sizing agent, glass fibre and basalt fibre
For the excellent convergence of fibre bundle, fibrillation and wellability with epoxy resin, can be used using the fiber of the epoxy emulsion starching
In preparing high interlayer shear and high-temperature resistant composite material.
Description of the drawings
Fig. 1 is the process flow chart of the preparation method of hyperbranched type epoxy emulsion provided in an embodiment of the present invention.
Specific embodiment
Technical solution of the present invention is described in detail with reference to the accompanying drawings and examples.
As shown in Figure 1, the embodiment of the present invention provides a kind of preparation method of hyperbranched type epoxy emulsion, including walking as follows
Suddenly：
Step 110：Polyamine is reacted with epoxy resin, synthesis of super branched type epoxy resin；
Specifically, the step 110 includes the following steps：
Determine in polyamine can reactive hydrogen mole be a, the mole for determining the epoxy group of epoxy resin is b, by a:b
The ratio being worth for 1~30 once or in batches puts into polyamine and epoxy resin in reaction kettle, is warming up to 40~120 DEG C of reactions
1-8 hours, obtain hyperbranched type epoxy resin or hyperbranched type epoxy resin solution.The polyamine for ethylenediamine, propane diamine,
It is one or more in N, N- dimethylated propyl diethylenetriamine, diethylene triamine, diethylenetriamines, triethylene tetramine, season penta tetramine；
The epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, diglycidyl ether type epoxy
It is one or more in resin；
The step 110 further includes following steps：
Described that polyamine and epoxy resin is primary or after put into reaction kettle in batches, if reaction system viscosity is big,
Solvent can be added in reduce reaction system viscosity；The solvent is dichloromethane, chloroform, acetone, glycol dimethyl ether, second
One kind in dibutyl ether.
Step 120：The hyperbranched type epoxy resin under the effect of the catalyst, reacts into Hydrophilicrto polyether and obtains parent
The hyperbranched type epoxy resin that water is modified；
Specifically, the step 120 includes the following steps：
Step 1201：The hyperbranched type epoxy resin is dissolved using solvent；The solvent is dichloromethane, three chloromethanes
One kind in alkane, acetone, glycol dimethyl ether, butyl cellosolve；
Step 1202：Hydrophilicrto polyether and catalyst, stirring are added in the over-expense chemistry epoxy resin upon dissolution
Reaction 4-12 hours, 0~80 DEG C of reaction temperature；The addition of the Hydrophilicrto polyether is the hyperbranched type ring oxygen resin quality
5-40%, the addition of the catalyst is the 0.01%-0.5% of the Hydrophilicrto polyether weight；The catalyst is three
The one kind being fluorinated in borate ether, alchlor, ferric trichloride；The Hydrophilicrto polyether is polyethylene glycol, polyethylene glycol monoether, is gathered
It is one or more in ethylene glycol ester class；
Step 1203：It adds in deionized water and terminates reaction, by vacuum distillation, remove the solvent in solution, obtain hydrophilic
Modified hyperbranched type epoxy resin.
Step 130：Deionized water is added in the over-expense chemistry epoxy resin of the hydrophilic modifying, by shear agitation,
It is prepared into hyperbranched type epoxy emulsion；
Specifically, it is primary into the hyperbranched type epoxy resin of the hydrophilic modifying or deionized water is added portionwise, it is described
The addition of deionized water is 1-5 times of the hyperbranched type weight epoxy of the hydrophilic modifying.
Embodiment 1：
The present embodiment provides a kind of preparation methods of hyperbranched type epoxy resin latex, include the following steps：
(1) by 1 mole of diethylenetriamines, 10 moles of bisphenol A type ring oxygen E51 and 5 moles of butyl cellosolves are added to
In three-necked flask, 80 DEG C are warming up to, after reacting 2 hours, adding in 10 moles of propane diamine, the reaction was continued 4 hours, then puts into 40 again
The reaction was continued 4 hours for moles of bisphenol A type ring oxygen E51 resins, obtains hyperbranched type epoxy resin solution；
(2) after the hyperbranched type epoxy resin solution of preparation being cooled to 40 DEG C, prepared hyperbranched type ring oxygen is added in
The PEG2000 resins (average molecular weight is 2000 polyethyleneglycol resins) of resin quality 20% and 0.2% boron trifluoride ether
Solution after being kept for 40 DEG C and being stirred 2 hours, adds in the deionized water of system weight 30%, by being evaporated under reduced pressure out solvent second two
Alcohol butyl oxide obtains the hyperbranched type epoxy resin of hydrophilic modifying；
(3) the hyperbranched type epoxy resin of hydrophilic modifying is warming up to 60 DEG C, adds in the hyperbranched type ring oxygen of hydrophilic modifying
After 50% deionized water of resin quality stirs evenly, 40 DEG C are cooled to, is then added in again into mixed system hydrophilic
Hyperbranched type ring is prepared in stirring or high-shear emulsifying after 1 times of deionized water of modified hyperbranched type ring oxygen resin quality
Oxygen lotion.
Embodiment 2：
(1) by 1 mole of propane diamine, 5 moles of polyetheramines D230,25 moles of bisphenol A type ring oxygen E44 are disposably added to three mouthfuls
In flask, 100 DEG C are warming up to, after reacting 3 hours, obtains hyperbranched type epoxy resin；
(2) after the hyperbranched type epoxy resin of preparation being cooled to 40 DEG C, prepared hyperbranched type epoxy resin is added in
After the acetone stirring and dissolving of quality 30%, the PEG4000 for continuously adding prepared hyperbranched type ring oxygen resin quality 15% is (flat
Average molecular weight be 4000 polyethyleneglycol resins) and 0.2% boron trifluoride ether solution, keep 40 DEG C and stir 2 hours after, add
Enter the deionized water of system weight 30%, by being evaporated under reduced pressure out solvent ethylene glycol butyl oxide, obtain the hyperbranched of hydrophilic modifying
Type epoxy resin；
(3) the hyperbranched type epoxy resin of hydrophilic modifying is warming up to 60 DEG C, adds in the hyperbranched type ring oxygen of hydrophilic modifying
After 50% deionized water of resin quality stirs evenly, 40 DEG C are cooled to, is then added in again into mixed system hydrophilic
Hyperbranched type ring is prepared in stirring or high-shear emulsifying after 1 times of deionized water of modified hyperbranched type ring oxygen resin quality
Oxygen lotion.
Embodiment 3：
(1) by 1 mole season penta tetramine, 8 moles of bisphenol A type ring oxygen E51 and 5 moles of butyl cellosolves are added to three mouthfuls of burnings
In bottle, 80 DEG C are warming up to, after reacting 2 hours, adding in 10 moles of dimethylene triamines, the reaction was continued 2 hours, then puts into 40 again
The reaction was continued 2 hours for moles of bisphenol A type ring oxygen E51 resins, obtains hyperbranched type epoxy resin solution；
(2) after the hyperbranched type epoxy resin solution of preparation being cooled to 40 DEG C, prepared hyperbranched type ring oxygen is added in
The PEG10000 (average molecular weight is 10000 polyethyleneglycol resins) of resin quality 15% and 0.2% boron trifluoride ether are molten
Liquid after being kept for 40 DEG C and being stirred 2 hours, adds in the deionized water of system weight 30%, by being evaporated under reduced pressure out solvent ethylene glycol
Butyl oxide obtains the hyperbranched type epoxy resin of hydrophilic modifying；
(3) the hyperbranched type epoxy resin of hydrophilic modifying is warming up to 60 DEG C, adds in the hyperbranched type ring oxygen of hydrophilic modifying
After 50% deionized water of resin quality stirs evenly, 40 DEG C are cooled to, is then added in again into mixed system hydrophilic
Hyperbranched type is prepared in stirring or high-shear emulsifying after 1.5 times of deionized water of modified hyperbranched type ring oxygen resin quality
Epoxy emulsion.
Compared with prior art, the present invention it has at least the following advantages：
(1) present invention first synthesizes a kind of hyperbranched type epoxy resin of stabilization, and compare ordinary epoxy resin, hyperbranched type
Epoxy resin has tree, and resin viscosity is low, and active function groups are more, can provide higher mechanical property after hardening.
(2) present invention is prepared into steady by preparing a kind of hydrophilic polyether modified hyperbranched type epoxy resin through emulsification
Fixed hyperbranched type epoxy emulsion, can use, energy as the size of carbon fiber sizing agent, glass fibre and basalt fibre
It enough provides fibre bundle excellent convergence, fibrillation and the wellability with epoxy resin, can be used using the fiber of the lotion starching
In preparing high interlayer shear and high-temperature resistant composite material.
The above is presently most preferred embodiment of the invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification for all within the spirits and principles of the present invention, being made,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of preparation method of hyperbranched type epoxy emulsion, which is characterized in that include the following steps：
Polyamine is reacted with epoxy resin, synthesis of super branched type epoxy resin；The polyamine is ethylenediamine, propane diamine, N,
N- dimethylated propyl diethylenetriamines, diethylenetriamines, triethylene tetramine, penta tetramine of season, one or more, the ring in polyether polyamine
Oxygen resin is bisphenol A type epoxy resin, in bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, diglycidyl ether type epoxy resin
It is one or more；
The hyperbranched type epoxy resin under the effect of the catalyst, reacts into Hydrophilicrto polyether and obtains the over-expense of hydrophilic modifying
Change type epoxy resin；
Deionized water is added in the over-expense chemistry epoxy resin of the hydrophilic modifying, by shear agitation, is prepared into hyperbranched
Type epoxy emulsion；
Wherein, described to react polyamine with epoxy resin, synthesis of super branched type epoxy resin includes the following steps：
Determine in polyamine can reactive hydrogen mole be a, the mole for determining the epoxy group of epoxy resin is b, is by a: b value
1~30 ratio is primary by polyamine and epoxy resin or puts into reaction kettle in batches, is warming up to 40~120 DEG C of reaction 1-8
Hour, obtain hyperbranched type epoxy resin or hyperbranched type epoxy resin solution；
Wherein, the hyperbranched type epoxy resin under the effect of the catalyst, reacts into Hydrophilicrto polyether and obtains hydrophilic modifying
Hyperbranched type epoxy resin, include the following steps：
The hyperbranched type epoxy resin is dissolved using solvent；
Hydrophilicrto polyether and catalyst are added in the over-expense chemistry epoxy resin upon dissolution, is stirred to react 2 hours, is reacted
40 DEG C of temperature；The addition of the Hydrophilicrto polyether is the 20% of the hyperbranched type ring oxygen resin quality, the catalyst
Addition is the 0.2% of the Hydrophilicrto polyether weight；
The deionized water for adding in system weight 30% terminates reaction, by vacuum distillation, removes the solvent in solution, obtains hydrophilic
Modified hyperbranched type epoxy resin；
Wherein, described to react polyamine with epoxy resin, synthesis of super branched type epoxy resin further includes following steps：
Described that polyamine and epoxy resin is primary or after put into reaction kettle in batches, according to reaction system viscosity, add in
Solvent is to reduce reaction system viscosity；
Wherein, it is described to add in deionized water in the over-expense chemistry epoxy resin of the hydrophilic modifying, include the following steps：
It is primary or deionized water is added portionwise into the hyperbranched type epoxy resin of the hydrophilic modifying, the deionized water plus
Enter 1-5 times of the hyperbranched type weight epoxy that amount is the hydrophilic modifying.
2. preparation method as described in claim 1, which is characterized in that the catalyst for boron trifluoride ether, alchlor,
One kind in ferric trichloride.
3. preparation method as described in claim 1, which is characterized in that the Hydrophilicrto polyether is polyethylene glycol, polyethylene glycol
It is one or more in monoether, polyethylene glycol monoesters.
4. preparation method as described in claim 1, which is characterized in that the solvent for dichloromethane, chloroform, acetone,
One kind in glycol dimethyl ether, butyl cellosolve.
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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 |
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| CN109251305B (en) * | 2018-07-10 | 2020-09-22 | 吉林乾仁新材料有限公司 | Self-assembly self-emulsifying amphiphilic water-based cationic epoxy resin type high-performance fiber sizing agent/impregnating agent/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 |
| 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 |
| CN114622293B (en) * | 2021-12-07 | 2023-05-16 | 嘉兴逸鹏化纤有限公司 | Production process for spinning fine denier yarn on iBox32 head equipment |
| CN114395130B (en) * | 2022-01-24 | 2023-05-09 | 常州大学 | Emulsifier for preparing low-viscosity aqueous epoxy emulsion, preparation method of emulsifier and aqueous epoxy emulsion containing emulsifier |
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