CN111978514A - Preparation method of high-temperature-resistant nonionic waterborne epoxy curing agent emulsion - Google Patents
Preparation method of high-temperature-resistant nonionic waterborne epoxy curing agent emulsion Download PDFInfo
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- CN111978514A CN111978514A CN202010866047.1A CN202010866047A CN111978514A CN 111978514 A CN111978514 A CN 111978514A CN 202010866047 A CN202010866047 A CN 202010866047A CN 111978514 A CN111978514 A CN 111978514A
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- 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
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- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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Abstract
The invention discloses a preparation method of a high-temperature-resistant nonionic waterborne epoxy hardener emulsion, which is characterized in that an emulsifier with amino groups at two ends is prepared from epoxy resin, hydrophilic polymer and polyamine, and the emulsifier and POSS modified epoxy resin-polyamine addition product are co-emulsified by a phase inversion method to prepare a heat-resistant nonionic waterborne epoxy hardener with uniform particle size distribution. The water-based epoxy curing agent prepared by the invention is non-ionic, the hydrophilicity is adjusted by adjusting the molecular weight of polyether polyol, the salinity is adjusted without adopting organic acid, the environment pollution caused by the volatilization of the organic acid is avoided, meanwhile, the water-based epoxy curing agent is insensitive to the pH value of the use environment, and the performance is stable when the water-based epoxy curing agent is matched with alkaline filler for use, so that the water-based epoxy curing agent can be used in the fields of carbon fiber sizing agent curing agent, metal corrosion. The preparation method is simple, the raw materials are cheap and easy to obtain, the particle size distribution of the product is uniform, and the particle size of the emulsion is between 100 and 200 nm.
Description
Technical Field
The invention belongs to the technical field of chemical industry, relates to a preparation method of an epoxy curing agent, and particularly relates to a preparation method of a high-temperature-resistant nonionic waterborne epoxy curing agent emulsion.
Background
The aqueous epoxy resin refers to a stable dispersion system formed by dispersing an epoxy resin in the form of droplets or fine particles in a dispersion medium having water as a continuous phase by a physical or chemical method. The main component of the water-based epoxy resin is epoxy resin, the epoxy resin is thermosetting resin with a linear structure, and a curing agent is added to be cured when the water-based epoxy resin is used, so that a three-dimensional cross-linked network can be formed. In recent years, due to the increase of environmental awareness, aqueous epoxy systems have been widely used, and the aqueous epoxy systems contain little or no organic solvent and have a low VOC content. With the rapid development of aerospace industry in China, the water-based epoxy system is widely applied to the field of carbon fiber sizing agents. However, when the epoxy resin is applied to the field of carbon fiber sizing agents, a cured product is required to have certain heat resistance, and if the epoxy resin is not modified, the heat resistance is not ideal. The improvement of the heat resistance of the cured epoxy resin can be achieved from two aspects: firstly, the structure of the epoxy resin is directly improved, and rigid groups such as benzene rings and the like are introduced into the structure; secondly, the epoxy resin curing agent is modified, and the curing agent becomes a part of the epoxy resin cured product along with the curing reaction, so the modification of the curing agent is an important way for improving the heat resistance of the epoxy resin. The research on the waterborne epoxy curing agent matched with the waterborne epoxy resin also influences the application of the waterborne epoxy system in the field of high temperature resistance.
Most of common water-based epoxy curing agents belong to cationic water-soluble epoxy curing agents, the curing agents are sensitive to pH value change and cannot be used together with alkaline pigments and fillers, and organic acid contained in the curing agents can corrode metal substrates and seriously affect the performance of a coating film. The nonionic waterborne epoxy curing agent does not contain ions in the structure, can well make up for the defects, has wide application range, and is also the key research direction of the waterborne epoxy curing agent in the future. At present, the waterborne epoxy system is modified by using fatty amine as a main amine, most of the waterborne epoxy systems are not high-temperature resistant, and the application of the waterborne epoxy system in the high-temperature field is severely limited.
The nano particles have excellent heat resistance, and the thermal stability, strength, oxidation resistance and the like of the nano particles can be effectively improved through the nano particle modified polymer. Polyhedral oligomeric silsesquioxane (POSS) is a nano particle with a cage-shaped framework structure, and the surface of reactive POSS can be provided with active groups such as epoxy groups, amino groups and the like and can be connected in a polymer through chemical bonds, so that the reactive POSS is more stably and uniformly distributed in the polymer and is an excellent material for improving the heat resistance of the polymer.
Disclosure of Invention
Aiming at the defects of sensitivity to pH value, incapability of being used together with alkaline pigment and filler, poor heat resistance and the like of the waterborne epoxy curing agent, the invention provides a preparation method of a high-temperature-resistant nonionic waterborne epoxy curing agent emulsion. The invention discloses a high-temperature-resistant nonionic waterborne epoxy curing agent prepared by introducing nano-particle polyhedral oligomeric silsesquioxane (POSS) into a nonionic waterborne epoxy curing agent.
The purpose of the invention is realized by the following technical scheme:
a preparation method of high temperature resistant non-ionic waterborne epoxy hardener emulsion is provided, an emulsifier with amino groups at two ends is prepared by epoxy resin, hydrophilic polymer and polyamine, and the emulsifier and POSS modified epoxy resin-polyamine addition product are co-emulsified by a phase inversion method to prepare a heat resistant non-ionic waterborne epoxy hardener with uniform particle size distribution, and the preparation method specifically comprises the following steps:
the method comprises the following steps: preparation of POSS-modified epoxy resin-polyamine adducts
The method comprises the following steps: dissolving 10-20 parts by mass of POSS and 100 parts by mass of epoxy resin in an organic solvent, uniformly dispersing the POSS and the epoxy resin in the organic solvent by ultrasonic treatment for 20-30 min, adding the mixture into 150 parts by mass of polyamine, carrying out heat preservation reaction at 30-120 ℃ for 0.5-5 h, and removing the solvent under reduced pressure after the reaction is finished to obtain the POSS modified epoxy resin-polyamine adduct.
The second method comprises the following steps: dissolving 10-20 parts by mass of POSS and 150 parts by mass of polyamine in an organic solvent, uniformly mixing the POSS and the polyamine by ultrasonic treatment, wherein the ultrasonic time is 20-30 min, dissolving 100 parts by mass of epoxy resin in the organic solvent, uniformly dispersing by ultrasonic treatment, wherein the ultrasonic time is 10-20 min, adding the epoxy resin into an ultrasonic blend of the POSS and the polyamine, carrying out heat preservation reaction at 30-120 ℃ for 0.5-5 h, and after the reaction is finished, removing the solvent by pressure reduction to obtain the POSS modified epoxy resin-polyamine adduct.
Step two: preparation of nonionic aqueous epoxy curing agent emulsion
Adding an emulsifier into a POSS modified epoxy resin-polyamine addition product, controlling the mass fraction of POSS to be 1-10%, wherein the mass of the emulsifier is 0.4-1 times of that of the epoxy resin-polyamine addition product, adding deionized water at 30-120 ℃ and preparing a nano-emulsion with small particle size and uniform distribution by a phase inversion method, wherein: the particle size of the emulsion is within 200nm, and the mass of the deionized water is 30-70%.
In the invention, the emulsifier is an emulsifier with amino groups at two ends, and can be prepared from 10-20 parts by mass of epoxy resin, 20-50 parts by mass of polyether polyol, 20-50 parts by mass of alkylphenol polyoxyethylene and 20-80 parts by mass of polyamine, wherein: the polyether polyol can be one or a mixture of two of polyethylene glycol and polypropylene glycol, wherein the molecular weight of the polyethylene glycol is 400-10000, and the molecular weight of the polypropylene glycol is 400-2000.
In the invention, the epoxy resin is one or a mixture of more of bisphenol A type liquid epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and novolac epoxy resin.
In the invention, the polyamine is one or a mixture of several of aliphatic polyamine, alicyclic polyamine and aromatic polyamine, and specifically is one or a mixture of several of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, tetramethylene diamine, hexamethylene diamine, dodecamethylene diamine, hexamethylene diamine, diaminomethylcyclohexane, aminoethylpiperazine, diaminomethylcyclohexyl methane, diaminocyclohexyl methane, isophorone diamine, menthane diamine, m-phenylenediamine, m-xylylenediamine, p-phenylenediamine, diaminodiphenyl methane and diaminodiphenyl sulfone.
In the invention, the solvent used in the reaction process is one of acetone, butanone, propylene glycol methyl ether, toluene and the like.
In the invention, POSS is cage-type POSS with epoxy group or cage-type POSS with amino group.
Compared with the prior art, the invention has the following advantages:
(1) the water-based epoxy curing agent prepared by the invention is non-ionic, the hydrophilicity is adjusted by adjusting the molecular weight of polyether polyol, the salinity is adjusted without adopting organic acid, the environment pollution caused by the volatilization of the organic acid is avoided, meanwhile, the water-based epoxy curing agent is insensitive to the pH value of the use environment, and the performance is stable when the water-based epoxy curing agent is matched with alkaline filler for use, so that the water-based epoxy curing agent can be used in the fields of carbon fiber sizing agent curing agent, metal corrosion.
(2) The preparation method is simple, the raw materials are cheap and easy to obtain, the particle size distribution of the product is uniform, and the particle size of the emulsion is between 100 and 200 nm.
(3) According to the invention, POSS is chemically bonded into the curing agent, so that the blend modification is more stable.
(4) The present invention can significantly improve the heat resistance of a cured product with a small amount of POSS.
(5) The curing agent emulsion prepared by the invention has high stability and is convenient to store and transport.
(6) The solvent used in the invention can be recycled, which is beneficial to environmental protection and cost saving.
Drawings
FIG. 1 is a particle size distribution diagram of a high temperature resistant non-ionic waterborne epoxy hardener emulsion prepared in example 1;
FIG. 2 is a TG analysis of a high temperature-resistant non-ionic aqueous epoxy hardener curing sizing prepared in example 1.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
This example prepares a high temperature resistant non-ionic waterborne epoxy hardener emulsion according to the following steps:
the method comprises the following steps: preparation of POSS-modified epoxy resin-polyamine adducts
Dissolving 10 parts by mass of epoxy cage type POSS and 100 parts by mass of epoxy resin E51 in butanone serving as an organic solvent, uniformly dispersing the epoxy cage type POSS and the epoxy resin E51 in the organic solvent by utilizing ultrasonic treatment, carrying out ultrasonic treatment for 30min, then adding the mixture into 150 parts by mass of aromatic amine, carrying out heat preservation reaction for 4h at 80 ℃, and after the reaction is finished, removing the solvent by pressure reduction to obtain the POSS modified epoxy resin-polyamine addition product.
Step two: preparation of nonionic aqueous epoxy curing agent emulsion
Adding an emulsifier with amino groups at two ends into a POSS modified epoxy resin-polyamine addition product, wherein the emulsifier is prepared from 10 parts by mass of epoxy resin E51, 30 parts by mass of polyethylene glycol, 18 parts by mass of alkylphenol polyoxyethylene ether and 40 parts by mass of aromatic amine, controlling the mass fraction of POSS to be 1%, and adding deionized water at 50 ℃ to prepare a nano-emulsion with small particle size and uniform distribution by a phase inversion method, wherein the particle size of the emulsion is within 200nm, and the mass of the deionized water is 60%.
The emulsion prepared in this example has stability: the mixture is not layered after being centrifuged for 1 hour at 6000r/min, and the particle size is kept stable after centrifugation. As can be seen from FIG. 1, the particle size of the emulsion prepared by the embodiment is between 100 nm and 200 nm. As can be seen from FIG. 2, when the amount of POSS added was 1%, the T5% of the cured product increased by 10 ℃.
Example 2
This example prepares a high temperature resistant non-ionic waterborne epoxy hardener emulsion according to the following steps:
the method comprises the following steps: preparation of POSS-modified epoxy resin-polyamine adducts
Dissolving 10 parts by mass of epoxy cage type POSS and 100 parts by mass of epoxy resin E44 in an organic solvent propylene glycol methyl ether, uniformly dispersing the two in the organic solvent by ultrasonic treatment for 30min, adding the mixture into 150 parts by mass of aromatic amine, carrying out heat preservation reaction at 90 ℃ for 4h, and removing the solvent under reduced pressure after the reaction is finished to obtain the POSS modified epoxy resin-polyamine adduct.
Step two: preparation of nonionic aqueous epoxy curing agent emulsion
Adding an emulsifier with amino groups at two ends into a POSS modified epoxy resin-polyamine addition product, wherein the emulsifier is prepared from 10 parts by mass of epoxy resin E44, 20 parts by mass of polyethylene glycol, 10 parts by mass of polypropylene glycol, 25 parts by mass of alkylphenol polyoxyethylene ether and 45 parts by mass of aromatic amine, controlling the mass fraction of POSS to be 1%, and adding deionized water at 50 ℃ to prepare a nano-scale emulsion with small particle size and uniform distribution by a phase inversion method, wherein the particle size of the emulsion is within 200nm, and the mass of the deionized water is 60%.
The emulsion prepared in this example has stability: no separation is carried out after centrifugation for 1h at 6000 r/min.
Example 3
This example prepares a high temperature resistant non-ionic waterborne epoxy hardener emulsion according to the following steps:
the method comprises the following steps: preparation of POSS-modified epoxy resin-polyamine adducts
Dissolving 10 parts by mass of cage-type POSS with amino and 150 parts by mass of aliphatic amine in an organic solvent propylene glycol methyl ether, uniformly mixing the two by ultrasonic treatment for 30min, dissolving 50 parts by mass of epoxy resin E44 and 50 parts by mass of epoxy resin F51 in the organic solvent, uniformly dispersing by ultrasonic treatment for 20min, adding the epoxy resin into the alicyclic amine, carrying out heat preservation reaction at 80 ℃ for 5h, and removing the solvent under reduced pressure after the reaction is finished to obtain the POSS modified epoxy resin-polyamine addition product.
Step two: preparation of nonionic aqueous epoxy curing agent emulsion
Adding an emulsifier with amino groups at two ends into a POSS modified epoxy resin-polyamine addition product, wherein the emulsifier is prepared from 15 parts by mass of epoxy resin E44, 15 parts by mass of polyethylene glycol, 15 parts by mass of polypropylene glycol, 30 parts by mass of alkylphenol polyoxyethylene and 30 parts by mass of alicyclic amine, controlling the mass fraction of POSS to be 3%, the mass of the emulsifier is 0.5 times of that of the epoxy resin-polyamine addition product, adding deionized water at 60 ℃ to prepare a nano-scale emulsion with small particle size and uniform distribution by a phase inversion method, and the particle size of the emulsion is within 200nm, wherein the mass of the deionized water is 50%.
The emulsion prepared in this example has stability: no separation is carried out after centrifugation for 1h at 6000 r/min.
Example 4
This example prepares a high temperature resistant non-ionic waterborne epoxy hardener emulsion according to the following steps:
the method comprises the following steps: preparation of POSS-modified epoxy resin-polyamine adducts
Dissolving 15 parts by mass of cage-type POSS with amino and 150 parts by mass of alicyclic amine in an organic solvent acetone, uniformly mixing the two by ultrasonic treatment for 30min, dissolving 100 parts by mass of epoxy resin F48 in the organic solvent, uniformly dispersing by ultrasonic treatment for 20min, adding the epoxy resin into polyamine, carrying out heat preservation reaction at 80 ℃ for 5h, and after the reaction is finished, removing the solvent by pressure reduction to obtain the POSS modified epoxy resin-polyamine adduct.
Step two: preparation of nonionic aqueous epoxy curing agent emulsion
Adding an emulsifier with amino groups at two ends into a POSS modified epoxy resin-polyamine addition product, wherein the emulsifier is prepared from 20 parts by mass of epoxy resin F48, 60 parts by mass of polyethylene glycol, 30 parts by mass of alkylphenol polyoxyethylene ether and 40 parts by mass of alicyclic amine, controlling the mass fraction of POSS to be 5%, and adding deionized water at 60 ℃ to prepare a nano-emulsion with small particle size and uniform distribution by a phase inversion method, wherein the particle size of the emulsion is within 200nm, and the mass of the deionized water is 50%.
The emulsion prepared in this example has stability: no separation is carried out after centrifugation for 1h at 6000 r/min.
Example 5
This example prepares a high temperature resistant non-ionic waterborne epoxy hardener emulsion according to the following steps:
the method comprises the following steps: preparation of POSS-modified epoxy resin-polyamine adducts
Dissolving 20 parts by mass of cage-type POSS with amino, 120 parts by mass of alicyclic amine and 30 parts by mass of aromatic amine in an organic solvent acetone, uniformly mixing the two by ultrasonic treatment, carrying out ultrasonic treatment for 30min, dissolving 100 parts by mass of epoxy resin E51 in the organic solvent acetone, carrying out ultrasonic dispersion for 20min, adding an acetone solution of epoxy resin E51 into polyamine, carrying out heat preservation reaction at 80 ℃ for 5h, and after the reaction is finished, removing the solvent by pressure reduction to obtain the POSS modified epoxy resin-polyamine adduct.
Step two: preparation of nonionic aqueous epoxy curing agent emulsion
Adding an emulsifier with amino groups at two ends into a POSS modified epoxy resin-polyamine addition product, wherein the emulsifier is prepared from 20 parts by mass of epoxy resin E51, 10 parts by mass of polypropylene glycol, 30 parts by mass of alkylphenol polyoxyethylene ether and 40 parts by mass of alicyclic amine, controlling the mass fraction of POSS to be 5%, and adding deionized water at 60 ℃ to prepare a nano-emulsion with small particle size and uniform distribution by a phase inversion method, wherein the particle size of the emulsion is within 200nm, and the mass of the deionized water is 50%.
The emulsion prepared in this example has stability: no separation is carried out after centrifugation for 1h at 6000 r/min.
Claims (10)
1. A preparation method of high-temperature-resistant nonionic waterborne epoxy curing agent emulsion is characterized by comprising the following steps:
the method comprises the following steps: preparation of POSS-modified epoxy resin-polyamine adducts
Dissolving 10-20 parts by mass of POSS and 100 parts by mass of epoxy resin in an organic solvent, uniformly dispersing the POSS and the epoxy resin in the organic solvent by ultrasonic treatment for 20-30 min, adding the mixture into 150 parts by mass of polyamine, carrying out heat preservation reaction at 30-120 ℃ for 0.5-5 h, and removing the solvent under reduced pressure after the reaction is finished to obtain a POSS modified epoxy resin-polyamine adduct;
step two: preparation of nonionic aqueous epoxy curing agent emulsion
Adding an emulsifier with amino groups at two ends into a POSS modified epoxy resin-polyamine addition product, controlling the mass fraction of POSS to be 1-10%, wherein the mass of the emulsifier is 0.4-1 times of that of the epoxy resin-polyamine addition product, and adding deionized water at 30-120 ℃ to prepare the nano-scale emulsion through a phase inversion method, wherein: the mass of the deionized water is 30-70%.
2. The method for preparing the high-temperature-resistant nonionic waterborne epoxy curing agent emulsion according to claim 1, characterized in that the first step is replaced by:
dissolving 10-20 parts by mass of POSS and 150 parts by mass of polyamine in an organic solvent, uniformly mixing the POSS and the polyamine by ultrasonic treatment, wherein the ultrasonic time is 20-30 min, dissolving 100 parts by mass of epoxy resin in the organic solvent, uniformly dispersing by ultrasonic treatment, wherein the ultrasonic time is 10-20 min, adding the epoxy resin into an ultrasonic blend of the POSS and the polyamine, carrying out heat preservation reaction at 30-120 ℃ for 0.5-5 h, and after the reaction is finished, removing the solvent by pressure reduction to obtain the POSS modified epoxy resin-polyamine adduct.
3. The method for preparing the high-temperature-resistant nonionic aqueous epoxy hardener emulsion according to claim 1, wherein the emulsifier is prepared from 10 to 20 parts by mass of an epoxy resin, 20 to 50 parts by mass of a polyether polyol, 20 to 50 parts by mass of an alkylphenol ethoxylate and 20 to 80 parts by mass of a polyamine.
4. The method for preparing the high temperature resistant non-ionic waterborne epoxy hardener emulsion according to claim 3, wherein the polyether polyol is one or a mixture of two of polyethylene glycol and polypropylene glycol, the molecular weight of the polyethylene glycol is 400-10000, and the molecular weight of the polypropylene glycol is 400-2000.
5. The method for preparing the high-temperature-resistant nonionic waterborne epoxy hardener emulsion according to claim 1, 2 or 3, wherein the epoxy resin is one or a mixture of bisphenol A type liquid epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and novolac epoxy resin.
6. The method for preparing the high-temperature-resistant nonionic aqueous epoxy hardener emulsion according to claim 1, 2 or 3, wherein the polyamine is one or a mixture of aliphatic polyamine, alicyclic polyamine and aromatic polyamine.
7. The method for preparing the high temperature resistant non-ionic waterborne epoxy hardener emulsion according to claim 6, wherein the polyamine is one or a mixture of more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetramethylenediamine, hexamethylenediamine, dodecamethylenediamine, hexamethylenediamine, diaminomethylcyclohexane, aminoethylpiperazine, diaminomethylcyclohexylmethane, diaminocyclohexylmethane, isophoronediamine, menthane diamine, m-phenylenediamine, m-xylylenediamine, p-phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.
8. The method for preparing the high-temperature-resistant nonionic waterborne epoxy curing agent emulsion according to claim 1 or 2, wherein the solvent is one of acetone, butanone, propylene glycol methyl ether and toluene.
9. The method for preparing the high-temperature-resistant nonionic aqueous epoxy curing agent emulsion as claimed in claim 1 or 2, wherein the POSS is a cage-type POSS with epoxy group or a cage-type POSS with amino group.
10. The method for preparing the high-temperature-resistant nonionic aqueous epoxy curing agent emulsion according to claim 1, wherein the particle size of the emulsion is within 200 nm.
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