CN113214455A - Toughening type water-based epoxy curing agent and preparation method and application thereof - Google Patents
Toughening type water-based epoxy curing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN113214455A CN113214455A CN202110711545.3A CN202110711545A CN113214455A CN 113214455 A CN113214455 A CN 113214455A CN 202110711545 A CN202110711545 A CN 202110711545A CN 113214455 A CN113214455 A CN 113214455A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- epoxy resin
- curing agent
- toughening type
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Abstract
The invention discloses a toughening type waterborne epoxy curing agent and a preparation method and application thereof, wherein the curing agent is prepared from the following raw materials in parts by weight: 1 part of epoxy resin; 0.65-6 parts of polyamine compound; 0.1-1 part of toughened epoxy resin; 0.25-1.25 parts of mono-epoxy reactive diluent; 0.2-1 part of alkyl polyethylene glycol monoglycidyl ether. The epoxy curing agent has good hydrophilic property, good flexibility and good compatibility with epoxy resin, and a paint film of the epoxy resin coating has excellent salt spray resistance, water resistance and toughness, strong adhesive force and high hardness.
Description
Technical Field
The invention relates to an epoxy curing agent, in particular to a toughening type water-based epoxy curing agent and a preparation method and application thereof, belonging to the technical field of water-based epoxy coating.
Background
The epoxy resin coating has excellent adhesive force, mechanical property and chemical resistance, and is widely applied to the fields of coating corrosion prevention, civil engineering, adhesives and the like. With the increasing pressure on the requirement of environmental protection, the research on the water-based epoxy coating is an important trend in the development of the current coatings. The epoxy resin and a proper curing agent react to form a three-dimensional network structure, so that the epoxy resin has good mechanical property and corrosion resistance, and the curing agent is the key of the application value of the epoxy resin. As a waterborne anticorrosive coating, epoxy resin has common defects of brittle quality, poor impact toughness, easy falling off of a base material, pulverization and the like due to more rigid chain segments and smaller curing volume shrinkage rate of the epoxy resin after curing, so that the application of the epoxy resin is limited to a certain extent, and the toughening modification of the epoxy resin curing agent is always popular in domestic and foreign researches. At present, most of the existing waterborne epoxy curing agents in the market are prepared by taking polyamine and the like as basic raw materials through hydrophilic and oleophilic modification, and then a nonionic hydrophilic chain segment with a long alkyl chain is introduced to achieve the effect of improving the toughness. For example:
in patent CN 1958639 a, a two-step chain extension method is proposed to prepare a water-based epoxy curing agent, in which polyether polyol is used to perform a chain extension reaction on epoxy, then the chain extension product is continuously subjected to a secondary chain extension reaction with polyethylene polyamine, and finally monobasic acid is used to neutralize the chain extension product, thereby preparing the water-based curing agent with a flexible chain segment. However, the addition of organic acid not only causes environmental pollution, but also causes the reduction of film forming property, and flash rust is easily generated when the organic acid is used for metal corrosion prevention.
Patent CN 1084864A proposes the preparation of polyamide-based curing agent by reacting oxidized polyethylene glycol with polyamine, which has good flexibility, but the synthesis technology is difficult, and needs additional catalyst to achieve curing at room temperature.
At present, no good solution to the problems exists, and a curing agent with good water dispersion performance, good compatibility with epoxy resin and good flexibility is urgently needed.
Disclosure of Invention
In order to solve the above technical problems, a first object of the present invention is to provide a toughening type aqueous epoxy hardener, which has good hydrophilic property, good flexibility and good compatibility with epoxy resin.
The second purpose of the invention is to provide the preparation method of the toughening type water-based epoxy curing agent, and the preparation method is simple in process and easy to operate.
The third purpose of the invention is to provide the application of the toughening type water-based epoxy curing agent in the preparation of epoxy resin paint, and the epoxy resin paint prepared from the curing agent has excellent salt spray resistance, water resistance and toughness, and has strong adhesive force and high hardness.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the toughening type waterborne epoxy curing agent is prepared from the following raw materials in parts by weight:
the person skilled in the art understands that epoxy resin refers to a compound containing at least 2 epoxy groups. Further, the epoxy resin is selected from one or more of aliphatic epoxy resin and aromatic epoxy resin. In a preferred embodiment, the epoxy resin is any one or combination of polyhydric alcohol glycidyl ether, polyhydric phenol glycidyl ether and polyhydric carboxylic acid glycidyl ester, preferably polyhydric alcohol glycidyl ether and/or polyhydric phenol glycidyl ether; it is further preferred that the epoxy equivalent of the epoxy resin is 150-4000g/mol, preferably 200-2000g/mol, such as 300g/mol, 500g/mol, 700g/mol, 1000g/mol, 1500g/mol and 1800 g/mol.
Further, in the process for preparing the polyhydric phenol glycidyl ether, the polyhydric phenol raw material is selected from the group consisting of resorcinol, hydroquinone, 2-bis (4' -hydroxyphenyl) -propane (bisphenol a), dihydroxydiphenylmethane (bisphenol F) and a mixture of isomers thereof, 4' -dihydroxydiphenylcyclohexane, 4' -dihydroxy-3, 3' -dimethyldiphenylpropane, 4' -dihydroxybiphenyl, 4' -dihydroxybenzophenone, bis (4' -hydroxyphenyl) -1, 1-ethane, bis (4' -hydroxyphenyl) -1, 1-isobutane, bis (4' -hydroxy-t-butylphenyl) -2, 2-propane, bis (2-hydroxynaphthyl) -methane, bisphenol a mixture of two or more of phenol, a mixture of phenol and its isomers, 1, 5-dihydroxynaphthalene, tris (4-hydroxyphenyl) -methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, and chlorinated or brominated products of the foregoing.
Further, the polyhydric alcohol glycidyl ether is selected from the group consisting of ethylene glycol-1, 2-diglycidyl ether, propylene glycol-1, 3-diglycidyl ether, butylene glycol diglycidyl ether, pentanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, higher polyoxyalkylene glycol diglycidyl ether (e.g., higher polyoxyethylene glycol diglycidyl ether and polyoxypropylene glycol diglycidyl ether, mixed polyoxyethylene-propylene glycol diglycidyl ether), polyoxybutylene glycol diglycidyl ether, polyglycidyl ether of glycerin, polyglycidyl ether of trimethylolpropane, polyglycidyl ether of trimethylolethane, polyglycidyl ether of pentaerythritol, polyglycidyl ether of propylene glycol, and mixtures thereof, Polyglycidyl ethers of sorbitol, polyglycidyl ethers of cyclohexanedimethanol, polyglycidyl ethers of bis (4-hydroxycyclohexyl) methane, diglycidyl ethers of 2, 2-bis (4-hydroxycyclohexyl) propane, polyglycidyl ethers of castor oil or polyglycidyl ethers of triglycidyl tris (2-hydroxyethyl) isocyanurate.
Further, the glycidyl ester of polycarboxylic acid is obtained by reacting epichlorohydrin or a similar epoxy compound with a polycarboxylic acid (e.g., oxalic acid, succinic acid, adipic acid, glutaric acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 2, 6-naphthalenedicarboxylic acid), for example, a diglycidyl ester of adipic acid, a diglycidyl ester of phthalic acid or a diglycidyl ester of hexahydrophthalic acid.
Further preferably, the epoxy resins used in the present invention have a molecular weight of 1000 daltons or less. In a further embodiment, the epoxy resin is any one or combination of bisphenol a type epoxy resin, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. For example, the epoxy resin is epoxy resin E51 or epoxy resin E44.
Preferably, the polyamine compound is one or more of aliphatic polyamine, alicyclic polyamine and aromatic polyamine; in a preferred embodiment, the polyamine compound is selected from primary amines with at least 4 active hydrogens, for example, the aliphatic polyamine is an aliphatic diamine and/or an aliphatic triamine; the alicyclic polyamine is alicyclic diamine and/or alicyclic triamine; the aromatic polyamine is aromatic diamine and/or aromatic triamine. In a more preferred embodiment, the polyamine compound is a combination of any one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methyl-1, 5-pentylenediamine, 1, 6-hexylenediamine, diethylenetriamine, m-xylylenediamine, 1, 3-bisaminomethylcyclohexane, 1-ethyl-1, 3-propylenediamine, p-aminodicyclohexylmethane, 2, 4-trimethyl-1, 6-hexylenediamine, p-xylylenediamine, polyetheramine, triethylenetetramine, tetraethylenepentamine, isophoronediamine, polyethyleneimine and diethyltoluenediamine; further preferred is a combination of one or more of m-xylylenediamine, diethylenetriamine, polyetheramine, isophoronediamine, and triethylenetetramine.
Preferably, the toughening epoxy resin is dimer acid addition modified epoxy resin, and has at least 2 epoxy groups. It will be appreciated by those skilled in the art that in the modification reaction of the dimer acid with the epoxy resin, the epoxy resin may be selected from any one or combination of the foregoing epoxy resins.
Preferably, the monoepoxy reactive diluent is any one or more of epoxy ethers of phenols, epoxy esters of unsaturated alcohols, epoxy esters of unsaturated carboxylic acids, aliphatic glycidyl ethers, and aromatic glycidyl ethers. It is understood by those skilled in the art that the epoxy ether of a phenol is selected from the group consisting of epoxy ethers of phenols, epoxy ethers of cresols, epoxy ethers of C1-C21 alkyl-substituted phenols, epoxy ethers of C7-C21 aralkyl-substituted phenols, epoxy ethers of C7-C21 alkaryl-substituted phenols, cardanol glycidyl ether, and epoxy ethers of alkoxy-substituted phenols. The epoxy ester of an unsaturated carboxylic acid is selected from the group consisting of glycidyl monocarboxylate (glycidyl octanoate, glycidyl decanoate, glycidyl laurate, glycidyl stearate, glycidyl arachidic acid), glycidyl neodecanoate, epoxidized methyl oleate, epoxidized n-butyl oleate, epoxidized methyl palmitate and epoxidized ethyl linoleate. The aliphatic glycidyl ether is preferably an aliphatic glycidyl ether with the carbon number of C1-C18, and is preferably selected from butyl glycidyl ether, C12-C14 long alkyl chain glycidyl ether, tert-butyl glycidyl ether, cyclohexyl glycidyl ether, allyl glycidyl ether, octyl glycidyl ether, isopropyl glycidyl ether, decyl glycidyl ether and p-tert-butyl phenyl glycidyl ether. The aromatic glycidyl ether is preferably an aromatic glycidyl ether with carbon atoms of C10-C18, and is preferably selected from phenyl glycidyl ether, o-tolyl glycidyl ether and benzyl glycidyl ether. In a preferred embodiment, the monoepoxy reactive diluent is any one or combination of cardanol glycidyl ether, butyl glycidyl ether, alkyl glycidyl ether of C12-C14, tolyl glycidyl ether, phenyl glycidyl ether, nonylphenyl glycidyl ether, and p-tert-butylphenyl glycidyl ether. In a further preferred embodiment, the monoepoxy reactive diluent is any one or combination of butyl glycidyl ether, alkyl glycidyl ether of C12-C14, cresyl glycidyl ether, phenyl glycidyl ether, nonylphenyl glycidyl ether, and p-tert-butylphenyl glycidyl ether.
Preferably, the alkyl polyethylene glycol monoglycidyl ether has a structural expression shown in formula I; in the formula I, R is selected from H or C1-C12 alkyl, preferably H or C1-C4 alkyl; n is an integer of 5 or more, preferably n is an integer of 11 to 180;
further, the average molecular weight of the toughening type epoxy resin is 350-.
The preparation method of the toughening type water-based epoxy curing agent comprises the following steps:
1) blending epoxy resin and toughened epoxy resin to obtain an epoxy composition;
2) dripping the epoxy composition into a polyamine compound for reaction, and preserving heat for 0.5-3h after dripping is finished; distilling under reduced pressure to remove excessive polyamine compound to obtain intermediate;
3) optionally, in the presence of a solvent or water, dropwise adding a monoepoxy reactive diluent and alkyl polyethylene glycol monoglycidyl ether into the intermediate for end-capping reaction, and preserving heat for 0.5-3h after the dropwise adding is finished to obtain an end-capped product;
4) and adding water into the end-capped product, and mixing to prepare the curing agent.
It will be appreciated by those skilled in the art that the solvent may be an organic solvent commonly used in the art, such as any one or combination of propylene glycol methyl ether, ethylene glycol butyl ether, dipropylene glycol dimethyl ether, acetone, methyl ethyl ketone and butanol.
In step 2), in order to obtain the structure of the intermediate, it is necessary to ensure that the polyamine compound is excessive during the reaction, and if the epoxy composition is added too quickly, the local resin concentration is too high to affect the structure of the obtained intermediate, so the epoxy composition is added dropwise (preferably dropwise) to the polyamine compound in the invention to avoid adverse effects caused by too fast addition.
Further, the reaction temperature in step 2) is 60-120 ℃, preferably 80-100 ℃, such as 85 ℃, 90 ℃, 95 ℃ and the like; preferably, the dropping time of the epoxy composition is 0.5 to 5h, preferably 1 to 3h, such as 1.5h, 2h, 2.5h, etc.
Further, the reaction temperature in step 3) is 60-120 ℃, preferably 80-100 ℃, such as 85 ℃, 90 ℃, 95 ℃ and the like; preferably, the dropping time of the monoepoxy reactive diluent and the alkyl polyethylene glycol monoglycidyl ether is 0.5 to 4 hours, preferably 1 to 3 hours, such as 1.5 hours, 2 hours, 2.5 hours and the like.
Further, the water is added in step 4) to a solid content of the curing agent of 40-80%, for example, 50%, 60%, 70%, etc.
Further, the preparation method of the toughening type epoxy resin comprises the following steps: the dimer acid and the epoxy resin are reacted under the condition of a catalyst, the reaction temperature is 120-150 ℃, preferably 130-140 ℃, and the reaction time is 2-5h, preferably 1-3 h.
Further, in the preparation method of the toughened epoxy resin, the raw materials are used in the following amounts: the molar ratio of the total amount of epoxy groups in the epoxy resin to the total amount of carboxyl groups in the dimer acid is (2-100):1, preferably (2-10):1, such as 2.2:1, 2.5:1, 2.7:1, 3:1, 5:1, 10:1, etc.
It is understood by those skilled in the art that in the ring-opening reaction of the dimer acid with the epoxy resin, a catalyst and/or a solvent known in the art may also be used, as necessary. Preferably, the catalyst is one or more of triphenylphosphine, tetrabutylammonium bromide, triphenylphosphine and boron trifluoride diethyl etherate; more preferably, the catalyst is used in an amount of 0.05 to 1% by weight, such as 0.1 wt%, 0.2 wt%, 0.5 wt%, 0.8 wt%, etc., based on the total mass of the raw materials. The solvent can be water, propylene glycol methyl ether, ethylene glycol butyl ether, acetone, butanone, toluene, xylene, etc.
According to the production method of the present invention, other undesirable structures (such as a structure obtained by ring-opening reaction of one-molecule polyamine compound with a multi-molecule epoxy resin) may be produced in the resulting aqueous epoxy curing agent product, but the production process does not involve separation of by-products, but uses it as a whole, and all the evaluation effects are also carried out on a whole basis. The reaction process is monitored by a near infrared method and a nuclear magnetic method, the disappearance of the epoxy group proves that the reaction is finished, and the performance indexes of the finally obtained waterborne epoxy curing agent system comprise: amine number, solid content, and pH. In a preferred embodiment, the amine value of the aqueous epoxy curing agent is 100-500mgKOH/g, preferably 150-350mgKOH/g, such as 200mgKOH/g, 250mgKOH/g, 300mgKOH/g, etc.; the solid content is 40-80 wt%; the pH value is 8-12, preferably 9-11, such as 9.5, 10, 10.5, etc.
The application of the toughening type water-based epoxy curing agent in preparing epoxy resin paint.
The invention has the beneficial effects that:
(1) the toughening type water-based epoxy curing agent disclosed by the invention has good hydrophilicity and good water dispersion performance, can be dispersed or dissolved in water, and has good stability and construction performance; meanwhile, a flexible poly diacid long chain structure is introduced, so that a cured paint film has higher toughness, the capability of absorbing external impact energy of the paint film is improved, and the prepared paint film has excellent adhesive force.
(2) The chain extension is carried out on the polyamine by adopting the difunctional epoxy, and the epoxy resin structure is introduced, so that the good compatibility with the epoxy resin is ensured, meanwhile, the end capping is carried out by the reaction of the monoepoxy compound and the active hydrogen on the primary amine, the cross-linking sites are reduced, the reaction activity is reduced, the stress release in the curing process is facilitated, and when the epoxy resin coating prepared by matching the epoxy resin emulsion with the monoepoxy compound is coated and used, the paint film has excellent salt fog resistance, water resistance and strong adhesive force.
(3) The preparation method of the toughening type water-based epoxy curing agent has the advantages of simple process, easy operation and strong industrial applicability.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The sources of the starting materials used in the following examples and comparative examples are shown in Table 1:
sources of raw materials used in Table 1, examples 1-12 and comparative examples 1-3
| Name of substance | Suppliers of goods | CAS number |
| Isophoronediamine | Basf-Fr | 2855-13-2 |
| Diethylenetriamine | Dow's disease | 111-40-0 |
| Triethylene tetramine | Dow's disease | 112-24-3 |
| M-xylylenediamine | Ningbo national trade | 1477-55-0 |
| Polyetheramine D230 | Basf-Fr | 9046-10-0 |
| Epoxy resin E51/E44/E20 | Linglin chemical | 25068-38-6 |
| Dimer acid | Shanghai Bangheng | 61788-89-4 |
| Diethylene glycol diglycidyl ether | New and distant place of Anhui | 4206-61-5 |
| Butyl glycidyl ether | New and distant place of Anhui | 2426-08-06 |
| Phenyl glycidyl ether | New and distant place of Anhui | 122-60-1 |
| Tolyl glycidyl ether | Wuhan pulofu | 26447-14-3 |
| Cardanol glycidyl ether | Nantong Runfeng | 171263-25-5 |
| P-tert-butylphenyl glycidyl ether | Wuhan pulofu | 3101-60-8 |
| Nonyl phenyl glycidyl ether | Guanao province in Hubei province | 6178-32-1 |
| Methoxy polyethylene glycol monoglycidyl ether | Kelong Liaoning medicine | 2224-15-9 |
The test method is as follows:
the impact resistance of the paint film refers to GB/T1732 'determination method for impact resistance of paint film';
the hardness of the swing rod refers to GB/T1730 pendulum rod damping test for paint film hardness determination method;
the adhesion refers to GB/T9286 test for marking out paint films of colored paint and varnish;
the water resistance refers to GB/T1733 'determination method for water resistance of paint film';
the salt fog resistance is referred to GB/T1765 "paint film preparation method for determining humidity and heat resistance, salt fog resistance and weather resistance (artificial acceleration)".
Testing the thermal storage stability of the waterborne epoxy curing agent for 30 days: and (3) placing the sample to be tested in a constant-temperature oven at 50 ℃ and testing whether layering occurs within 30 days.
Amine number testing of waterborne epoxy curing agents: the test is carried out by a titration method, a sample to be tested is firstly dissolved in methanol, then a di-n-butylamine-chlorobenzene solution is added into the methanol, potentiometric titration is carried out by using a hydrochloric acid standard solution until mutation occurs, blank titration is carried out by using the same method, and the finally obtained result is calculated by the mass of KOH equivalent to the sample, and the unit is mg KOH/g.
Infrared spectrum test: in the reaction process of preparing the waterborne epoxy curing agent, sampling is carried out from a reaction system and the sample is taken as a sample to be detected; then, a Fourier infrared spectrometer is used for measuring a sample to be measured until the sample to be measured is 913cm-1The peak of the wavenumber (epoxy group) was not observed, and the reaction was considered complete.
Nuclear magnetic testing: in the reaction process of preparing the waterborne epoxy curing agent, sampling is carried out from a reaction system and the sample is taken as a sample to be detected; and then dissolving the sample to be detected by using a deuterated reagent, and then performing hydrogen spectrum analysis on the dissolved sample to be detected by using nuclear magnetism, wherein the hydrogen of the epoxy group has an absorption peak at about 4.3 chemical shift until the signal peak disappears completely, and the reaction is considered to be complete.
In the following examples and comparative examples, the reaction end point of the aqueous epoxy curing agent in the preparation process was judged by the comprehensive consideration of the infrared spectrum and the nuclear magnetism, that is, when both the test means show that the signal peak of the epoxy group disappears, the reaction end point of the aqueous epoxy curing agent in the preparation process can be judged.
[ PREPARATION EXAMPLE 1 ]
And (3) injecting 100g of dimer acid into the kettle, then injecting 135g of epoxy resin E51, uniformly stirring, adding a catalyst triphenylphosphine, reacting at the constant temperature of 100 ℃ for 3 hours, and discharging to obtain the toughened epoxy resin A1. Wherein the molar ratio n1 of the total amount of epoxy groups in the epoxy resin to the total amount of carboxyl groups in the dimer acid is 2: 1.
[ preparative examples 2 to 4 ]
Toughened epoxy resins, designated as a2 and A3, a4, were prepared according to the method of preparative example 1, respectively, with the reaction conditions shown in table 2:
TABLE 2 preparation of the different reaction conditions of examples 1 to 4
[ EXAMPLE 1 ] (i.e., S1)
The aqueous epoxy curing agent was prepared according to the following procedure:
step A, adding 80g of epoxy resin E51 and 20g of toughened epoxy resin A1 into a beaker, uniformly stirring, adding 300g of isophorone diamine into a reaction bottle, and preheating the temperature to 80 ℃; gradually dripping the resin components into a reaction bottle through a peristaltic pump for ring-opening reaction, wherein the dripping time is 2 hours, and continuously preserving heat for 1 hour after the dripping is finished; and then, carrying out reduced pressure distillation on the materials in the reaction bottle by using a vacuum pump, and removing redundant isophorone diamine in the reaction system.
And step B, adding 35g of propylene glycol methyl ether into the system, gradually dripping 52g of butyl glycidyl ether and 80g of methoxypolyethylene glycol monoglycidyl ether (450 molecular weight) into a reaction bottle by using a peristaltic pump for reaction, wherein the dripping time is 1h, and continuously preserving heat for 1h after the dripping is finished.
And C, after the reaction is finished, adding deionized water into the mixture, uniformly stirring and mixing the mixture, and discharging the mixture to obtain the water-based epoxy curing agent C1, wherein the solid content is 45 wt%, the amine value is 170mgKOH/g, and the pH value is 9.5.
Examples 2-6, comparative examples 1-3 (i.e., S2-S6, D1-D3)
Waterborne epoxy curing agents C2-C6 and C1 '-C3' were prepared according to the method of example 1 and are identified as examples 2-6 and comparative examples 1-3, respectively. The substances and amounts used in examples 2 to 6 are shown in Table 3, the substances and amounts used in comparative examples 1 to 3 are shown in Table 4, the reaction conditions in the respective steps in examples 2 to 6 and comparative examples 1 to 3 are shown in Table 5, and the relevant parameters of the obtained aqueous epoxy curing agent are shown in Table 6.
Materials and amounts shown in tables 3 and S1-S6
Materials and amounts shown in tables 4 and D1-D3
Reaction conditions for the steps in tables 5, S1-S6 and D1-D3 and the resulting products
TABLE 6 relevant parameters for waterborne epoxy hardeners prepared in the examples and comparative examples
And (3) performance testing:
the aqueous epoxy curing agents C1-C6 and C1 '-C3' prepared in examples 1 to 6 and comparative examples 1 to 3 were mixed with the aqueous epoxy emulsion to prepare paint films, in which the formulations of the A component and the B component used for preparing the paint films are shown in tables 7 and 8 below.
TABLE 7 formulation of the A component of the paint film
TABLE 7 formulation of the B component of the paint film
| Composition of | Suppliers of goods | Mass dispersion wt% |
| H2O | / | 30 |
| Ethylene glycol butyl ether | Chemistry of Dow | 30 |
| Aqueous epoxy curing agent | 40 | |
| Total up to | 100 |
Mixing the component A obtained according to the table 1 with the component B obtained according to the table 2 according to the mass ratio of 10:1, stirring for 15min, adding a small amount of deionized water to adjust the construction viscosity (the viscosity of a coating 4 cup is 20-50s, namely a sample flows down from the coating 4 cup within 20-50 s), and preparing a mixed paint liquid; and then, preparing the mixed paint liquid into a board according to the industrial operation standard (flash drying leveling is carried out for 10min, and baking is carried out for 30min at 80 ℃) to obtain paint films Q1-Q6 and Q1 '-Q3'. Standing and curing each paint film for 7d under the standard conditions of 23 +/-2 ℃ and 50 +/-5% of humidity, and then carrying out various tests according to corresponding test methods.
The resulting films were tested according to the test methods described above and the results of the performance tests are shown in Table 9.
TABLE 9 Performance of waterborne epoxy curatives C1-C6 and C1 ' -C3 ' and paint films Q1-Q6 and Q1 ' -Q3
Each test is executed according to the national standard, and the specific test method is shown in the test method part; tolerance data are test results after 20 days of follow-up.
Wherein, the grade of the adhesion test result is 0-5 grade, the 0 grade adhesion is optimal, and the 5 grade is worst;
the grade of the water resistance test result is 0-5 grade, the 5 grade is optimal, and the 0 grade is worst;
the grade of the salt spray resistance test result is 0-5 grade, 5 grade is optimal, and 0 grade is worst.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. The toughening type waterborne epoxy curing agent is characterized by being prepared from the following raw materials in parts by weight:
2. the toughening type aqueous epoxy hardener of claim 1, wherein the epoxy resin is selected from one or more of an aliphatic epoxy resin and an aromatic epoxy resin;
preferably, the polyamine compound is one or more of aliphatic polyamine, alicyclic polyamine and aromatic polyamine;
preferably, the toughening epoxy resin is dimer acid addition modified epoxy resin, and has at least 2 epoxy groups;
preferably, the monoepoxy reactive diluent is any one or more of epoxy ethers of phenols, epoxy esters of unsaturated alcohols, epoxy esters of unsaturated carboxylic acids, aliphatic glycidyl ethers, and aromatic glycidyl ethers;
preferably, the alkyl polyethylene glycol monoglycidyl ether has a structural expression shown in formula I; in the formula I, R is selected from H or C1-C12 alkyl, preferably H or C1-C4 alkyl; n is an integer of 5 or more, preferably n is an integer of 11 to 180;
3. the toughening type waterborne epoxy curing agent of claim 2, wherein the toughening type epoxy resin has an average molecular weight of 350-.
4. A method for preparing the toughening type aqueous epoxy hardener according to any one of claims 1 to 3, comprising the steps of:
1) blending epoxy resin and toughened epoxy resin to obtain an epoxy composition;
2) dripping the epoxy composition into a polyamine compound for reaction, and preserving heat for 0.5-3h after dripping is finished; distilling under reduced pressure to remove excessive polyamine compound to obtain intermediate;
3) optionally, in the presence of a solvent or water, dropwise adding a monoepoxy reactive diluent and alkyl polyethylene glycol monoglycidyl ether into the intermediate for end-capping reaction, and preserving heat for 0.5-3h after the dropwise adding is finished to obtain an end-capped product;
4) and adding water into the end-capped product, and mixing to prepare the curing agent.
5. The preparation method of the toughening type waterborne epoxy curing agent according to claim 4, wherein the reaction temperature in the step 2) is 60-120 ℃;
preferably, the dropping time of the epoxy composition is 0.5 to 5 hours.
6. The preparation method of the toughening type waterborne epoxy curing agent according to claim 4, wherein the reaction temperature in the step 3) is 60-120 ℃;
preferably, the dropping time of the monoepoxy reactive diluent and the alkyl polyethylene glycol monoglycidyl ether is 0.5 to 4 hours.
7. The preparation method of the toughening type waterborne epoxy curing agent according to claim 4, wherein the water is added in the step 4) until the solid content of the curing agent is 40-80%.
8. The preparation method of the toughening type waterborne epoxy curing agent according to any one of claims 4 to 7, wherein the preparation method of the toughening type epoxy resin comprises the following steps: the dimer acid and the epoxy resin are reacted under the condition of a catalyst, the reaction temperature is 120-150 ℃, preferably 130-140 ℃, and the reaction time is 2-5h, preferably 1-3 h.
9. The preparation method of the toughening type waterborne epoxy hardener as claimed in claim 8, wherein in the preparation method of the toughening type epoxy resin, the raw materials are used in amounts: the molar ratio of the total amount of epoxy groups in the epoxy resin to the total amount of carboxyl groups in the dimer acid is (2-100) to 1, preferably (2-10) to 1;
preferably, the catalyst is one or more of triphenylphosphine, tetrabutylammonium bromide, triphenylphosphine and boron trifluoride diethyl etherate; more preferably, the amount of the catalyst is 0.05 to 1% of the total mass of the raw materials.
10. The toughening type water-based epoxy curing agent as claimed in claims 1 to 3 and the application of the toughening type water-based epoxy curing agent prepared by the method as claimed in claims 4 to 9 in preparing epoxy resin paint.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110711545.3A CN113214455B (en) | 2021-06-25 | 2021-06-25 | Toughening type water-based epoxy curing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110711545.3A CN113214455B (en) | 2021-06-25 | 2021-06-25 | Toughening type water-based epoxy curing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113214455A true CN113214455A (en) | 2021-08-06 |
| CN113214455B CN113214455B (en) | 2022-04-22 |
Family
ID=77081407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110711545.3A Active CN113214455B (en) | 2021-06-25 | 2021-06-25 | Toughening type water-based epoxy curing agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113214455B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980248A (en) * | 2021-10-22 | 2022-01-28 | 江苏扬农锦湖化工有限公司 | Water-based epoxy curing agent and preparation method and application thereof |
| CN114031748A (en) * | 2021-11-15 | 2022-02-11 | 康达新材料(集团)股份有限公司 | Low-viscosity water-based epoxy curing agent and preparation method thereof |
| CN115073713A (en) * | 2022-07-22 | 2022-09-20 | 安徽衡光新材料科技有限公司 | Waterborne toughening epoxy curing agent, preparation method and waterborne epoxy composition prepared from waterborne toughening epoxy curing agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999029756A1 (en) * | 1997-12-09 | 1999-06-17 | Kansai Paint Co., Ltd. | Amine-base curing agent, curable resin composition containing said agent, and corrosionproofing coating composition containing said agent |
| CN103113716A (en) * | 2013-01-28 | 2013-05-22 | 北京化工大学常州先进材料研究院 | Preparation method of dimer acid modified epoxy resin toughened carbon fiber prepreg |
| CN103408726A (en) * | 2013-07-31 | 2013-11-27 | 江苏博特新材料有限公司 | Toughening epoxy resin curing agent and preparation method and application thereof |
| CN108084404A (en) * | 2017-01-06 | 2018-05-29 | 上海拓径新材料科技股份有限公司 | A kind of high-toughness epoxy resin curing agent and preparation method thereof |
| CN113004495A (en) * | 2019-12-20 | 2021-06-22 | 万华化学集团股份有限公司 | Nonionic waterborne epoxy curing agent and preparation method and application thereof |
-
2021
- 2021-06-25 CN CN202110711545.3A patent/CN113214455B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999029756A1 (en) * | 1997-12-09 | 1999-06-17 | Kansai Paint Co., Ltd. | Amine-base curing agent, curable resin composition containing said agent, and corrosionproofing coating composition containing said agent |
| CN103113716A (en) * | 2013-01-28 | 2013-05-22 | 北京化工大学常州先进材料研究院 | Preparation method of dimer acid modified epoxy resin toughened carbon fiber prepreg |
| CN103408726A (en) * | 2013-07-31 | 2013-11-27 | 江苏博特新材料有限公司 | Toughening epoxy resin curing agent and preparation method and application thereof |
| CN108084404A (en) * | 2017-01-06 | 2018-05-29 | 上海拓径新材料科技股份有限公司 | A kind of high-toughness epoxy resin curing agent and preparation method thereof |
| CN113004495A (en) * | 2019-12-20 | 2021-06-22 | 万华化学集团股份有限公司 | Nonionic waterborne epoxy curing agent and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113980248A (en) * | 2021-10-22 | 2022-01-28 | 江苏扬农锦湖化工有限公司 | Water-based epoxy curing agent and preparation method and application thereof |
| CN114031748A (en) * | 2021-11-15 | 2022-02-11 | 康达新材料(集团)股份有限公司 | Low-viscosity water-based epoxy curing agent and preparation method thereof |
| CN115073713A (en) * | 2022-07-22 | 2022-09-20 | 安徽衡光新材料科技有限公司 | Waterborne toughening epoxy curing agent, preparation method and waterborne epoxy composition prepared from waterborne toughening epoxy curing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113214455B (en) | 2022-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11597796B2 (en) | Ionic aqueous epoxy curing agent, preparation method therefor and use thereof | |
| CN113214455B (en) | Toughening type water-based epoxy curing agent and preparation method and application thereof | |
| US4886845A (en) | Stable aqueous epoxy resin dispersion, process for the preparation thereof and use thereof | |
| JP5325791B2 (en) | Epoxy resin containing alicyclic diamine curing agent | |
| JP2749876B2 (en) | Stable aqueous dispersion of epoxy resin, its production method and its use | |
| US7300963B2 (en) | Hardeners for water-based epoxy resin systems and processes for using the same | |
| TWI579314B (en) | Curing agent for epoxy coatings | |
| CN102037086A (en) | Epoxy resin reactive diluent compositions | |
| KR20150123795A (en) | Composition and method of making water borne epoxy hardener for use in two-component epoxy self levelling compounds with long pot life, fast cure and low shrinkage characteristics | |
| CN110511356A (en) | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof | |
| AU2011224629A1 (en) | Storage stable water based epoxy-amine curable systems | |
| CN114605616B (en) | Quick-drying nonionic water-based epoxy curing agent, and preparation method and application thereof | |
| CN113004495B (en) | Nonionic aqueous epoxy curing agent, and preparation method and application thereof | |
| CN109369888B (en) | Radiation-resistant self-emulsifying water-based epoxy curing agent | |
| JP2017508011A (en) | Epoxy resin composition | |
| CN112646124B (en) | Room-temperature quick-drying epoxy curing agent dispersoid and preparation method and application thereof | |
| CN114591492A (en) | Water-based epoxy curing agent and preparation method and application thereof | |
| CN113683754B (en) | Epoxy curing agent and preparation method and application thereof | |
| US20220290001A1 (en) | Self-emulsifying epoxy composition and the coating composition prepared from the same | |
| CN115975154A (en) | Flexible waterborne epoxy curing agent and preparation method and application thereof | |
| US20070003767A1 (en) | Hardeners for coating compositions (IV) | |
| CN117624554A (en) | Flexible aqueous epoxy curing agent and preparation method and application thereof | |
| WO2022006874A1 (en) | Epoxy-amine adduct |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |