CN113698578A - Preparation method and application of water-based cardanol epoxy curing agent - Google Patents
Preparation method and application of water-based cardanol epoxy curing agent Download PDFInfo
- Publication number
- CN113698578A CN113698578A CN202110891718.4A CN202110891718A CN113698578A CN 113698578 A CN113698578 A CN 113698578A CN 202110891718 A CN202110891718 A CN 202110891718A CN 113698578 A CN113698578 A CN 113698578A
- Authority
- CN
- China
- Prior art keywords
- cardanol
- curing agent
- water
- epoxy curing
- 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.)
- Pending
Links
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 title claims abstract description 79
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 79
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 76
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 68
- 239000004593 Epoxy Substances 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 239000013067 intermediate product Substances 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229920000768 polyamine Polymers 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 18
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 16
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003973 paint Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 6
- 229920006334 epoxy coating Polymers 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- -1 amine compounds Chemical class 0.000 claims description 4
- 229920006332 epoxy adhesive Polymers 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- SSOZBCCITNPUMJ-UHFFFAOYSA-N 1-methoxycyclohexan-1-ol Chemical compound COC1(O)CCCCC1 SSOZBCCITNPUMJ-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000006683 Mannich reaction Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
Images
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
- C08G59/62—Alcohols or phenols
-
- 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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4453—Polyepoxides characterised by the nature of the curing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method and application of a water-based cardanol epoxy curing agent, belonging to the field of water-based epoxy curing agents, and the technical scheme is as follows: the method comprises the following steps: s1, adding epoxy resin and organic monoamine into the reactor to react to obtain an intermediate product I; s2, cooling the intermediate product I to below 50 ℃, and adding cardanol into the intermediate product I; s3, adding mixed organic polyamine into S2 to react for 2h-6 h; s4, adding paraformaldehyde or formaldehyde into S3 in batches, stirring for 1h after the materials are added, and dehydrating at 90-150 ℃ to obtain a finished product, namely a transparent liquid, which is the reaction end point; and S5, cooling to 70 ℃, and adding a small amount of alcohol ether solvent and water into S4 to obtain the waterborne cardanol modified epoxy curing agent. The preparation method is mainly used for improving the performance of the waterborne cardanol epoxy curing agent, is environment-friendly and safe, has a simple process, can effectively relieve the pressure of three-waste treatment, and has the advantages of insensitivity to PH, good stability and no free amine.
Description
Technical Field
The invention relates to the field of waterborne epoxy curing agents, in particular to a preparation method and application of a waterborne cardanol epoxy curing agent.
Background
At present, in order to meet the environmental protection requirements of atmospheric pollution, low VOC (volatile organic compounds) emission and the like, the development and application of water-based materials are wider, and water-based epoxy coatings and adhesives are the most important products. The film-forming material of the water-based epoxy coating is composed of resin and a curing agent, and the performance of the curing agent plays an important role in the coating, so that the development of the high-performance water-based epoxy curing agent promotes the application development in the field of the water-based epoxy coating. The waterborne epoxy hardener is widely used in the anticorrosion fields of terraces, containers, ships, bridges, steel structures and the like.
Currently, most of the prior art waterborne epoxy curing agents are epoxy resin-amine adducts, such as CN101676316A discloses a preparation method of the waterborne epoxy curing agent. CN109517141A discloses a preparation method of a cardanol modified waterborne epoxy curing agent, which takes cardanol, polyethylene glycol and epichlorohydrin as raw materials to respectively synthesize polyethylene glycol diglycidyl ether and cardanol glycidyl, and then the waterborne epoxy curing agent is prepared by chain extension through epoxy-amine adduct addition reaction.
In order to solve the problems, the invention provides a preparation method and application of a water-based cardanol epoxy curing agent on the basis of the prior art.
Disclosure of Invention
The invention aims to provide a preparation method and application of a water-based cardanol epoxy curing agent, the water-based cardanol epoxy curing agent prepared by the preparation method disclosed by the invention is excellent in performance, low in volatile substance content, environment-friendly and safe, the preparation method is simple in process, and the pressure of three-waste treatment can be effectively relieved; meanwhile, the curing agent prepared by the preparation method is insensitive to PH, has good stability and does not contain free amine.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a water-based cardanol epoxy curing agent comprises the following steps:
s1, adding epoxy resin into the reactor, adding organic monoamine into the reactor within the temperature range of 15-100 ℃, and reacting for 1-6 h to obtain an intermediate product I;
s2, cooling the intermediate product I obtained in the step S1 to be below 50 ℃, adding cardanol into the intermediate product I, and uniformly mixing the intermediate product I and the cardanol to obtain a mixture of the intermediate product I and the cardanol;
s3, adding mixed organic polyamine into the mixture obtained in the step S2, and reacting for 2h-6h at the temperature of 30-90 ℃;
s4, starting cooling water, adding paraformaldehyde or formaldehyde into S3 in batches, wherein the feeding temperature is lower than 90 ℃, stirring for 1h, heating to 90-150 ℃ after the reaction temperature is stable, and dehydrating until the finished product becomes transparent liquid, namely the reaction end point, so as to obtain the finished product;
s5, when the temperature is cooled to be lower than 70 ℃ after the reaction is finished in the step S4, adding a small amount of alcohol ether solvent and water into the finished product in the step S4 to obtain the waterborne cardanol modified epoxy curing agent;
by adopting the technical scheme, the performance of the curing agent in application can be effectively improved, in application, curing agent molecules are firstly contacted with the surface of epoxy resin dispersion phase particles to generate a curing reaction, the molecular weight and the glass transition temperature of the epoxy resin dispersion phase are gradually increased along with the progress of the curing reaction, so that the diffusion speed of the curing agent molecules to the interior of the epoxy resin dispersion phase is gradually reduced, the difference of the curing degree between the interior and the surface of the epoxy resin is caused, and whether the epoxy resin coating can form a homogeneous and completely cured coating layer or not is possibly influenced; the epoxy resin and the organic monoamine are reacted to generate an intermediate product, so that a nonpolar group is introduced into a molecular chain of a final product, the finally prepared waterborne cardanol modified epoxy curing agent has an amphiphilic structure, the compatibility of the curing agent and the epoxy resin can be effectively improved, the crosslinking density of an epoxy cured material can be increased, and the coating performance of the curing agent in application can be improved.
Adding cardanol, organic polyamine and paraformaldehyde into the intermediate product, wherein ortho-position hydrogen in a benzene ring of the cardanol can be influenced by phenolic hydroxyl in the cardanol, so that hydrogen adjacent to the phenolic hydroxyl becomes more active, the cardanol amine with a long aliphatic hydrocarbon chain is prepared through a Mannich reaction, and the long chain substituted by hydrocarbon on the benzene ring has better hydrophobicity and flexibility so as to obtain better flexibility, water resistance, corrosion resistance and adhesive force; the alcohol ether solvent and water are utilized, so that the viscosity and solid content of the waterborne cardanol modified epoxy curing agent can be adjusted, and the waterborne cardanol modified epoxy curing agent is convenient to use.
By adopting the scheme, the water-based cardanol epoxy curing agent with excellent performance can be prepared, the content of volatile substances is low, the environment is protected, the safety is realized, the preparation method is simple in process, and the pressure of three-waste treatment can be effectively relieved; meanwhile, the curing agent prepared by the preparation method is insensitive to PH, has good stability and does not contain free amine.
Further, in step S1, the epoxy value of the epoxy resin is 0.06-0.75; the purity of the cardanol is 85-98%; the purity of the paraformaldehyde is more than or equal to 92; the equivalent weight of active hydrogen of the mixed organic polyamine is more than or equal to 22; the organic monoamine is RNHR1Wherein R represents CH3(CH2)nO-，n＝1-30，R1Represents CH3(CH2)n1O-or H, n1 ═ 1 to 30.
By adopting the technical scheme, the amount of the epoxy resin, the cardanol, the paraformaldehyde and the mixed organic polyamine which are required to be added can be calculated conveniently according to actual requirements, so that the waterborne cardanol modified epoxy curing agent with better performances in all aspects can be obtained.
Further, in step S1, the mass ratio of the epoxy resin to the organic monoamine is 100: 5-50.
By adopting the technical scheme, the molecular chains of the epoxy resin are introduced in a certain proportion, so that the finally prepared waterborne cardanol modified epoxy curing agent has an amphiphilic structure, the compatibility of the curing agent and the epoxy resin is improved conveniently, meanwhile, in the reaction process, the number of primary amines is reduced, the activity of the curing agent is reduced, the service life of the curing agent can be prolonged, and the balance between the compatibility and the activity of the curing agent is kept conveniently by controlling the proportion.
Further, the mass ratio of the cardanol to the reactant in the S1 is 100: 100-; the mixed organic polyamine comprises ethylenediamine, diethylenetriamine, triethylenetetramine, m-xylylenediamine, hexamethylenediamine, isophorone diamine, hydrogenated m-xylylenediamine and polyether amine, and the mass ratio of the mixed organic polyamine to the mixture in the step S2 is 100: 10-100 parts of; the mass ratio of the paraformaldehyde to the reactant in the step S3 is 1: 5-30.
By adopting the technical scheme, the proportion of cardanol, organic polyamine and paraformaldehyde is adjusted, the content of groups which can participate in a crosslinking reaction in the waterborne cardanol modified epoxy curing agent can be adjusted according to actual needs, and the hydrophobicity, flexibility, water resistance, corrosion resistance and adhesive force can be adjusted.
Further, the alcohol ether solvent is ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol butyl ether, cyclohexanediol monomethyl ether or diethylene glycol monomethyl ether; the mass ratio of the reactant of the step S4 to the cosolvent and the water is 100: 5-50: 10-150; in step S5, the solid content of the finished product of the waterborne cardanol modified epoxy curing agent is 40-87%.
By adopting the technical scheme, the alcohol ether solvent is utilized to help to adjust the viscosity and solid content of the finished product of the waterborne cardanol modified epoxy curing agent, and the waterborne cardanol modified epoxy curing agent is convenient to use in production.
Further, the mass percentages of the epoxy resin, the cardanol, the amine compound, the paraformaldehyde, the alcohol ether solvent and the water in the water-based cardanol epoxy curing agent are 4-25: 10-50: 5-30: 5-20: 5-20: 10-30.
The invention also provides an application of the preparation method of the waterborne cardanol epoxy curing agent, and the preparation method of the waterborne cardanol epoxy curing agent is applied to preparation of waterborne epoxy coating, waterborne epoxy adhesive, electrophoretic paint, epoxy anticorrosive paint and high-temperature baking paint for electronic or electric products.
In conclusion, the invention has the following beneficial effects: 1. the waterborne cardanol epoxy curing agent prepared by the preparation method disclosed by the invention is excellent in performance, low in volatile substance content, environment-friendly and safe, and simple in preparation method process, and can effectively relieve the pressure of three-waste treatment;
2. the curing agent prepared by the preparation method disclosed by the invention is insensitive to PH, good in stability and free of free amine.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following figures and embodiments:
example 1: a preparation method of a water-based cardanol epoxy curing agent comprises the following steps:
s1, adding epoxy resin into the reactor, wherein the epoxy value of the epoxy resin is 0.06-0.075, adding organic monoamine into the reactor at about 25 ℃, the mass ratio of the epoxy resin to the organic monoamine is 100:10, reacting for 2h to obtain an intermediate product I, and reacting the epoxy resin and the organic monoamine to generate the intermediate product, so that a nonpolar group is introduced into a molecular chain of a final product, and the finally prepared waterborne cardanol modified epoxy curing agent has an amphiphilic structure, can effectively improve the compatibility of the curing agent and the epoxy resin, can increase the crosslinking density of an epoxy cured substance, and can improve the coating performance of the curing agent in application.
S2, cooling the intermediate product obtained in the step S1 to below 50 ℃, adding cardanol into the intermediate product, wherein the mass ratio of the cardanol to the reactant in the S1 is 100: 200, the purity of the cardanol is 92%, and the intermediate product I and the cardanol are uniformly mixed to obtain a mixture of the intermediate product I and the cardanol.
S3, adding mixed polyamine such as ethylenediamine, diethylenetriamine, triethylenetetramine, m-xylylenediamine, hexamethylenediamine, isophorone diamine, hydrogenated m-xylylenediamine and polyether amine into the mixture in the step S2, wherein the mass ratio of the mixed organic polyamine to the reactant in the step S2 is 100: 20; the equivalent of active hydrogen of the mixed organic polyamine is more than 22, the reaction lasts for 2 hours, and the reaction temperature is controlled to be about 40 ℃.
S4, starting cooling water, and adding paraformaldehyde into S3 in batches, wherein the purity of the paraformaldehyde is 94%, and the mass ratio of the paraformaldehyde to reactants in S3 is 1: 10; and (3) the feeding temperature is lower than 90 ℃, stirring is continued for 1h after the feeding is finished, the reaction temperature is heated to 100 ℃ after being stabilized, and dehydration is carried out until the finished product becomes transparent liquid, namely the reaction end point, so as to obtain the finished product.
The cardanol, the organic polyamine and the paraformaldehyde are added into the intermediate product, because the phenolic hydroxyl in the cardanol can influence the ortho-position hydrogen in the benzene ring, the hydrogen adjacent to the phenolic hydroxyl becomes more active, the cardanol amine with a long aliphatic hydrocarbon chain is prepared through a Mannich reaction, and the long chain substituted by the hydrocarbon group on the benzene ring has better hydrophobicity and flexibility, so that better flexibility, water resistance, corrosion resistance and adhesive force can be obtained.
S5, when the temperature is cooled to be lower than 70 ℃ after the reaction is finished in the step S4, adding a small amount of ethylene glycol monobutyl ether and water into the finished product in the step S4 to obtain the waterborne cardanol modified epoxy curing agent, and the viscosity and the solid content of the waterborne cardanol modified epoxy curing agent can be adjusted by utilizing the alcohol ether solvent and the water, so that the waterborne cardanol modified epoxy curing agent is convenient to use.
The qualified detection conditions of the finished product of the waterborne cardanol epoxy curing agent prepared in the step S5 are as follows: viscosity (25 deg.C) lower than 50000CPS, solid content higher than 40%, amine value higher than 120, and HLB value of 6-9.
Example 2: the difference from example 1 is that: the temperature of the added organic monoamine is 40 ℃, and the mass ratio of the epoxy resin to the organic monoamine is 100: 20; the mass ratio of cardanol to the reactant in S1 is 100: 400, respectively; the mass ratio of the mixed organic polyamine to the reactant in the S2 is 100:40, controlling the reaction temperature of S3 to be about 50 ℃; the mass ratio of the polyformaldehyde to the reactant in the S3 is 1: 15.
example 3: the difference from example 1 is that: the temperature of the added organic monoamine is 60 ℃, and the mass ratio of the epoxy resin to the organic monoamine is 100: 30; the mass ratio of cardanol to the reactant in S1 is 100: 600, preparing a mixture; the mass ratio of the mixed organic polyamine to the reactant in the S2 is 100: 60, controlling the reaction temperature of S3 to be about 60 ℃; the mass ratio of the polyformaldehyde to the reactant in the S3 is 1: 20.
example 4: the difference from example 1 is that: the temperature of the added organic monoamine is 80 ℃, the mass ratio of the epoxy resin to the organic monoamine is 100:40, and the mass ratio of the cardanol to the reactant in S1 is 100: 800; the mass ratio of the mixed organic polyamine to the reactant in the S2 is 100: 80, controlling the reaction temperature of S3 to be about 70 ℃; the mass ratio of the polyformaldehyde to the reactant in the S3 is 1: 25.
example 5: the difference from example 1 is that: the temperature of the added organic monoamine is 100 ℃, and the mass ratio of the epoxy resin to the organic monoamine is 100: 50; the mass ratio of cardanol to the reactant in S1 is 100: 1000, parts by weight; the mass ratio of the mixed organic polyamine to the reactant in the S2 is 100: 100, controlling the reaction temperature of S3 to be about 80 ℃; the mass ratio of the polyformaldehyde to the reactant in the S3 is 1: 30.
the above embodiments of the invention have application in: the water-based cardanol epoxy curing agent prepared by the preparation method is applied to preparation of water-based epoxy coating, water-based epoxy adhesive, electrophoretic paint, epoxy anticorrosive paint and high-temperature baking paint for electronic or electric products.
In the embodiment of the invention, the waterborne cardanol epoxy curing agent prepared by the preparation method disclosed by the invention is excellent in performance, low in volatile substance content, environment-friendly, safe and simple in process, and can effectively relieve the pressure of three-waste treatment.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (7)
1. A preparation method of a water-based cardanol epoxy curing agent is characterized by comprising the following steps:
s1, adding epoxy resin into the reactor, adding organic monoamine into the reactor within the temperature range of 15-100 ℃, and reacting for 1-6 h to obtain an intermediate product I;
s2, cooling the intermediate product I obtained in the step S1 to be below 50 ℃, adding cardanol into the intermediate product I, and uniformly mixing the intermediate product I and the cardanol to obtain a mixture of the intermediate product I and the cardanol;
s3, adding mixed organic polyamine into the mixture obtained in the step S2, and reacting for 2h-6h at the temperature of 30-90 ℃;
s4, starting cooling water, adding paraformaldehyde or formaldehyde into S3 in batches, wherein the feeding temperature is lower than 90 ℃, stirring for 1h, heating to 90-150 ℃ after the reaction temperature is stable, and dehydrating until the finished product becomes transparent liquid, namely the reaction end point, so as to obtain the finished product;
s5, when the temperature is cooled to be lower than 70 ℃ after the reaction is finished in the step S4, adding a small amount of alcohol ether solvent and water into the finished product in the step S4 to obtain the waterborne cardanol modified epoxy curing agent.
2. The preparation method of the water-based cardanol epoxy curing agent as claimed in claim 1, characterized in that: in step S1, the epoxy value of the epoxy resin is 0.06-0.75; the purity of the cardanol is 85-98%; the purity of the paraformaldehyde is more than or equal to 92; the equivalent weight of active hydrogen of the mixed organic polyamine is more than or equal to 22; the organic monoamine is RNHR1Wherein R represents CH3(CH2)nO-，n＝1-30，R1Represents CH3(CH2)n1O-or H, n1 ═ 1 to 30.
3. The preparation method of the water-based cardanol epoxy curing agent as claimed in claim 1, characterized in that: in the step S1, the mass ratio of the epoxy resin to the organic monoamine is 100: 5-50.
4. The preparation method of the water-based cardanol epoxy curing agent as claimed in claim 1, characterized in that: the mass ratio of the cardanol to the reactant in the S1 is 100: 100-; the mixed organic polyamine comprises ethylenediamine, diethylenetriamine, triethylenetetramine, m-xylylenediamine, hexamethylenediamine, isophorone diamine, hydrogenated m-xylylenediamine and polyether amine, and the mass ratio of the mixed organic polyamine to the mixture in the step S2 is 100: 10-100 parts of; the mass ratio of the paraformaldehyde to the reactant in the step S3 is 1: 5-30.
5. The preparation method of the water-based cardanol epoxy curing agent as claimed in claim 1, characterized in that: the alcohol ether solvent is ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol butyl ether, cyclohexanediol monomethyl ether or diethylene glycol monomethyl ether; the mass ratio of the reactant of the step S4 to the cosolvent and the water is 100: 5-50: 10-150; in step S5, the solid content of the finished product of the waterborne cardanol modified epoxy curing agent is 40-87%.
6. The preparation method of the water-based cardanol epoxy curing agent as claimed in claim 1, characterized in that: the mass percentages of epoxy resin, cardanol, amine compounds, paraformaldehyde, alcohol ether solvent and water in the waterborne cardanol epoxy curing agent are 4-25: 10-50: 5-30: 5-20: 5-20: 10-30.
7. The application of the preparation method of the water-based cardanol epoxy curing agent according to any one of claims 1 to 6, characterized in that: the waterborne cardanol epoxy curing agent prepared by the preparation method of the waterborne cardanol epoxy curing agent is applied to preparation of waterborne epoxy coating, waterborne epoxy adhesive, electrophoretic paint, epoxy anticorrosive paint and high-temperature baking paint for electronic or electric products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110891718.4A CN113698578A (en) | 2021-08-04 | 2021-08-04 | Preparation method and application of water-based cardanol epoxy curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110891718.4A CN113698578A (en) | 2021-08-04 | 2021-08-04 | Preparation method and application of water-based cardanol epoxy curing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113698578A true CN113698578A (en) | 2021-11-26 |
Family
ID=78651529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110891718.4A Pending CN113698578A (en) | 2021-08-04 | 2021-08-04 | Preparation method and application of water-based cardanol epoxy curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113698578A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109370384A (en) * | 2018-10-30 | 2019-02-22 | 绵阳惠利环氧工程有限公司 | A kind of preparation method of self-emulsifying type non-ionic water epoxy hardener |
| CN110938209A (en) * | 2019-12-17 | 2020-03-31 | 岳阳中展科技有限公司 | Preparation method and application of cardanol-based waterborne epoxy resin curing agent |
| CN113072686A (en) * | 2021-05-06 | 2021-07-06 | 上海经天新材料科技有限公司 | Preparation method of aldehyde-free waterborne cardanol ketone amine epoxy curing agent |
-
2021
- 2021-08-04 CN CN202110891718.4A patent/CN113698578A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109370384A (en) * | 2018-10-30 | 2019-02-22 | 绵阳惠利环氧工程有限公司 | A kind of preparation method of self-emulsifying type non-ionic water epoxy hardener |
| CN110938209A (en) * | 2019-12-17 | 2020-03-31 | 岳阳中展科技有限公司 | Preparation method and application of cardanol-based waterborne epoxy resin curing agent |
| CN113072686A (en) * | 2021-05-06 | 2021-07-06 | 上海经天新材料科技有限公司 | Preparation method of aldehyde-free waterborne cardanol ketone amine epoxy curing agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR830001473B1 (en) | Method for preparing permeable polymer network composed of epoxy polymer and polysiloxane | |
| US6329473B1 (en) | Amine-modified epoxy resin composition | |
| US5688905A (en) | Primary-tertiary diamines mixed with polyamines as epoxy resin hardeners | |
| US20050113553A1 (en) | Hardeners for water-based epoxy resin systems and processes for using the same | |
| CN113980248A (en) | Water-based epoxy curing agent and preparation method and application thereof | |
| WO2013138994A1 (en) | A modified epoxy resin composition used in high solids coating | |
| CN104583266A (en) | Curable compositions based on epoxy resins without benzyl alcohol | |
| US5847027A (en) | Hardeners for elastic epoxy resin systems | |
| US9102829B2 (en) | Method of producing hybrid polyhydroxyurethane network on a base of carbonated-epoxidized unsaturated fatty acid triglycerides | |
| EP2718355A1 (en) | Water-based amine curing agents for curable resin systems | |
| CN103224612A (en) | Solvent-free self-leveling epoxy resin curing agent and preparation method thereof | |
| US5977286A (en) | Amine-modified epoxy resin reacted with polyisocyanate | |
| CN110511356A (en) | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof | |
| EP0786481B1 (en) | Reactive accelerators for amine cured epoxy resins | |
| JP2022145636A (en) | Water-based epoxy curing agent | |
| US5681907A (en) | Fast cure amines for ambient and subambient cure of epoxy resins comprising methylamine adducts | |
| EP0014207A4 (en) | Epoxy surfacer cements cured with polyamine-ketimine mixtures. | |
| CN110684178A (en) | Preparation and application method of nonionic waterborne epoxy curing agent | |
| CN115594825B (en) | Preparation method of isocyanate modified waterborne epoxy curing agent | |
| CN113698578A (en) | Preparation method and application of water-based cardanol epoxy curing agent | |
| CN114349935B (en) | Low-viscosity aqueous epoxy curing agent and preparation method thereof | |
| CN116284805A (en) | Nonionic water-based epoxy curing agent and preparation method and application thereof | |
| CN114591492B (en) | Water-based epoxy curing agent and preparation method and application thereof | |
| JPS6144918A (en) | Curable resin composition | |
| JPS5825323A (en) | Elasticized adduct based on polyalkylene ether-polyol and polyisocyanate and use |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211126 |