CN114149566A - Imidazoline epoxy curing agent and application thereof - Google Patents
Imidazoline epoxy curing agent and application thereof Download PDFInfo
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- CN114149566A CN114149566A CN202111565791.9A CN202111565791A CN114149566A CN 114149566 A CN114149566 A CN 114149566A CN 202111565791 A CN202111565791 A CN 202111565791A CN 114149566 A CN114149566 A CN 114149566A
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- epoxy
- imidazoline
- curing agent
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 61
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 32
- 239000000194 fatty acid Substances 0.000 claims abstract description 32
- 229930195729 fatty acid Natural products 0.000 claims abstract description 32
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 30
- 239000003607 modifier Substances 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- -1 alkyl glycidyl ether Chemical compound 0.000 claims description 11
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 8
- 239000004848 polyfunctional curative Substances 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000003784 tall oil Substances 0.000 claims description 5
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 3
- 230000007123 defense Effects 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 2
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000005303 weighing Methods 0.000 description 8
- 229960001124 trientine Drugs 0.000 description 6
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 5
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- MYIGUVWXDJBPEV-UHFFFAOYSA-N piperazin-2-amine Chemical compound NC1CNCCN1 MYIGUVWXDJBPEV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 150000004658 ketimines Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- WVJRIURRQOEQKL-UHFFFAOYSA-N 12-piperazin-1-yldodecan-1-amine Chemical compound NCCCCCCCCCCCCN1CCNCC1 WVJRIURRQOEQKL-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HOBMRXDCLMDRKJ-UHFFFAOYSA-N n,n-dimethylpiperazin-2-amine Chemical compound CN(C)C1CNCCN1 HOBMRXDCLMDRKJ-UHFFFAOYSA-N 0.000 description 1
- IYPZRUYMFDWKSS-UHFFFAOYSA-N piperazin-1-amine Chemical compound NN1CCNCC1 IYPZRUYMFDWKSS-UHFFFAOYSA-N 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an imidazoline epoxy curing agent, which comprises fatty acid, fatty amine, an epoxy modifier and an accelerant; the preparation process comprises the following steps: s1, mixing fatty acid and epoxy modifier uniformly, heating to 130-150 ℃, and stirring for reaction for 1-3 h; s2, adding fatty amine, heating to 170-190 ℃, and stirring for reaction for 2-3 h; s3, decompressing the mixture prepared in the step S2 to-0.095 to-0.085 MPa, heating to 220 ℃ and 250 ℃, and reacting for 4-6 h; s4, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the product. The product has low viscosity, is convenient to operate, can be quickly reacted and cured with resin, can be reacted with water on a wet surface without influencing the bonding property of the resin, has excellent water resistance and corrosion resistance, and is particularly suitable for being used in a wet environment.
Description
Technical Field
The invention relates to the technical field of epoxy curing agents, and particularly relates to an imidazoline epoxy curing agent and application thereof.
Background
Epoxy resin materials generally consist of two parts, namely resin and a curing agent, are important thermosetting materials, have the advantages of high bonding strength, low shrinkage, good stability, high mechanical strength, good processability and the like, and can be widely applied to the fields of machinery, electronics, civil engineering, buildings and the like as coatings, adhesives, infusions and the like. Unlike the mechanical and electronic fields, in the civil and architectural fields, the conditions encountered are more complex, many of which are in the case of wet surfaces, in addition to the normal dry surfaces, and thus require epoxy materials that can be used in special conditions. The curing agent is decisive for the processing of the epoxy resin material and the final properties of the cured product.
The wet surface curing agent used in the prior art is mainly a ketimine curing agent or a Mannich base curing agent, which have advantages and disadvantages, wherein the ketimine curing agent has slow reaction time, high required temperature and long curing time; the Mannich base curing agent has a plurality of groups with high hydrophobicity and high activity in the structure, so that the Mannich base curing agent can show excellent curing performance in environments such as low temperature, humidity and the like, but most of the Mannich base curing agent has high viscosity and large smell, and is inconvenient for subsequent actual operation.
Therefore, many schemes adopting physical compounding are provided in the market, different curing agents are simply mixed, and due to different properties of the curing agents, a solvent is sometimes required to be additionally added to reduce the viscosity of the whole system, and an additive is sometimes required to be additionally added to promote solubilization.
Disclosure of Invention
In order to solve the problems that the prior curing agent used in a humid environment is purely and physically compounded by different components, the product quality is unstable, local instability occurs after curing, and environmental pollution is caused by using a solvent and various additives, the invention aims to provide the imidazoline epoxy curing agent which has low viscosity, is convenient to operate, can be quickly reacted and cured with resin, can be reacted with water on a humid surface without influencing the bonding property, has excellent water resistance and corrosion resistance, and is particularly suitable for being used in the humid environment. In addition, the invention also provides application of the imidazoline epoxy curing agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an imidazoline epoxy curing agent, which comprises the following components in parts by weight: 42-47 parts of fatty acid, 41-51 parts of fatty amine, 10-15 parts of epoxy modifier and 0.5-2 parts of accelerator;
the preparation process of the imidazoline epoxy curing agent is as follows:
s1, mixing fatty acid and epoxy modifier uniformly, heating to 130-150 ℃, and stirring for reaction for 1-3 h;
s2, adding fatty amine, heating to 170-190 ℃, and stirring for reaction for 2-3 h;
s3, decompressing the mixture prepared in the step S2 to-0.095 to-0.085 MPa, heating to 220 ℃ and 250 ℃, and reacting for 4-6 h;
s4, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
Specifically, in the step S3, the mixture prepared in the step S2 is decompressed to-0.092 to-0.090 MPa and heated to 230 ℃ and 240 ℃.
Specifically, in step S2, after the fatty amine is added, the temperature is raised to 180-190 ℃.
Specifically, the fatty acid is one or more of C16-C20 higher fatty acid, oleic acid, linoleic acid, abietic acid and tall oil.
Specifically, the aliphatic amine is one or a mixture of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
Specifically, the epoxy modifier is one or a mixture of two of C12-C14 alkyl glycidyl ether, 1, 4-butanediol diglycidyl ether, o-cresol glycidyl ether and trimethylolpropane triglycidyl ether.
Specifically, the accelerator is one or more of 2,4,6 tri- (dimethylaminomethyl) phenol and piperazine compounds. The piperazine compound is preferably an aminopiperazine compound, and further, 1- (12-aminododecyl) piperazine, 1-aminopiperazine, 2-aminopiperazine, 3-dimethylaminopiperazine, and the like can be selected.
In a second aspect of the invention, an application of the imidazoline epoxy curing agent is provided, wherein the imidazoline epoxy curing agent is mixed with epoxy resin to obtain the epoxy resin adhesive suitable for treating the defects of the damp environment of buildings such as cofferdam concrete pouring, chemical grouting, dams, tunnels, water pipes, pools, aqueducts, civil air defense engineering and the like. When in use, the dosage ratio of the amido amine epoxy curing agent to the epoxy resin is 2: (2-7).
Compared with the prior art, the invention has the following beneficial effects:
(1) the imidazoline epoxy curing agent is prepared by compounding fatty acid, fatty amine, an epoxy modifier and an accelerant, wherein the fatty acid and the fatty amine are subjected to amidation reaction at a certain temperature and then subjected to cyclodehydration under the condition of reduced pressure and high temperature, so that the prepared imidazoline epoxy curing agent not only retains the flexible structure of the amide curing agent and has a certain flexible function, meanwhile, the curing agent has an imidazoline ring structure and has certain corrosion inhibition resistance, and the imidazoline epoxy curing agent contains hydrophilic groups and hydrophobic groups, the hydrophilic group can perform addition reaction with water molecules on a wet surface, and can also perform chemical adsorption with the surfaces of various metals, cement and the like to enhance the adhesive force, the hydrophobic group can form a hydrophobic layer on the surfaces of different media, so that the contact and the erosion of moisture are effectively prevented or isolated, and the effect of isolating the moisture inside and outside is achieved;
(2) the finally prepared product has uniform performance, and the situation that a solvent and other substances are required to be added for solubilization or the product performance is not uniform in a simple compounding process can not occur;
(3) the product does not contain solvent, and does not pollute the environment;
(4) after the product is mixed with epoxy resin and used for a wet surface, the adhesive capacity is strong, the product is not easy to fall off, and the conditions of degumming, obvious strength reduction, whitening and the like can not occur in use;
(5) the product preparation process is simple, does not need a special production device, and is suitable for large-scale production.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Example 1
The preparation method of the imidazoline epoxy curing agent comprises the following steps:
s1, weighing 46 parts of fatty acid (oleic acid and linoleic acid in a weight ratio of 1: 1), 45 parts of fatty amine (triethylene tetramine), 15 parts of epoxy modifier (C12-C14 alkyl glycidyl ether) and 0.5 part of accelerator (2,4,6 tri- (dimethylaminomethyl) phenol);
s2, uniformly mixing the fatty acid and the epoxy modifier, heating to 140 ℃, and stirring for reacting for 2 hours;
s3, adding fatty amine, heating to 180 ℃, and stirring for reacting for 2 hours;
s4, decompressing the mixture prepared in the step S2 to-0.09 MPa, heating to 220 ℃, and reacting for 4 hours;
s5, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
Example 2
The preparation method of the imidazoline epoxy curing agent comprises the following steps:
s1, weighing 43 parts of fatty acid (C16-C20 higher fatty acid), 41 parts of fatty amine (diethylenetriamine and tetraethylenepentamine in a weight ratio of 1: 1), 12 parts of epoxy modifier (trimethylolpropane triglycidyl ether) and 1 part of accelerator (2,4,6 tri- (dimethylaminomethyl) phenol);
s2, uniformly mixing the fatty acid and the epoxy modifier, heating to 130 ℃, and stirring for reacting for 1 h;
s3, adding fatty amine, heating to 170 ℃, and stirring for reacting for 2 hours;
s4, decompressing the mixture prepared in the step S2 to-0.092 MPa, heating to 240 ℃, and reacting for 4 h;
s5, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
Example 3
The preparation method of the imidazoline epoxy curing agent comprises the following steps:
s1, weighing 45 parts of fatty acid (the weight ratio of C16-C20 higher fatty acid to abietic acid to tall oil is 1: 1: 1), 42 parts of fatty amine (triethylene tetramine), 10 parts of epoxy modifier (C12-C14 alkyl glycidyl ether) and 1 part of accelerator (3-dimethyl amino piperazine);
s2, uniformly mixing the fatty acid and the epoxy modifier, heating to 150 ℃, and stirring for reacting for 1 h;
s3, adding fatty amine, heating to 190 ℃, and stirring for reacting for 1 h;
s4, decompressing the mixture prepared in the step S2 to-0.088 MPa, heating to 250 ℃, and reacting for 4 hours;
s5, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
Example 4
The preparation method of the imidazoline epoxy curing agent comprises the following steps:
s1, weighing 47 parts of fatty acid (the weight ratio of abietic acid to oleic acid is 2: 1), 51 parts of fatty amine (the weight ratio of diethylenetriamine to pentavinyl hexamine is 2: 1), 15 parts of epoxy modifier (C12-C14 alkyl glycidyl ether) and 2 parts of accelerator (2,4,6 tri- (dimethylaminomethyl) phenol);
s2, uniformly mixing the fatty acid and the epoxy modifier, heating to 140 ℃, and stirring for reacting for 1 h;
s3, adding fatty amine, heating to 180 ℃, and stirring for reacting for 2 hours;
s4, decompressing the mixture prepared in the step S2 to-0.095 MPa, heating to 230 ℃, and reacting for 4 hours;
s5, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
Example 5
The preparation method of the imidazoline epoxy curing agent comprises the following steps:
s1, weighing 42 parts of fatty acid (the weight ratio of C16-C20 higher fatty acid to tall oil is 1: 1), 41 parts of fatty amine (triethylene tetramine), 10 parts of epoxy modifier (trimethylolpropane triglycidyl ether) and 0.5 part of accelerator (2,4,6 tri- (dimethylaminomethyl) phenol);
s2, uniformly mixing the fatty acid and the epoxy modifier, heating to 130 ℃, and stirring for reacting for 3 hours;
s3, adding fatty amine, heating to 170 ℃, and stirring for reacting for 3 hours;
s4, decompressing the mixture prepared in the step S2 to-0.085 MPa, heating to 240 ℃, and reacting for 6 h;
s5, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
Example 6
The preparation method of the imidazoline epoxy curing agent comprises the following steps:
s1, weighing 46 parts of fatty acid (tall oil), 48 parts of fatty amine (triethylene tetramine), 13 parts of epoxy modifier (C12-C14 alkyl glycidyl ether) and 1 part of accelerator (2,4,6 tri- (dimethylaminomethyl) phenol);
s2, uniformly mixing the fatty acid and the epoxy modifier, heating to 140 ℃, and stirring for reacting for 2 hours;
s3, adding fatty amine, heating to 180 ℃, and stirring for reacting for 2 hours;
s4, decompressing the mixture prepared in the step S2 to-0.095 MPa, heating to 240 ℃, and reacting for 6 h;
s5, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
Example 7
The preparation method of the imidazoline epoxy curing agent comprises the following steps:
s1, weighing 42 parts of fatty acid (the weight ratio of C16-C20 higher fatty acid to abietic acid is 2: 1), 46 parts of fatty amine (triethylene tetramine), 14 parts of epoxy modifier (C12-C14 alkyl glycidyl ether) and 1 part of accelerator (2-aminopiperazine);
s2, uniformly mixing the fatty acid and the epoxy modifier, heating to 150 ℃, and stirring for reacting for 1 h;
s3, adding fatty amine, heating to 190 ℃, and stirring for reacting for 1 h;
s4, decompressing the mixture prepared in the step S2 to-0.094 MPa, heating to 240 ℃, and reacting for 5 h;
s5, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
Example 8
The preparation method of the imidazoline epoxy curing agent comprises the following steps:
s1, weighing 45 parts of fatty acid (abietic acid and oleic acid in a weight ratio of 2: 1), 48 parts of fatty amine (diethylenetriamine and pentavinyl hexamine in a weight ratio of 2: 1), 14 parts of epoxy modifier (C12-C14 alkyl glycidyl ether), and 1 part of accelerator (2,4,6 tri- (dimethylaminomethyl) phenol and 2-aminopiperazine in a weight ratio of 1: 1);
s2, uniformly mixing the fatty acid and the epoxy modifier, heating to 140 ℃, and stirring for reacting for 1 h;
s3, adding fatty amine, heating to 180 ℃, and stirring for reacting for 2 hours;
s4, decompressing the mixture prepared in the step S2 to-0.092 MPa, heating to 250 ℃, and reacting for 4 hours;
s5, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
The imidazoline-based epoxy curing agents prepared in examples 1 to 8 were subjected to the following tests, and the test results are shown in table 1.
Amine value: amine curing agents, which are widely used in epoxy resins, are generally characterized by their functionality in terms of amine number, i.e., milligrams of perchloric acid and equivalent potassium hydroxide, required to neutralize 1g of imidazoline based epoxy curing agents, in mgKOH/g.
Viscosity: the viscosity of the imidazoline based epoxy curative was measured in cP at 25 ℃.
Curing time: 100 parts of 628 liquid epoxy resin and 35 parts of imidazoline epoxy curing agent are mixed to obtain the epoxy resin adhesive, and the time required by the epoxy resin adhesive to reach the maximum heat release value in min is tested.
Bonding strength: the adhesive strength of the cured wet concrete and the cured concrete is respectively tested by adopting JGJ110-2008 'inspection standard for adhesive strength of facing bricks in building engineering' to test, 100 parts of 628 liquid epoxy resin and 35 parts of imidazoline epoxy curing agent are mixed, and the unit is MPa.
Meanwhile, the adhesive force of the epoxy resin adhesive is measured according to GB/T1720, the impact strength of the epoxy resin adhesive is measured according to GB/T1732, the water resistance of the epoxy resin adhesive is measured according to GB/T1733, and the neutral salt spray resistance of the epoxy resin adhesive is measured according to GB/T1763-89.
TABLE 1
As can be seen from the test results in Table 1, the imidazoline based epoxy hardener prepared in examples 1-8 and 628 liquid epoxy resin are mixed and cured to have a bonding strength of greater than 1MPa to concrete and a bonding strength of greater than 0.7MPa to wet concrete, while the general epoxy hardener has no bonding strength to wet concrete, an adhesion rating of less than or equal to 1, an impact strength of greater than or equal to 50kg.cm, good water resistance and neutral salt spray resistance, no solvent in the hardener, no environmental pollution and the like. In the using process, after the imidazoline epoxy curing agent prepared in the embodiments 1 to 8 is mixed with epoxy resin and applied to a wet surface, the adhesive capacity is strong, the agent is not easy to fall off, the situations of degumming, obvious strength reduction, whitening and the like can not occur, and the agent is particularly suitable for treating the defects of the wet environment of buildings such as cofferdam concrete pouring, chemical grouting, dams, tunnels, water pipes, pools, aqueducts, civil air defense engineering and the like.
In conclusion, the imidazoline epoxy curing agent has low viscosity, is convenient to operate, can be quickly reacted and cured with resin, can be reacted with water on a wet surface without influencing the bonding performance, has excellent water resistance and corrosion resistance, and is particularly suitable for being used in a wet environment; and the preparation process of the product is simple, does not need a special production device, and is suitable for large-scale production.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (8)
1. The imidazoline epoxy curing agent is characterized by comprising the following components in parts by weight: 42-47 parts of fatty acid, 41-51 parts of fatty amine, 10-15 parts of epoxy modifier and 0.5-2 parts of accelerator;
the preparation process of the imidazoline epoxy curing agent is as follows:
s1, mixing fatty acid and epoxy modifier uniformly, heating to 130-150 ℃, and stirring for reaction for 1-3 h;
s2, adding fatty amine, heating to 170-190 ℃, and stirring for reaction for 2-3 h;
s3, decompressing the mixture prepared in the step S2 to-0.095 to-0.085 MPa, heating to 220 ℃ and 250 ℃, and reacting for 4-6 h;
s4, cooling the mixture prepared in the step S4 to the temperature of the mixture which is less than or equal to 70 ℃, adding an epoxy accelerator, uniformly stirring, and discharging to obtain the imidazoline epoxy curing agent.
2. The imidazoline based epoxy curing agent as claimed in claim 1, wherein in step S3, the mixture obtained in step S2 is decompressed to-0.092 to-0.090 MPa and heated to 230-240 ℃.
3. The imidazoline based epoxy curing agent as claimed in claim 1, wherein the temperature is increased to 180-190 ℃ after the fatty amine is added in step S2.
4. The imidazoline based epoxy hardener of claim 1, wherein the fatty acid is one or more of C16-C20 higher fatty acids, oleic acid, linoleic acid, rosin acid, tall oil.
5. The imidazoline-based epoxy hardener of claim 1, wherein the fatty amine is one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
6. The imidazoline epoxy curing agent of claim 1, wherein the epoxy modifier is one or a mixture of two of C12-C14 alkyl glycidyl ether, 1, 4-butanediol diglycidyl ether, o-cresol glycidyl ether, and trimethylolpropane triglycidyl ether.
7. The imidazoline based epoxy hardener of claim 1, wherein the accelerator is one or more of 2,4,6 tris- (dimethylaminomethyl) phenol, piperazine based compounds.
8. Use of the imidazoline based epoxy hardener of any one of claims 1-7 in the mixing of imidazoline based epoxy hardeners with epoxy resins to obtain epoxy resin adhesives suitable for the treatment of wet environmental defects in cofferdam concrete placement, chemical grouting, dams, tunnels, water pipes, ponds, aqueducts, civil air defense engineering and other buildings.
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| CN114701031A (en) * | 2022-04-08 | 2022-07-05 | 山东摩登港家具有限公司 | Wood veneer dyeing process |
| CN114891470A (en) * | 2022-04-12 | 2022-08-12 | 重庆邦锐特新材料有限公司 | Epoxy sealant and preparation method thereof |
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| GB1212276A (en) * | 1968-07-29 | 1970-11-11 | Coates Brothers & Co | Amino amides and/or imidazolines and their use as curing agents for epoxy resins |
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