CN116496491A - Bio-based epoxy curing agent and preparation method thereof - Google Patents
Bio-based epoxy curing agent and preparation method thereof Download PDFInfo
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- CN116496491A CN116496491A CN202310059597.6A CN202310059597A CN116496491A CN 116496491 A CN116496491 A CN 116496491A CN 202310059597 A CN202310059597 A CN 202310059597A CN 116496491 A CN116496491 A CN 116496491A
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 156
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000004952 Polyamide Substances 0.000 claims abstract description 64
- 229920002647 polyamide Polymers 0.000 claims abstract description 64
- 150000001412 amines Chemical class 0.000 claims abstract description 61
- -1 polyethylene Polymers 0.000 claims abstract description 60
- 235000013311 vegetables Nutrition 0.000 claims abstract description 51
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 46
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 34
- 239000000194 fatty acid Substances 0.000 claims abstract description 34
- 229930195729 fatty acid Natural products 0.000 claims abstract description 34
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 34
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 34
- 238000006683 Mannich reaction Methods 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000004698 Polyethylene Substances 0.000 claims abstract description 30
- 239000003085 diluting agent Substances 0.000 claims abstract description 30
- 229920000768 polyamine Polymers 0.000 claims abstract description 30
- 229920000573 polyethylene Polymers 0.000 claims abstract description 30
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 27
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 81
- 238000010438 heat treatment Methods 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 38
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 34
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical group CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 claims description 27
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 27
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 24
- 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 24
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 24
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 102100025991 Betaine-homocysteine S-methyltransferase 1 Human genes 0.000 claims description 17
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 17
- 239000005770 Eugenol Substances 0.000 claims description 17
- 101000933413 Homo sapiens Betaine-homocysteine S-methyltransferase 1 Proteins 0.000 claims description 17
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 17
- 229960002217 eugenol Drugs 0.000 claims description 17
- 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 claims description 15
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 15
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 15
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 15
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 15
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 claims description 15
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 claims description 15
- 235000007746 carvacrol Nutrition 0.000 claims description 15
- WYXXLXHHWYNKJF-UHFFFAOYSA-N isocarvacrol Natural products CC(C)C1=CC=C(O)C(C)=C1 WYXXLXHHWYNKJF-UHFFFAOYSA-N 0.000 claims description 15
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 14
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000000539 dimer Substances 0.000 claims description 11
- 239000003784 tall oil Substances 0.000 claims description 11
- IVKFHHPNCASANI-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-butan-2-ylpropane-1,3-diamine Chemical compound NCCCN(C(C)CC)CCCN IVKFHHPNCASANI-UHFFFAOYSA-N 0.000 claims description 9
- 239000004848 polyfunctional curative Substances 0.000 claims description 8
- 239000005639 Lauric acid Substances 0.000 claims description 7
- 235000021314 Palmitic acid Nutrition 0.000 claims description 7
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims description 5
- 235000021360 Myristic acid Nutrition 0.000 claims description 5
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims 3
- 239000000853 adhesive Substances 0.000 abstract description 12
- 230000001070 adhesive effect Effects 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004383 yellowing Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 229960001124 trientine Drugs 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 235000020778 linoleic acid Nutrition 0.000 description 4
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- VNMOWKHAHQJUJI-UHFFFAOYSA-N 9-[3-(tert-butylamino)propyl]-8-(2-iodo-5-methoxyphenyl)sulfanylpurin-6-amine Chemical group COC1=CC=C(I)C(SC=2N(C3=NC=NC(N)=C3N=2)CCCNC(C)(C)C)=C1 VNMOWKHAHQJUJI-UHFFFAOYSA-N 0.000 description 2
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical group NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of epoxy curing agents, and in particular relates to a bio-based epoxy curing agent and a preparation method thereof, wherein the bio-based epoxy curing agent is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 40-60 parts of polyethylene polyamine, 90-100 parts of vegetable fatty acid, 60-70 parts of long-chain fatty amine, 80-100 parts of plant polyphenol, 15-20 parts of paraformaldehyde, 10-20 parts of epoxy accelerator and 10-20 parts of diluent; the solid content is 85-95 wt%, the active hydrogen equivalent is 135-160 g/eq, and the amine value is 280-300 mgKOH/g. The invention provides a bio-based epoxy curing agent which has moderate curing speed, difficult yellowing, good flexibility and excellent comprehensive performance, can be widely applied to industries such as epoxy floors, structural adhesives and the like, solves the problems of narrow application range, singleness and the like of the existing epoxy curing agent, and solves the problems of high preparation cost, environmental pollution and the like of the existing epoxy curing agent due to the fact that raw materials are mostly extracted from plants, and is environment-friendly and low in cost.
Description
Technical Field
The invention belongs to the technical field of epoxy curing agents, and particularly relates to a bio-based epoxy curing agent and a preparation method thereof.
Background
The epoxy curing agent is a substance which reacts with the epoxy resin to form a net-shaped three-dimensional polymer, and the composite material aggregate is enveloped in the net-shaped body to promote the curing reaction.
The epoxy curing agents used with liquid epoxy resin at present mainly comprise polyamide epoxy curing agents, phenolic amine epoxy curing agents and polyamide modified phenolic amine epoxy curing agents; wherein:
(1) the unmodified polyamide epoxy curing agent is not easy to yellow and has better flexibility, but has lower activity, and the curing speed is slower when the polyamide epoxy curing agent is matched with liquid epoxy resin for use, and the polyamide epoxy curing agent can be completely cured after a few days at normal temperature, so that the application range of the polyamide epoxy curing agent is greatly limited;
(2) the non-modified phenolic aldehyde amine epoxy curing agent has the advantages that although the promotion effect of phenolic hydroxyl groups is obtained, the reaction activity is greatly improved, the curing speed is high when the non-modified phenolic aldehyde amine epoxy curing agent is matched with liquid epoxy resin, and meanwhile, the phenolic hydroxyl groups are extremely unstable, so that the epoxy system is extremely easy to yellow after being cured, and the application scene of the epoxy system is limited in higher requirements;
(3) whether the epoxy curing agent is polyamide epoxy curing agent or phenolic amine epoxy curing agent, after the epoxy system is cured, a large amount of benzene rings are introduced into the epoxy system, so that the rigidity is high, the brittleness of a cured product is high, a paint film is easy to crack when the epoxy resin is applied to an epoxy terrace, the problem of insufficient colloid impact resistance when the epoxy resin is applied to a dry-hanging structural adhesive is solved, and the defect is obvious;
(4) the epoxy curing agents such as polyamide, phenolic amine, polyamide modified phenolic amine and the like are mostly prepared from industrial chemical synthesis, have high cost, are not easy to biodegrade and pollute the ecological environment, and do not accord with the development concept of green and environment protection.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the bio-based epoxy curing agent, wherein the polyamide chain segment can be grafted into the phenolic amine chain segment through polyamide reaction, so that partial activity of phenolic hydroxyl groups can be effectively inhibited, the curing speed of the polyamide modified phenolic amine epoxy curing agent is moderate, yellowing is not easy to occur, meanwhile, long-chain fatty amine, plant fatty acid and plant polyphenol grafted and introduced in Mannich reaction all have a large number of fatty chains, the whole flexibility of the epoxy curing agent can be improved to a great extent, the problems of slow curing speed, easy yellowing of the phenolic amine epoxy curing agent, high brittleness of an epoxy system and the like of the traditional polyamide epoxy curing agent are solved, the bio-based epoxy curing agent can be widely applied to industries such as epoxy terrace, structural adhesive and the like, the problems of narrow application range, single epoxy curing agent and the like are solved, the plant fatty acid and the plant polyphenol are extracted from plants, the specific gravity of the curing agent is more than 50%, and the raw materials are green and environment-friendly, the cost is low, and the problems of high preparation cost, environmental pollution and the like of the traditional epoxy curing agent are solved. In addition, the bio-based epoxy curing agent has the solid content of 85-95 wt%, the active hydrogen equivalent weight of 135-160 g/eq, the amine value of 280-300 mgKOH/g, and moderate active hydrogen equivalent weight and amine value, so that the reactivity and the pot life of the curing agent are moderate, and the pot life and the excellent curing performance of construction are ensured.
The invention also provides a preparation method of the bio-based epoxy curing agent, which comprises the steps of firstly utilizing vegetable fatty acid and polyethylene polyamine to carry out polyamidation reaction at 180-200 ℃, distilling and dehydrating to synthesize an amino-terminated polyamide intermediate, then cooling to 80 ℃, adding long-chain fatty amine, vegetable polyphenol and paraformaldehyde to carry out Mannich reaction, simultaneously dehydrating to synthesize a polyamide modified phenolic amine curing agent by liquid separation, finally adding an epoxy accelerator and a diluent to mix and filter, and the whole preparation process is simple and easy to operate, and can effectively improve the production efficiency of the epoxy curing agent and corresponding products thereof.
The technical effects to be achieved by the invention are realized by the following technical scheme:
the bio-based epoxy curing agent is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 40-60 parts of polyethylene polyamine, 90-100 parts of vegetable fatty acid, 60-70 parts of long-chain fatty amine, 80-100 parts of plant polyphenol, 15-20 parts of paraformaldehyde, 10-20 parts of epoxy accelerator and 10-20 parts of diluent; the solid content is 85-95 wt%, the active hydrogen equivalent is 135-160 g/eq, and the amine value is 280-300 mgKOH/g.
Further, the polyethylene polyamine is one or more of Diethylenetriamine (DETA), triethylenetetramine (TETA) and Tetraethylenepentamine (TEPA).
Further, the vegetable fatty acid is one or more of linoleic acid, tall oil acid, dimer acid, lauric acid, palmitic acid and myristic acid.
Further, the long chain fatty amine is dihexyltriamine (BHMT) and/or N, N-di (3-aminopropyl) ethylethylamine (N4 amine).
Further, the plant polyphenol is one or more of cardanol, carvacrol and eugenol.
Further, the epoxy accelerator is 2-dimethylaminomethyl phenol (DMP-10) and/or 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30).
Further, the diluent is Benzyl Alcohol (BA) and/or propylene glycol methyl ether acetate (PMA).
The preparation method of the bio-based epoxy curing agent comprises the following steps:
s01, uniformly mixing and stirring the polyethylene polyamine and the vegetable fatty acid with the expected mass portions at normal temperature, heating to 180-200 ℃, then uniformly and stepwise heating to 220-240 ℃ within 2 hours, dehydrating the distilled liquid, and cooling to 80 ℃ to obtain an amino-terminated polyamide intermediate;
s02, adding the expected mass portion of long-chain fatty amine and plant polyphenol, stirring and mixing for 30-60 min, then heating the system to 105-110 ℃, adding the expected mass portion of paraformaldehyde for five times in equal amount for Mannich reaction, dehydrating, and cooling to 80 ℃ to obtain the pure solid polyamide modified phenolic amine curing agent;
s03, adding the epoxy accelerator and the diluent in the expected parts by weight, stirring and mixing for 30-60 min, and filtering and discharging through a 100-300-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy curing agent.
Further, in the step S01, after the temperature reaches 220-240 ℃, water is continuously distilled and removed for 1-2 h.
Further, in the step S02, after the Mannich reaction is carried out, the reaction is carried out for 1h to 2h at 105 ℃ to 110 ℃, then the temperature is continuously raised to 115 ℃ to 120 ℃ for 1h to 2h, meanwhile, liquid separation and dehydration are carried out, dehydration is carried out for 1h to 2h under the condition of negative pressure of 0.08MPa to 0.10MPa, and then the temperature is reduced to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
In summary, the present invention has at least the following advantages:
1. the bio-based epoxy curing agent disclosed by the invention is moderate in curing speed, not easy to yellow, good in flexibility and excellent in comprehensive performance, can be widely applied to industries such as epoxy floors and structural adhesives, solves the problems of narrow application range, singleness and the like of the epoxy curing agent, and solves the problems of high preparation cost, environmental pollution and the like of the existing epoxy curing agent due to the fact that most of raw materials are extracted from plants, and is environment-friendly and low in cost.
2. The preparation method of the bio-based epoxy curing agent is simple and easy to operate in the whole preparation process, and can effectively improve the production efficiency of the epoxy curing agent and corresponding products.
Detailed Description
In a first aspect, the invention provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through a polyamide reaction and a Mannich reaction: 40-60 parts of polyethylene polyamine, 90-100 parts of vegetable fatty acid, 60-70 parts of long-chain fatty amine, 80-100 parts of plant polyphenol, 15-20 parts of paraformaldehyde, 10-20 parts of epoxy accelerator and 10-20 parts of diluent; the solid content is 85-95 wt%, the active hydrogen equivalent is 135-160 g/eq, and the amine value is 280-300 mgKOH/g.
Further, the polyethylene polyamine is one or more of Diethylenetriamine (DETA), triethylenetetramine (TETA) and Tetraethylenepentamine (TEPA); the vegetable fatty acid is one or more of linoleic acid, tall oil acid, dimer acid, lauric acid, palmitic acid and myristic acid; the long-chain fatty amine is di-hexenetriamine (BHMT) and/or N, N-di (3-aminopropyl) ethylethylamine (N4 amine); the plant polyphenol is one or more of cardanol, carvacrol and eugenol; the epoxy accelerator is 2-dimethylaminomethyl phenol (DMP-10) and/or 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30); the diluent is Benzyl Alcohol (BA) and/or propylene glycol methyl ether acetate (PMA).
In a second aspect, the invention also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
s01, uniformly mixing and stirring the polyethylene polyamine and the vegetable fatty acid with the expected mass portions at normal temperature, heating to 180-200 ℃, then uniformly and stepwise heating to 220-240 ℃ within 2 hours, dehydrating the distilled liquid, and cooling to 80 ℃ to obtain an amino-terminated polyamide intermediate;
s02, adding the expected mass portion of long-chain fatty amine and plant polyphenol, stirring and mixing for 30-60 min, then heating the system to 105-110 ℃, adding the expected mass portion of paraformaldehyde for five times in equal amount for Mannich reaction, dehydrating, and cooling to 80 ℃ to obtain the pure solid polyamide modified phenolic amine curing agent;
s03, adding the epoxy accelerator and the diluent in the expected parts by weight, stirring and mixing for 30-60 min, and filtering and discharging through a 100-300-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy curing agent.
Further, in the step S01, after the temperature reaches 220-240 ℃, continuously distilling and dehydrating for 1-2 h; in the S02 step, after the Mannich reaction is carried out, the reaction is carried out for 1h to 2h at 105 ℃ to 110 ℃, then the temperature is continuously raised to 115 ℃ to 120 ℃ for 1h to 2h, meanwhile, liquid is separated and water is removed, dehydration is carried out for 1h to 2h under the condition of negative pressure of 0.08MPa to 0.10MPa, and then the temperature is reduced to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used, unless otherwise specified, are commercially available.
Example 1:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 40 parts of polyethylene polyamine, 90 parts of vegetable fatty acid, 70 parts of long-chain fatty amine, 80 parts of vegetable polyphenol, 15 parts of paraformaldehyde, 20 parts of epoxy accelerator and 10 parts of diluent; the solid content was 85wt%, the active hydrogen equivalent was 135g/eq, and the amine value was 280mgKOH/g.
Preferably, the polyethylene polyamine is Diethylenetriamine (DETA), the vegetable fatty acid is linoleic acid, the long-chain fatty amine is dihexylenetriamine (BHMT), the vegetable polyphenol is cardanol, the epoxy accelerator is 2-dimethylaminomethylphenol (DMP-10), and the diluent is Benzyl Alcohol (BA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
and S01, uniformly mixing and stirring 40 parts of DETA and 90 parts of linoleic acid at normal temperature, heating to 180 ℃, then uniformly and stepwise heating to 220 ℃ within 2 hours, continuously distilling and dehydrating after the distilled liquid is dehydrated to 220 ℃ for 1 hour, and then cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 70 parts of BHMT and 80 parts of cardanol, stirring and mixing for 30min, heating the system to 105 ℃, adding 15 parts of paraformaldehyde for five times in equal amount to carry out Mannich reaction, keeping the temperature at 105 ℃ for reacting for 1h, then continuously heating to 115 ℃ for reacting for 1h, simultaneously separating liquid and removing water, dehydrating for 1h under the condition of negative pressure of 0.08MPa, and then cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 20 parts of DMP-10 and 10 parts of BA, stirring and mixing for 30min, and filtering and discharging through a 100-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy hardener 1.
Example 2:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 50 parts of polyethylene polyamine, 92 parts of vegetable fatty acid, 68 parts of long-chain fatty amine, 85 parts of vegetable polyphenol, 16 parts of paraformaldehyde, 18 parts of epoxy accelerator and 12 parts of diluent; the solid content was 88wt%, the active hydrogen equivalent was 145g/eq, and the amine value was 290mgKOH/g.
Preferably, the polyethylene polyamine is triethylene tetramine (TETA), the vegetable fatty acid is tall oil acid, the long chain fatty amine is N, N-di (3-aminopropyl) ethyl ethylamine (N4 amine), the vegetable polyphenol is carvacrol, the epoxy accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), and the diluent is propylene glycol methyl ether acetate (PMA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
s01, after 50 parts of TETA and 92 parts of tall oil acid are mixed and stirred uniformly at normal temperature, heating to 190 ℃, then heating to 230 ℃ in a stepwise manner at constant speed within 2 hours, and after the distilled liquid is dehydrated, continuously distilling and dehydrating to keep 1.5 hours after the temperature reaches 230 ℃, and then cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 68 parts of N4 amine and 85 parts of carvacrol, stirring and mixing for 45min, heating the system to 105 ℃, adding 16 parts of paraformaldehyde for Mannich reaction in five times in equal amount, keeping the temperature at 105 ℃ for reaction for 1.5h, continuously heating to 115 ℃ for reaction for 1h, simultaneously separating liquid and water, dehydrating for 1.5h under the condition of negative pressure of 0.08MPa, and then cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 18 parts of DMP-30 and 12 parts of PMA, stirring and mixing for 45min, and filtering and discharging through a 200-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy hardener 2.
Example 3:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 60 parts of polyethylene polyamine, 94 parts of vegetable fatty acid, 66 parts of long-chain fatty amine, 90 parts of vegetable polyphenol, 17 parts of paraformaldehyde, 16 parts of epoxy accelerator and 14 parts of diluent; the solid content was 90wt%, the active hydrogen equivalent was 150g/eq, and the amine value was 300mgKOH/g.
Preferably, the polyethylene polyamine is Tetraethylenepentamine (TEPA), the vegetable fatty acid is 50 parts linoleic acid and 44 parts tall oil acid, the long chain fatty amine is 30 parts dihexyltriamine (BHMT) and 36 parts N, N-di (3-aminopropyl) ethyl ethylamine (N4 amine), the vegetable polyphenol is eugenol, the epoxy accelerator is 8 parts 2-dimethylaminomethylphenol (DMP-10) and 8 parts 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), the diluent is 8 parts Benzyl Alcohol (BA) and 6 parts propylene glycol methyl ether acetate (PMA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
and S01, uniformly mixing and stirring 60 parts of TEPA, 50 parts of linolenic acid and 44 parts of tall oil acid at normal temperature, heating to 200 ℃, then uniformly and stepwise heating to 240 ℃ within 2 hours, simultaneously dehydrating the distilled liquid, continuously distilling and dehydrating for 2 hours after the temperature reaches 240 ℃, and then cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 30 parts of BHMT, 36 parts of N4 amine and 90 parts of eugenol, stirring and mixing for 60min, heating the system to 110 ℃, adding 16 parts of paraformaldehyde for Mannich reaction in five equal parts, keeping the temperature at 110 ℃ for 2h, continuously heating to 120 ℃ for 1.5h, simultaneously separating water, dehydrating for 1.5h under the condition of negative pressure of 0.09MPa, and cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 8 parts of DMP-10, 8 parts of DMP-30, 8 parts of BA and 6 parts of PMA, stirring and mixing for 60min, and filtering and discharging through a 200-mesh filter screen after the system is uniformly dispersed to obtain the bio-based epoxy curing agent 3.
Example 4:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 55 parts of polyethylene polyamine, 96 parts of vegetable fatty acid, 64 parts of long-chain fatty amine, 95 parts of vegetable polyphenol, 18 parts of paraformaldehyde, 14 parts of epoxy accelerator and 16 parts of diluent; the solid content was 95wt%, the active hydrogen equivalent was 160g/eq, and the amine value was 300mgKOH/g.
Preferably, the polyethylene polyamine is 25 parts of Diethylenetriamine (DETA) and 20 parts of triethylenetetramine (TETA), the vegetable fatty acid is 50 parts of linoleic acid and 46 parts of dimer acid, the long-chain fatty amine is dihexyltriamine (BHMT), the vegetable polyphenol is 50 parts of cardanol and 45 parts of carvacrol, the epoxy accelerator is 2-dimethylaminomethylphenol (DMP-10), and the diluent is Benzyl Alcohol (BA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
and S01, mixing and stirring 25 parts of DETA, 20 parts of TETA, 50 parts of linoleic acid and 46 parts of dimer acid uniformly at normal temperature, heating to 200 ℃, then heating to 240 ℃ at uniform speed step by step within 2h, distilling to remove water after the distillate is dehydrated, continuing to distill and remove water for 2h, and then cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 64 parts of BHMT, 50 parts of cardanol and 45 parts of carvacrol, stirring and mixing for 60min, heating the system to 110 ℃, adding 18 parts of paraformaldehyde for Mannich reaction in five equal parts, keeping the temperature at 110 ℃ for 2h, continuously heating to 120 ℃ for 2h, simultaneously removing water from the liquid, dehydrating for 2h under the condition of negative pressure of 0.10MPa, and cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 14 parts of DMP-10 and 16 parts of BA, stirring and mixing for 60min, and filtering and discharging through a 300-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy hardener 4.
Example 5:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 55 parts of polyethylene polyamine, 98 parts of vegetable fatty acid, 62 parts of long-chain fatty amine, 100 parts of vegetable polyphenol, 19 parts of paraformaldehyde, 12 parts of epoxy accelerator and 18 parts of diluent; the solid content was 92wt%, the active hydrogen equivalent was 140g/eq, and the amine number was 285mgKOH/g.
Preferably, the polyethylene polyamine is 30 parts of Diethylenetriamine (DETA) and 25 parts of Tetraethylenepentamine (TEPA), the vegetable fatty acid is 50 parts of tall oil acid and 48 parts of dimer acid, the long chain fatty amine is N, N-di (3-aminopropyl) ethyl ethylamine (N4 amine), the vegetable polyphenol is 50 parts of cardanol and 50 parts of eugenol, the epoxy accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), and the diluent is propylene glycol methyl ether acetate (PMA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
s01, mixing and stirring 30 parts of DETA, 25 parts of TEPA, 50 parts of tall oil acid and 48 parts of dimer acid uniformly at normal temperature, heating to 200 ℃, then heating to 240 ℃ in a uniform speed step manner within 2 hours, distilling to remove water after the distillate is dehydrated, continuing to distill and remove water for 2 hours, and then cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 62 parts of N4 amine, 50 parts of cardanol and 50 parts of eugenol, stirring and mixing for 60min, heating the system to 110 ℃, adding 19 parts of paraformaldehyde for Mannich reaction in five equal parts, keeping the temperature at 110 ℃ for 2h, continuously heating to 120 ℃ for 2h, simultaneously removing water from the liquid, dehydrating for 2h under the condition of negative pressure of 0.10MPa, and cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 12 parts of DMP-30 and 18 parts of PMA, stirring and mixing for 60min, and filtering and discharging through a 300-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy hardener 5.
Example 6:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 50 parts of polyethylene polyamine, 100 parts of vegetable fatty acid, 60 parts of long-chain fatty amine, 90 parts of vegetable polyphenol, 20 parts of paraformaldehyde, 20 parts of epoxy accelerator and 20 parts of diluent; the solid content was 95wt%, the active hydrogen equivalent was 155g/eq, and the amine value was 295mgKOH/g.
Preferably, the polyethylene polyamine is 25 parts of triethylene tetramine (TETA) and 25 parts of tetraethylene pentamine (TEPA), the vegetable fatty acid is 30 parts of linoleic acid, 30 parts of tall oil acid and 40 parts of dimer acid, the long chain fatty amine is dihexyltriamine (BHMT), the vegetable polyphenol is 45 parts of carvacrol and 45 parts of eugenol, the epoxy accelerator is 2-dimethylaminomethylphenol (DMP-10), the diluent is 10 parts of Benzyl Alcohol (BA) and 10 parts of propylene glycol methyl ether acetate (PMA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
and S01, mixing and stirring 25 parts of TETA, 25 parts of TEPA, 30 parts of linoleic acid, 30 parts of tall oil acid and 40 parts of dimer acid uniformly at normal temperature, heating to 200 ℃, then heating to 240 ℃ at uniform speed in 2h in a stepwise manner, distilling the distillate to remove water, continuously distilling to remove water for 2h after the temperature reaches 240 ℃, and then cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 60 parts of BHMT, 45 parts of carvacrol and 45 parts of eugenol, stirring and mixing for 60min, heating the system to 110 ℃, adding 20 parts of paraformaldehyde for Mannich reaction in five equal parts, keeping the temperature at 110 ℃ for 2h, continuously heating to 120 ℃ for 2h, simultaneously separating liquid and water, dehydrating for 2h under the condition of negative pressure of 0.10MPa, and cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 20 parts of DMP-10, 10 parts of BA and 10 parts of PMA, stirring and mixing for 60min, and filtering and discharging through a 300-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy hardener 6.
Example 7:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 50 parts of polyethylene polyamine, 95 parts of vegetable fatty acid, 65 parts of long-chain fatty amine, 90 parts of vegetable polyphenol, 18 parts of paraformaldehyde, 15 parts of epoxy accelerator and 15 parts of diluent; the solid content was 93wt%, the active hydrogen equivalent was 145g/eq, and the amine value was 300mgKOH/g.
Preferably, the polyethylene polyamine is 20 parts of Diethylenetriamine (DETA), 15 parts of triethylenetetramine (TETA) and 15 parts of Tetraethylenepentamine (TEPA), the vegetable fatty acid is dimer acid, the long chain fatty amine is 35 parts of dihexyltriamine (BHMT) and 30 parts of N, N-di (3-aminopropyl) ethyl ethylamine (N4 amine), the vegetable polyphenol is 40 parts of cardanol, 30 parts of carvacrol and 20 parts of eugenol, the epoxy accelerator is 10 parts of 2-dimethylaminomethylphenol (DMP-10) and 5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), and the diluent is Benzyl Alcohol (BA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
and S01, uniformly mixing and stirring 20 parts of DETA, 15 parts of TETA, 15 parts of TEPA and 95 parts of dimer acid at normal temperature, heating to 200 ℃, uniformly and stepwise heating to 240 ℃ within 2 hours, distilling the distillate to remove water, continuously distilling to remove water for 2 hours after the temperature reaches 240 ℃, and cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 35 parts of BHMT, 30 parts of N4 amine, 40 parts of cardanol, 30 parts of carvacrol and 20 parts of eugenol, stirring and mixing for 60min, heating the system to 110 ℃, adding 20 parts of paraformaldehyde for Mannich reaction in five equal parts, keeping the temperature at 110 ℃ for 2h, continuously heating to 120 ℃ for 2h, simultaneously separating liquid and dewatering, dehydrating for 2h under the condition of negative pressure of 0.10MPa, and cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 10 parts of DMP-10, 5 parts of DMP-30 and 15 parts of BA, stirring and mixing for 60min, and filtering and discharging through a 300-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy curing agent 7.
Example 8:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 55 parts of polyethylene polyamine, 98 parts of vegetable fatty acid, 62 parts of long-chain fatty amine, 100 parts of vegetable polyphenol, 19 parts of paraformaldehyde, 12 parts of epoxy accelerator and 18 parts of diluent; the solid content was 90wt%, the active hydrogen equivalent was 150g/eq, and the amine number was 285mgKOH/g.
Preferably, the polyethylene polyamine is 30 parts of Diethylenetriamine (DETA) and 25 parts of Tetraethylenepentamine (TEPA), the vegetable fatty acid is 50 parts of lauric acid and 48 parts of palmitic acid, the long chain fatty amine is N, N-di (3-aminopropyl) ethyl ethylamine (N4 amine), the vegetable polyphenol is 50 parts of cardanol and 50 parts of eugenol, the epoxy accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), and the diluent is propylene glycol methyl ether acetate (PMA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
s01, mixing and stirring 30 parts of DETA, 25 parts of TEPA, 50 parts of lauric acid and 48 parts of palmitic acid uniformly at normal temperature, heating to 200 ℃, then heating to 240 ℃ in a uniform speed step-wise manner within 2 hours, removing water from the distilled liquid, continuously distilling and removing water for 1.5 hours after the temperature reaches 240 ℃, and cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 62 parts of N4 amine, 50 parts of cardanol and 50 parts of eugenol, stirring and mixing for 45min, heating the system to 110 ℃, adding 19 parts of paraformaldehyde for Mannich reaction in five equal parts, keeping the temperature at 110 ℃ for reacting for 1.5h, continuously heating to 120 ℃ for reacting for 1.5h, simultaneously separating liquid and dewatering, dewatering for 1.5h under the condition of negative pressure of 0.10MPa, and cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 12 parts of DMP-30 and 18 parts of PMA, stirring and mixing for 45min, and filtering and discharging through a 200-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy hardener 8.
Example 9:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 50 parts of polyethylene polyamine, 100 parts of vegetable fatty acid, 60 parts of long-chain fatty amine, 90 parts of vegetable polyphenol, 20 parts of paraformaldehyde, 20 parts of epoxy accelerator and 20 parts of diluent; the solid content was 87wt%, the active hydrogen equivalent was 155g/eq, and the amine value was 295mgKOH/g.
Preferably, the polyethylene polyamine is 25 parts of triethylene tetramine (TETA) and 25 parts of tetraethylene pentamine (TEPA), the vegetable fatty acid is 30 parts of lauric acid, 30 parts of palmitic acid and 40 parts of myristic acid, the long chain fatty amine is dihexylene triamine (BHMT), the vegetable polyphenol is 45 parts of carvacrol and 45 parts of eugenol, the epoxy accelerator is 2-dimethylaminomethylphenol (DMP-10), the diluent is 10 parts of Benzyl Alcohol (BA) and 10 parts of propylene glycol methyl ether acetate (PMA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
and S01, uniformly mixing and stirring 25 parts of TETA, 25 parts of TEPA, 30 parts of lauric acid, 30 parts of palmitic acid and 40 parts of myristic acid at normal temperature, heating to 200 ℃, uniformly and stepwise heating to 240 ℃ within 2 hours, simultaneously dehydrating the distilled liquid, continuously distilling and dehydrating for 2 hours after the temperature reaches 240 ℃, and cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 60 parts of BHMT, 45 parts of carvacrol and 45 parts of eugenol, stirring and mixing for 45min, heating the system to 110 ℃, adding 20 parts of paraformaldehyde for Mannich reaction in five equal parts, keeping the temperature at 110 ℃ for reacting for 1.5h, continuously heating to 120 ℃ for reacting for 1.5h, simultaneously separating liquid and dewatering, dewatering for 1.5h under the condition of negative pressure of 0.10MPa, and cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 20 parts of DMP-10, 10 parts of BA and 10 parts of PMA, stirring and mixing for 45min, and filtering and discharging through a 200-mesh filter screen after the system is uniformly dispersed to obtain the bio-based epoxy hardener 9.
Example 10:
the embodiment provides a bio-based epoxy curing agent which is prepared from the following components in parts by weight through polyamide reaction and Mannich reaction: 50 parts of polyethylene polyamine, 95 parts of vegetable fatty acid, 65 parts of long-chain fatty amine, 90 parts of vegetable polyphenol, 18 parts of paraformaldehyde, 15 parts of epoxy accelerator and 15 parts of diluent; the solid content was 93wt%, the active hydrogen equivalent was 140g/eq, and the amine value was 290mgKOH/g.
Preferably, the polyethylene polyamine is 20 parts of Diethylenetriamine (DETA), 15 parts of triethylenetetramine (TETA) and 15 parts of Tetraethylenepentamine (TEPA), the vegetable fatty acid is myristic acid, the long chain fatty amine is 35 parts of dihexyltriamine (BHMT) and 30 parts of N, N-di (3-aminopropyl) ethylethylamine (N4 amine), the vegetable polyphenol is 40 parts of cardanol, 30 parts of carvacrol and 20 parts of eugenol, the epoxy accelerator is 10 parts of 2-dimethylaminomethylphenol (DMP-10) and 5 parts of 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), and the diluent is Benzyl Alcohol (BA).
The embodiment also provides a preparation method of the bio-based epoxy curing agent, which comprises the following steps:
and S01, uniformly mixing and stirring 20 parts of DETA, 15 parts of TETA, 15 parts of TEPA and 95 parts of myristic acid at normal temperature, heating to 200 ℃, uniformly and stepwise heating to 240 ℃ within 2 hours, simultaneously dehydrating the distilled liquid, continuously distilling and dehydrating for 2 hours after the temperature reaches 240 ℃, and cooling to 80 ℃ to obtain the amino-terminated polyamide intermediate.
S02, adding 35 parts of BHMT, 30 parts of N4 amine, 40 parts of cardanol, 30 parts of carvacrol and 20 parts of eugenol, stirring and mixing for 45min, heating the system to 110 ℃, adding 20 parts of paraformaldehyde for Mannich reaction in five equal parts, keeping the temperature at 110 ℃ for reaction for 1.5h, continuously heating to 120 ℃ for reaction for 1.5h, simultaneously separating water, dehydrating for 1.5h under the condition of negative pressure of 0.10MPa, and cooling to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
S03, adding 10 parts of DMP-10, 5 parts of DMP-30 and 15 parts of BA, stirring and mixing for 45min, and filtering and discharging through a 200-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy curing agent 10.
Comparative example 1:
polyamide epoxy curing agents are commercially available.
Comparative example 2:
phenolic amine epoxy curing agents are commercially available.
Comparative example 3:
commercially available polyamide modified phenolic amine epoxy curing agents.
Test example 1:
the bio-based epoxy curing agent prepared in examples 1 to 10 and the commercially available epoxy curing agent of comparative examples 1 to 3 were prepared into stone adhesives according to a weight ratio of 1:1.2 with liquid epoxy resin E51 (about 190g/eq in epoxy equivalent), and each stone adhesive was tested according to the standard of JC/T547-2005 ceramic tile adhesives to prepare test specimens having the properties of workability, yellowing resistance, tensile bond strength, water-immersion bond strength and transverse deformation (flexibility) after being completely cured, and the test results are shown in Table 1.
Table 1 results of performance test of each stone adhesive
As shown in Table 1, the bio-based epoxy curing agent of the invention has higher performance indexes such as operation time, yellowing resistance, tensile bond strength, soaking bond strength and the like than the commercially available epoxy curing agent when applied to stone adhesives, has prominent advantages in performance indexes such as yellowing resistance level, bond strength, transverse deformation (flexibility) and the like, and can be widely applied to the field of stone adhesives.
Test example 2:
the bio-based epoxy curing agent prepared in examples 1 to 10 and the commercially available epoxy curing agent of comparative examples 1 to 3 were prepared into industrial floor paints by mixing with liquid epoxy resin E51 (about 190g/eq in epoxy equivalent) in a weight ratio of 1:1.4, and each industrial floor paint was tested according to the standard of GB/T22374-2008 floor coating materials to prepare test specimens, which were dried after complete curing, hardness, adhesion rating, impact resistance and water resistance, and the test results thereof are shown in Table 2.
Table 2 table of results of performance test of various industrial floor paints
As shown in Table 2, the bio-based epoxy curing agent provided by the invention has the characteristics of short drying time, high hardness, strong adhesive force, good impact resistance and water resistance when being applied to industrial floors, has obvious advantages in performance indexes such as drying time, hardness, impact resistance and water resistance when being compared with industrial floor paint prepared from the commercially available epoxy curing agent, and can be widely applied to the field of industrial floor paint.
Test example 3:
raw material costs of the bio-based epoxy curing agent in examples 1 to 10 and the commercially available epoxy curing agent in comparative examples 1 to 3 were calculated, respectively, and the results are shown in table 3.
TABLE 3 raw material cost of epoxy curing Agents
As can be seen from Table 3, the bio-based epoxy curing agent of the present invention has low cost of raw materials, which is lower than the commercially available epoxy curing agent.
According to the technical scheme of the embodiment, the invention provides the bio-based epoxy curing agent, the polyamide chain segment can be grafted into the phenolic amine chain segment through polyamide reaction, so that partial activity of phenolic hydroxyl groups is effectively inhibited, the curing speed of the polyamide modified phenolic amine epoxy curing agent is moderate, yellowing is not easy to occur, meanwhile, long-chain fatty amine, plant fatty acid and plant polyphenol grafted and introduced in Mannich reaction all have a large number of fatty chains, the whole flexibility of the epoxy curing agent can be improved to a great extent, the problems that the traditional polyamide epoxy curing agent is slow in curing, the phenolic amine epoxy curing agent is easy to yellow, the epoxy system is high in brittleness and the like are solved, the epoxy curing agent can be widely applied to industries such as epoxy floors and structural adhesives, the problems of narrow application range, single application range and the like are solved, the plant fatty acid and the plant polyphenol account for plant extraction, the specific gravity of the curing agent is more than 50%, and the problems of green and environment-friendly raw materials, low cost and high preparation cost, environmental pollution and the like of the traditional epoxy curing agent are solved. The invention also provides a preparation method of the bio-based epoxy curing agent, the whole preparation process is simple and easy to operate, and the production efficiency of the epoxy curing agent and corresponding products can be effectively improved.
While the invention has been described in conjunction with the specific embodiments above, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, all such alternatives, modifications, and variations are included within the spirit and scope of the following claims.
Claims (10)
1. The bio-based epoxy curing agent is characterized by being prepared from the following components in parts by weight through a polyamide reaction and a Mannich reaction:
the solid content is 85-95 wt%, the active hydrogen equivalent is 135-160 g/eq, and the amine value is 280-300 mgKOH/g.
2. The biobased epoxy curative according to claim 1, wherein the polyethylene polyamine is one or more of Diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA).
3. The biobased epoxy curative according to claim 1, wherein the vegetable fatty acid is one or more of linoleic acid, tall oil acid, dimer acid, lauric acid, palmitic acid, myristic acid.
4. The biobased epoxy curative according to claim 1, wherein the long chain fatty amine is dihexyltriamine (BHMT) and/or N, N-di (3-aminopropyl) ethylethylamine (N4 amine).
5. The bio-based epoxy curing agent of claim 1, wherein the plant polyphenol is one or more of cardanol, carvacrol, eugenol.
6. The biobased epoxy curative according to claim 1, wherein the epoxy accelerator is 2-dimethylaminomethylphenol (DMP-10) and/or 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30).
7. The biobased epoxy curative according to claim 1, wherein the diluent is Benzyl Alcohol (BA) and/or propylene glycol methyl ether acetate (PMA).
8. A method for preparing a bio-based epoxy hardener according to any one of claims 1-7, comprising the steps of:
s01, uniformly mixing and stirring the polyethylene polyamine and the vegetable fatty acid with the expected mass portions at normal temperature, heating to 180-200 ℃, then uniformly and stepwise heating to 220-240 ℃ within 2 hours, dehydrating the distilled liquid, and cooling to 80 ℃ to obtain an amino-terminated polyamide intermediate;
s02, adding the expected mass portion of long-chain fatty amine and plant polyphenol, stirring and mixing for 30-60 min, then heating the system to 105-110 ℃, adding the expected mass portion of paraformaldehyde for five times in equal amount for Mannich reaction, dehydrating, and cooling to 80 ℃ to obtain the pure solid polyamide modified phenolic amine curing agent;
s03, adding the epoxy accelerator and the diluent in the expected parts by weight, stirring and mixing for 30-60 min, and filtering and discharging through a 100-300-mesh filter screen after the system is uniformly dispersed to prepare the bio-based epoxy curing agent.
9. The method for preparing a bio-based epoxy curing agent according to claim 8, wherein in the step S01, the water is distilled continuously for 1 to 2 hours after the temperature reaches 220 to 240 ℃.
10. The method for preparing the bio-based epoxy curing agent according to claim 8, wherein in the step S02, after the mannich reaction is performed, the reaction is performed for 1h to 2h at 105 ℃ to 110 ℃, then the temperature is continuously raised to 115 ℃ to 120 ℃ for 1h to 2h, meanwhile, liquid is separated and water is removed, dehydration is performed for 1h to 2h under the condition of negative pressure of 0.08MPa to 0.10MPa, and then the temperature is reduced to 80 ℃ to obtain the polyamide modified phenolic amine curing agent with pure solid.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633991A (en) * | 2012-04-10 | 2012-08-15 | 卡德莱化工(珠海)有限公司 | Alkylphenol modified phenolic amide curing agent and preparation method thereof |
| CN103980463A (en) * | 2014-04-23 | 2014-08-13 | 中科院广州化学有限公司南雄材料生产基地 | Epoxy resin solvent-free low temperature curing agent, preparation method and application thereof |
| CN112500553A (en) * | 2020-12-03 | 2021-03-16 | 武汉市科达云石护理材料有限公司 | Waterborne epoxy back-mesh adhesive curing agent, preparation method and back-mesh adhesive |
| CN112789308A (en) * | 2018-10-01 | 2021-05-11 | Sika技术股份公司 | Curing agent for epoxy resins |
| US20220298100A1 (en) * | 2019-12-13 | 2022-09-22 | Jayram Mangesh Nadkarni | Distilled cashew nut shell liquid based, water thinable phenalkamine as curing agent for epoxy paint compositions |
| CN115286768A (en) * | 2021-12-23 | 2022-11-04 | 常熟耐素生物材料科技有限公司 | Cardanol aldehyde amine epoxy curing agent and preparation method thereof |
-
2023
- 2023-01-18 CN CN202310059597.6A patent/CN116496491A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633991A (en) * | 2012-04-10 | 2012-08-15 | 卡德莱化工(珠海)有限公司 | Alkylphenol modified phenolic amide curing agent and preparation method thereof |
| CN103980463A (en) * | 2014-04-23 | 2014-08-13 | 中科院广州化学有限公司南雄材料生产基地 | Epoxy resin solvent-free low temperature curing agent, preparation method and application thereof |
| CN112789308A (en) * | 2018-10-01 | 2021-05-11 | Sika技术股份公司 | Curing agent for epoxy resins |
| US20220298100A1 (en) * | 2019-12-13 | 2022-09-22 | Jayram Mangesh Nadkarni | Distilled cashew nut shell liquid based, water thinable phenalkamine as curing agent for epoxy paint compositions |
| CN112500553A (en) * | 2020-12-03 | 2021-03-16 | 武汉市科达云石护理材料有限公司 | Waterborne epoxy back-mesh adhesive curing agent, preparation method and back-mesh adhesive |
| CN115286768A (en) * | 2021-12-23 | 2022-11-04 | 常熟耐素生物材料科技有限公司 | Cardanol aldehyde amine epoxy curing agent and preparation method thereof |
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