CN118005892A - Secondary amine curing agent and preparation method and application thereof - Google Patents
Secondary amine curing agent and preparation method and application thereof Download PDFInfo
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- CN118005892A CN118005892A CN202410062059.7A CN202410062059A CN118005892A CN 118005892 A CN118005892 A CN 118005892A CN 202410062059 A CN202410062059 A CN 202410062059A CN 118005892 A CN118005892 A CN 118005892A
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- curing agent
- secondary amine
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- amine
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 title abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 239000004593 Epoxy Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 150000001412 amines Chemical class 0.000 claims abstract description 33
- -1 amine compound Chemical class 0.000 claims abstract description 24
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 36
- 150000003141 primary amines Chemical group 0.000 claims description 25
- 229920006332 epoxy adhesive Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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 2
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- AKRJXOYALOGLHQ-UHFFFAOYSA-N 2-methylheptan-4-one Chemical compound CCCC(=O)CC(C)C AKRJXOYALOGLHQ-UHFFFAOYSA-N 0.000 claims description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 2
- BIFPSSTVLFHHEI-UHFFFAOYSA-N 4-methylheptan-2-one Chemical compound CCCC(C)CC(C)=O BIFPSSTVLFHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 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 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims 2
- NWOJEYNEKIVOOF-UHFFFAOYSA-N hexane-2,2-diamine Chemical compound CCCCC(C)(N)N NWOJEYNEKIVOOF-UHFFFAOYSA-N 0.000 claims 1
- 229940100684 pentylamine Drugs 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000004970 Chain extender Substances 0.000 abstract 1
- 238000005034 decoration Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 230000000638 stimulation Effects 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 54
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000007794 irritation Effects 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 150000004658 ketimines Chemical class 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- NOYXQFBTCCSKQG-UHFFFAOYSA-N 2-[[2-(oxiran-2-ylmethoxy)cyclohexyl]oxymethyl]oxirane Chemical compound C1OC1COC1CCCCC1OCC1CO1 NOYXQFBTCCSKQG-UHFFFAOYSA-N 0.000 description 1
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- 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)
Abstract
The invention provides a secondary amine curing agent, a preparation method and application thereof, wherein the secondary amine curing agent comprises structures shown in a formula I, a formula II and a formula III. The preparation method comprises the following steps: reacting basic amine with a difunctional epoxy compound to obtain an epoxy chain extender amine compound; adding a monofunctional epoxy reactive diluent into the reaction product of the previous step, and obtaining a mixture containing a small amount of primary amine functional groups and residual monomers after reaction; and adding ketone compounds into the reaction product of the previous step, vacuumizing to remove water, and reacting to obtain the secondary amine curing agent. The invention combines several modification modes to obtain a brand new secondary amine curing agent which has only secondary amino active hydrogen, multiple reaction points and quite reactive activity, and the curing agent has moderate price due to easily available raw materials and strong process operability, is matched with epoxy resin for use, and meets the environmental protection requirements of building decoration with low volatilization, low odor and low stimulation.
Description
Technical Field
The invention relates to the technical field of epoxy curing agents, in particular to a secondary amine curing agent, a preparation method and application thereof.
Background
The epoxy adhesive is an excellent adhesive variety which uses epoxy resin as a base resin system and is cured by being matched with a related epoxy curing agent, has high strength and good adhesive property, has good adhesive effect on most of base materials, has excellent water resistance and chemical resistance, is applied to various fields of industry and civilian use, has extremely wide application range, particularly in recent years, has endlessly developed research on the epoxy system, and is a plurality of excellent products.
However, with the progressive penetration of the application, epoxy adhesives also expose a number of problems, the most serious of which is environmental protection. In particular in the field of construction, the construction material has relatively low cost due to universality, so that a large amount of cheap and low-end epoxy adhesive materials are used in the construction engineering, and the health of constructors and owners is greatly influenced.
The epoxy adhesive for building is generally a normal temperature curing system, and is mainly prepared by stirring, reacting and curing epoxy resin and polyamine curing agent, and in order to reduce the toxicity of polyamine curing agent, certain chemical modification is required in production, so that the molecular weight is properly increased, the volatility is reduced, and the toxicity is reduced. However, in order to control the viscosity of the system, the conventional modification reaction often cannot thoroughly react the small molecular amine monomers, basically the basic amine is greatly excessive, and the residual monomer small molecular amine is easy to volatilize in use, so that the odor is large, and the people are allergic. The special amine curing agent with smaller odor is generally relatively high in price, so that the cost of the epoxy curing agent material can be greatly increased, and the conventional application of the epoxy system in the field of construction is limited to a certain extent.
As is known, the primary amine group has relatively stronger irritation than the secondary amine group, and the common amine curing agent has quite large primary amine group content even though being modified, so that the common amine curing agent has relatively stronger irritation to human bodies and is not environment-friendly. For the traditional polyamide curing agent, although the volatility is not strong and the irritation is not too great, the curing speed is very slow, the viscosity is high, the operation is inconvenient, and more importantly, the strength of the cured product is not high, so that the use is limited greatly. For general ketimine curing agents, the curing agent belongs to a latent curing agent, water vapor gradually permeates to slowly cure, the curing speed is very slow, and generally, in order to maintain equivalent activity, lower-level ketone compounds such as methyl isobutyl ketone are mostly adopted, and the curing agent can be released into the air after curing, so that the curing agent is environment-friendly, affects the strength and is not suitable for being widely used in the field of construction.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a novel secondary amine curing agent, and a preparation method and application thereof.
In a first aspect, the present invention provides a secondary amine curative comprising the structures of formula I, formula II, and formula III:
Formula I:
Formula II:
Formula III:
wherein n 1 =0 to 2;
r 1 is
R 2 is
R 3 is -C4H9,-C8H17,-C12H25,-C13H27,-C14H29,
R 4 is-CH 3 or-C 3H7;
R 5 is-C 5H11, Preferably, n 1 is 1 to 2;
r 1 is
R 2 is
R 3 is-C 4H9 orR 4 is-CH 3;
R 5 is
It should be noted that n 1、n2、n3、n4 mentioned in the present invention is an integer.
In the secondary amine curing agent, the mass ratio of the structure shown in the formula I in the secondary amine curing agent is more than 90%.
In a second aspect, the present invention provides a process for preparing the secondary amine curing agent described above.
The preparation method provided by the invention comprises the following steps:
s1, reacting basic amine with a difunctional epoxy compound to obtain an epoxy chain extension amine compound;
s2, adding a monofunctional epoxy reactive diluent into the reaction product of the step S1, and reacting to obtain a mixture containing a small amount of primary amine functional groups and residual monomers;
And S3, adding a ketone compound into the reaction product in the step S2, vacuumizing to remove water, and reacting to obtain the secondary amine curing agent.
According to the invention, through reasonable reaction step design, the small molecular amine monomers in the polyamine system are completely reacted, the molecular weight of the product and the number of branched reaction end points are effectively controlled, and the viscosity and the reactivity of the system are controlled, so that the curing agent disclosed by the invention meets the use requirements.
Further, in step S1, the base amine is selected from vinylamines (including ethylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine), pentylene diamine, methylpenta-diamine, N4 amine, hexamethylenediamine, dihexyltriamine, polyetheramine, m-xylylenediamine, 1, 3-cyclohexanedimethylamine (1, 3-BAC), isoparaffinone diamine.
The difunctional epoxy compound is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, hydrogenated bisphenol A epoxy resin, difunctional epoxy diluent (including diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, resorcinol diglycidyl ether).
Further, in step S1, the difunctional epoxy compound is added into the basic amine in a dropwise adding mode, the temperature of the basic amine is 50-60 ℃ in the initial dropwise adding process, the reaction exotherm is gradually increased in the dropwise adding process, the temperature is controlled to be 70-80 ℃, and the reaction is maintained at 70-80 ℃ for 2-2.5 hours after the dropwise adding is completed.
Further, in the step S2, the Shan Guan epoxy reactive diluent is selected from one or more of butyl glycidyl ether, octyl glycidyl ether, C12-14 alkyl glycidyl ether, benzyl glycidyl ether and cardanol glycidyl ether;
In the step S2, the reaction temperature is 70-80 ℃ and the reaction time is 2-2.5 hours.
Further, in the step S3, the ketone compound is selected from one or more of 2-heptanone, 4-methyl-2-heptanone, 2-methyl-4-heptanone and acetophenone;
in the step S3, the reaction temperature is 120-130 ℃, and the reaction is continued for 0.5-1 hour after the vacuum pumping is carried out until no water is generated.
In some embodiments of the invention, the specific steps of the preparation method are as follows:
Step 1: adding basic amine into a reactor provided with a condensate water reflux device, opening stirring, controlling the temperature to rise to 50-60 ℃, slowly adding a certain amount of difunctional epoxy compound in a dropwise adding mode, reacting while slowly rising the temperature, controlling the reaction temperature to be 70-80 ℃, and maintaining the reaction for 2-2.5 hours to obtain the epoxy chain-extending amine compound.
The reaction is as follows:
Step 2: and (2) dropwise adding a certain amount of monofunctional epoxy reactive diluent into the reaction product of the step (1), controlling the reaction temperature at 70-80 ℃ and maintaining the reaction for 2-2.5 hours to prepare a mixture containing only a few primary amine functional groups and residual monomers.
The reaction is as follows:
Step 3: and (2) adding a certain amount of ketone compounds into the reaction product of the step (2) at one time, removing the reflux device, connecting the vacuumizing and dewatering device, maintaining the temperature at 120-130 ℃, vacuumizing and dewatering while reacting until no water is generated, and continuing to perform heat preservation reaction for 0.5-1 hour to prepare the curing agent without primary amine functional groups and residual monomers, namely the novel secondary amine curing agent.
The reaction is as follows:
further, the molar ratio of the basic amine, the difunctional epoxy compound and the monofunctional epoxy reactive diluent is 1.5-3: 1: 1-4, wherein the mass of the ketone compound is 3-5% of the mass of the reaction product of the step S2.
In the technical scheme, the molar ratio of the 3 raw materials of basic amine, difunctional epoxy compound and monofunctional epoxy reactive diluent is controlled to be 1.5-3: 1: 1-4 to obtain proper viscosity and proper branching density to ensure proper operability and mechanical strength in the later application of the curing agent. In order to substantially consume the primary amine in step 1 and step 2, the ratio is such that the molar number of the epoxy groups contained in the difunctional epoxy compound and the monofunctional epoxy reactive diluent can be exactly equal to the molar number of the primary amine in the primary amine.
In the first step of the invention, the difunctional epoxy compound reacts with the basic amine compound, so that secondary amine hydrogen reaction points are increased in the molecular chain segments of the curing agent, the crosslinking density of the curing agent in use can be ensured, and the adhesive strength of the curing agent in curing epoxy is ensured. In the second step, the primary amine is converted into the secondary amine by further reaction of the monofunctional epoxy reactive diluent, preferably with the primary amine with higher reactivity, and the residual amine monomer is also substantially reacted. However, due to the problem of the probability of the competing reaction and the error of the content and molecular weight of the raw materials used, the basic amine monomer and primary amine cannot be completely reacted according to the theoretical value, the basic amine monomer and primary amine are required to be completely consumed through the third step, ketone compounds are added and selectively react with primary amine groups only under the condition of heating and dewatering to generate ketimine, under the condition that the ketone compounds are excessive and the reaction time is sufficient, the residual primary amine groups and small molecular amine monomers can be fully reacted, the excessive ketone compounds can be left in the system to act as an environment-friendly diluent, the obtained ketimine groups can also act as a latent curing agent in the later application, the amine groups can be released by moisture absorption and water reaction, and the epoxy resin can be further reacted and cured. Of course, because of the design proportioning reaction of the first two steps, ketimine components generated by the partial reaction are fewer, and basically the whole reaction speed in the later stage is not influenced.
In a third aspect, the present invention provides an epoxy adhesive comprising an epoxy resin base and any of the secondary amine curing agents described above.
The reactive group of the curing agent system of the invention and the epoxy resin has only secondary amino active hydrogen, no small molecular amine monomer, eliminates primary amine group with stronger irritation, really realizes low volatilization, low odor and low irritation, and is friendly to human and environment in the use process. The epoxy adhesive which is environment-friendly and green and can be widely used can be obtained.
The invention provides a secondary amine curing agent, a preparation method and application thereof, which are characterized in that a plurality of modification modes are combined to obtain a brand-new secondary amine active hydrogen only, multiple reaction points (each active hydrogen is a reaction point in the reaction process with epoxy resin) and quite reactive secondary amine curing agent.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Examples 1 to 7
Examples 1-7 each provided a secondary amine curing agent, the relative amounts of raw materials (all parts by weight) are shown in Table 1, and the preparation method is as follows:
Step 1: adding basic amine into a reactor provided with a condensate water reflux device, opening stirring, controlling the temperature to rise to 50-60 ℃, slowly adding a certain amount of difunctional epoxy compound in a dropwise adding mode, reacting while slowly rising the temperature, controlling the reaction temperature to be 70-80 ℃, and maintaining the reaction for 2-2.5 hours to obtain the epoxy chain-extending amine compound.
Step 2: and (2) dropwise adding a certain amount of monofunctional epoxy reactive diluent into the reaction product of the step (1), controlling the reaction temperature at 70-80 ℃ and maintaining the reaction for 2-2.5 hours to prepare a mixture containing only a few primary amine functional groups and residual monomers.
Step 3: and (2) adding a certain amount of environment-friendly ketone compounds into the reaction product of the step (2) at one time, removing the reflux device, connecting the vacuumizing and dewatering device, maintaining the temperature at 120-130 ℃, vacuumizing and dewatering, reacting until no water is generated, and continuing to perform heat preservation reaction for 0.5-1 hour to prepare the curing agent without primary amine functional groups and residual monomers, namely the secondary amine curing agent.
TABLE 1
Structural characterization: the basic amine and the product were simultaneously subjected to infrared spectroscopic analysis, and the FT-IR infrared spectrum showed that the original peaks at 3473cm -1 and 3357cm -1 were two absorption peaks, which changed to a single peak at 3384cm -1, indicating that the primary amine group had been converted. (in the infrared spectrum, the absorption peaks of the primary amine group and the secondary amine group are all in the range of 3300-3500cm -1, the primary amine group has two absorption peaks, the secondary amine group has only one absorption peak, when the primary amine group exists, the primary amine group absorption peak covers the absorption peak of the secondary amine group, so when the double peak is changed into the single peak, the primary amine group is completely reacted, and the system only contains the secondary amine group.)
Comparative example 1
The comparative example provides a commercially available curing agent with stronger environmental protection, namely polyamide 650 curing agent, and the conventional synthesis process is as follows:
Adding dimer acid and diethylenetriamine into a reactor, heating to 100-140 ℃, preserving heat for reaction for 1 hour, heating to 200-240 ℃, preserving heat for reaction for 2 hours, then vacuumizing and dehydrating to remove micromolecule amine while reacting at 180-200 ℃ until the central control amine value reaches theoretical requirements, stopping vacuumizing and heating, and cooling and discharging.
Comparative example 2
The comparative example provides a curing agent-ketimine curing agent with stronger environmental protection, which is prepared by the following conventional synthesis process:
Adding basic amine (aliphatic polybasic primary amine is adopted in the conventional way) and ketone compounds (methyl isobutyl ketone is adopted in the conventional way) into a reactor, heating to 120-150 ℃, vacuumizing and dehydrating while reacting, stopping the reaction until completely anhydrous discharging, and cooling and discharging.
Comparative example 3
The comparative example provides a commercially available curing agent with stronger environmental protection, namely an addition curing agent 593, and the conventional synthesis process is as follows:
Adding diethylenetriamine into a reactor, simultaneously dropwise adding butyl glycidyl ether, heating while reacting, controlling the temperature to be 70-80 ℃ after the dropwise adding, preserving heat and reacting for 1-2 hours, and cooling and discharging.
Performance testing
Performance tests were carried out on the finished secondary amine curing agent products obtained in examples 1 to 7 and the curing agents of comparative examples 1 to 3, respectively, by the following specific detection methods:
viscosity: the test was performed using a model NDJ-7 rotary viscometer.
Amine number: the test was performed by ethanol titration with hydrochloric acid.
Smell: the detection is carried out by referring to the standard HG/T4065-2008 adhesive odor evaluation method. ( Stage 1: no smell; 2 stages: the smell is slight but perceptible; 3 stages: odorous but without strong discomfort; 4 stages: a strong unpleasant smell; 5 stages: has a pungent and uncomfortable smell. )
Volatile matters: the test was carried out by applying a vacuum (negative pressure-0.1 MPa) at 80℃for 1 hour.
Proportioning: the ratio of the epoxy resin to the epoxy resin E51 is equal to E51: and (3) a curing agent.
Gel time: the detection is carried out by reference to the standard GBT 12954-1991 general test method for building adhesives.
Tensile shear strength: the detection is carried out with reference to standard GB/T7124-2008 "determination of tensile shear Strength of Adhesives (rigid Material vs rigid Material").
The measured technical indexes are shown in table 2.
TABLE 2
The comparison result shows that the novel secondary amine curing agent is equivalent to polyamide in volatility, is superior to the curing agent of the comparative example in odor, curing speed and mechanical property, is an environment-friendly curing agent with excellent comprehensive performance, and is very suitable for the field of building epoxy adhesives.
It should be noted that endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and that such range or value should be understood to include values approaching such range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "detailed description," or "some embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A secondary amine curing agent comprising the structures of formula I, formula II, and formula iii:
formula I:
formula II:
Formula III:
wherein n 1 =0 to 2;
r 1 is
-C4H8-，
R 2 is-C5H10-,-C6H12-，
R 3 is -C4H9,-C8H17,-C12H25,-C13H27,-C14H29,
R 4 is-CH 3 or-C 3H7;
R 5 is-C 5H11,
2. The secondary amine curative of claim 1, wherein n 1 is 1 to 2;
r 1 is
R 2 is
R 3 is-C 4H9 or
R 4 is-CH 3;
R 5 is
3. The secondary amine curative according to claim 1 or 2, wherein the mass ratio of the structure of formula I in the secondary amine curative is greater than 90%.
4. A process for preparing the secondary amine curing agent of any one of claims 1 to 3, comprising the steps of:
s1, reacting basic amine with a difunctional epoxy compound to obtain an epoxy chain extension amine compound;
s2, adding a monofunctional epoxy reactive diluent into the reaction product of the step S1, and reacting to obtain a mixture containing a small amount of primary amine functional groups and residual monomers;
And S3, adding a ketone compound into the reaction product in the step S2, vacuumizing to remove water, and reacting to obtain the secondary amine curing agent.
5. The method of producing a secondary amine curing agent according to claim 4, wherein in step S1, the base amine is selected from one or more of vinylamine, pentylamine, methylpentanediamine, N4 amine, hexamethylenediamine, dihexyltriamine, polyetheramine, m-xylylenediamine, 1, 3-cyclohexanedimethylamine, and isophthalone diamine;
the difunctional epoxy compound is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, hydrogenated bisphenol A epoxy resin and difunctional epoxy diluent.
6. The process for producing a secondary amine curing agent according to claim 4, wherein in step S1, the difunctional epoxy compound is added to the base amine by dropwise addition, the temperature of the base amine is 50 to 60℃at the beginning of the dropwise addition, the reaction exotherm gradually increases during the dropwise addition, the temperature is controlled to 70 to 80℃and the reaction is maintained at 70 to 80℃for 2 to 2.5 hours after the completion of the dropwise addition.
7. The process for preparing a secondary amine curing agent according to claim 4, wherein in step S2, the Shan Guan epoxy reactive diluent is selected from one or more of butyl glycidyl ether, octyl glycidyl ether, C12-14 alkyl glycidyl ether, benzyl glycidyl ether, cardanol glycidyl ether;
In the step S2, the reaction temperature is 70-80 ℃ and the reaction time is 2-2.5 hours.
8. The method for producing a secondary amine curing agent according to claim 4, wherein in step S3, the ketone compound is selected from one or more of 2-heptanone, 4-methyl-2-heptanone, 2-methyl-4-heptanone, acetophenone;
in the step S3, the reaction temperature is 120-130 ℃, and the reaction is continued for 0.5-1 hour after the vacuum pumping is carried out until no water is generated.
9. The process for preparing a secondary amine curing agent according to any one of claims 4 to 8, characterized in that the molar ratio of base amine, difunctional epoxy compound, monofunctional epoxy reactive diluent is from 1.5 to 3:1: 1-4, wherein the mass of the ketone compound is 3-5% of the mass of the reaction product of the step S2.
10. An epoxy adhesive comprising an epoxy resin base and the secondary amine curative of any one of claims 1-3.
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