CN104974094A - Acyl-substituted iminazole latent epoxy resin curing agent and preparation method thereof - Google Patents

Acyl-substituted iminazole latent epoxy resin curing agent and preparation method thereof Download PDF

Info

Publication number
CN104974094A
CN104974094A CN201510468673.4A CN201510468673A CN104974094A CN 104974094 A CN104974094 A CN 104974094A CN 201510468673 A CN201510468673 A CN 201510468673A CN 104974094 A CN104974094 A CN 104974094A
Authority
CN
China
Prior art keywords
acyl
curing agent
solvent
compound
acyl chloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510468673.4A
Other languages
Chinese (zh)
Inventor
马文石
雷定锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201510468673.4A priority Critical patent/CN104974094A/en
Publication of CN104974094A publication Critical patent/CN104974094A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring

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 belongs to the technical field of curing agents, and discloses an acyl-substituted iminazole latent epoxy resin curing agent and a preparation method thereof. The method comprises the following steps: (1) dissolving iminazole compounds in a solvent to prepare a solution, adding triethylamine into the solution, introducing N2, and dissolving to obtain an iminazole compound solution; (2) dissolving acyl chloride compounds in a solvent to prepare an acyl chloride compound solution; under N2 conditions, slowly and dropwisely adding the acyl chloride compound solution into the iminazole compound solution in the step (1), continuing reacting for 5-15 hours, carrying out vacuum filtration, and carrying out rotary evaporation to a dry state; and washing the rotary evaporation product with a solvent, and drying to obtain the acyl-substituted iminazole latent epoxy resin curing agent. The storage stability of the curing agent is greatly enhanced, and the latent period is 1-6 months. The acyl-substituted iminazole latent epoxy resin curing agent has favorable compatibility with epoxy resins, so that the curing product has higher mechanical properties.

Description

Acyl substituted imidazoles incubated epoxide curing agent and preparation method thereof
Technical field
The invention belongs to the technical field of solidifying agent, relate to a kind of epoxy curing agent, particularly a kind of acyl substituted imidazoles incubated epoxide curing agent and preparation method thereof.
Background technology
Be solid polymer that is liquid or low softening point under epoxy resin normal temperature, need could meet application requiring after curing reaction.Epoxy group(ing) in epoxy molecule easily with multiple solidifying agent generation chemical reaction, conventional amine and the activity of imidazole curing agent all higher, react very soon after mixing with epoxy resin, so the industrial solidifying agent of epoxy resin tackifier, coating etc. and epoxy resin must being separated packs, stores and transports.This brings a lot of inconvenience not only to epoxy resin tackifier, the packaging of coating, storage, transport, and site of deployment mixing may lack of proper care because of each component ratio control, mixes uneven and affect Solidified enzyme.
If a class incubated epoxide curing system can be developed, namely can incubated epoxide curing agent be added in epoxy resin, both can mix storage, by not only allowing, the packaging of epoxyn, coating, storage, transport and use are convenient, and be more conducive to the control of the manufacturer such as epoxyn, coating to product quality and performances, improve application performance.This just requires that solidifying agent has good latent, and latent is the key of this technology.Though have developed Dyhard RU 100 (Int J AdhesAdhes at present, 2010,30 (2): 105-110), the epoxy curing agent such as organic hydrazides (JP59131953), and there is good storage stability, but its solidification value is too high, generally will could by epoxy resin cure to more than 170 DEG C, a lot of electronic devices and components of encapsulation that need are made to be difficult to bear, and the poor compatibility of Dyhard RU 100, organic hydrazides and epoxy resin, this just causes cured article of poor quality, unstable properties.And though modified fatty amine, modified aniline class are better with epoxy resin compatibility, can at middle temperature fast setting, its latent period is very short, much in storage, in transit just solidification, and causes and cannot use.So a kind of quality of incubated epoxide curing agent, mainly contains three keys and important index: with epoxy resin compatibility quality, latent period length, solidify stable height, normally conflicting both rear.In order to address this problem, scientific worker is in continuous effort.
Imidazole curing agent is due to its higher curing efficiency, suitable solidification value and the mechanical property of cured product excellence and be widely used in epoxy resin product, its package stability is slightly excellent compared with fatty amines solidifying agent, but also only have the working life of a few days after mixing with epoxy resin, the preparation of " single-component " epoxyn, coating etc. can not be used for.Existing part is about the report improving imidazole curing agent package stability both at home and abroad, comprise substituting modification (US4335228, CN102964568A), chelating reaction (J Polm Sci, 2003,28 (4): 294-198), capsule method (EP543675, JP 05293178, CN101016369A) etc., wherein chelating reaction can give excellent latent for imidazole curing agent, but the consistency of imidazoles complex compound and epoxy resin is poor; The imidazole curing agent that substituting modification and capsule method obtain and epoxy resin have good consistency, and solidification value is suitable for, but its latent is still not ideal enough at present.
Summary of the invention
The object of the invention is to solve above-mentioned the deficiencies in the prior art, a kind of acyl substituted imidazoles incubated epoxide curing agent is provided.Solidifying agent latent of the present invention is good, solidification value is moderate and good with epoxy resin compatibility.
Another object of the present invention is to the preparation method that above-mentioned incubated epoxide curing agent is provided.
The object of the invention is achieved through the following technical solutions:
A kind of acyl substituted imidazoles incubated epoxide curing agent, its structure is such as formula shown in I, II or III:
R in formula 1for H, methyl, ethyl or phenyl, R 2for H or methyl, R 3for methyl, ethyl or phenyl, R 4for phenyl or p-methylphenyl, n=0,2 or 4.
Described acyl substituted imidazoles incubated epoxide curing agent reacts obtained by glyoxaline compound and acyl chloride compound.
Described glyoxaline compound is such as formula shown in IV:
R in formula 1for H, methyl, ethyl or phenyl; R 2for H or methyl.
Described acyl chloride compound is such as formula shown in V, VI or VII:
Described glyoxaline compound is preferably imidazoles, glyoxal ethyline or 2-ethyl-4-methylimidazole, and now described acyl chloride compound is Adipoyl Chloride.
Described glyoxaline compound is preferably 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole or 2-phenylimidazole, and now described acyl chloride compound is Acetyl Chloride 98Min. or Benzoyl chloride.
Described glyoxaline compound is preferably imidazoles, glyoxal ethyline or 2-ethyl imidazol(e), and now described acyl chloride compound is Tosyl chloride.
The preparation method of described acyl substituted imidazoles incubated epoxide curing agent, comprises the following steps:
(1) adopt solvent by glyoxaline compound wiring solution-forming, and add triethylamine in solution, pass into N 2, dissolve, obtain glyoxaline compound solution;
(2) adopt solvent by acyl chloride compound wiring solution-forming, obtain acyl chloride compound solution; At N 2under condition, acyl chloride compound solution is slowly added drop-wise in the glyoxaline compound solution of step (1), drips rear continuation reaction 5 ~ 15h;
(3) after having reacted, vacuum filtration, and filtrate is carried out rotary evaporation until evaporate to dryness at Rotary Evaporators;
(4) rotate the product of evaporate to dryness with solvent wash, be then placed in loft drier and carry out drying, obtain acyl substituted imidazoles incubated epoxide curing agent.
Solvent described in step (1) is more than one in tetrahydrofuran (THF), methylene dichloride, ethylene dichloride, acetonitrile, acetone or butanone; Described glyoxaline compound in the solution mass percent concentration is 2 ~ 13%.
Solvent described in step (2) is more than one in tetrahydrofuran (THF), methylene dichloride, ethylene dichloride, acetonitrile, acetone or butanone; By mass percentage, the concentration of acyl chloride compound solution is 5 ~ 20%.
The mol ratio of glyoxaline compound and triethylamine described in step (1) is (1:1) ~ (1:2).
In step (2) when acyl chloride compound is single functionality acyl chloride compound, the mol ratio of described glyoxaline compound and single functionality acyl chloride compound is (1:1) ~ (1:1.5); When acyl chloride compound is difunctionality acyl chloride compound, the mol ratio of described glyoxaline compound and difunctionality acyl chloride compound is (1:0.5) ~ (1:0.75).
Solvent described in step (4) be in polar solvent or non-polar solvent more than one; Described solvent preferably adopt polar solvent and non-polar solvent composite, polar solvent and non-polar solvent mass ratio are (1:1) ~ (1:4).Polar solvent described in step (4) is more than one in water, ethyl acetate or butylacetate; Non-polar solvent is more than one in sherwood oil, ether, solvent oil or toluene.The boiling range of described sherwood oil is 60 ~ 90 DEG C; The boiling range of described solvent oil is 60 ~ 90 DEG C.
The speed dripped described in step (2) is 10 ~ 20/min; The temperature of described reaction is room temperature.
The condition of rotary evaporation described in step (3) is temperature is 60 ~ 70 DEG C, and rotating speed is 90 ~ 100r/min, and vacuum tightness is 0.085 ~ 0.095Mpa.
Temperature dry described in step (4) is 50 ~ 80 DEG C, and the dry time is 2 ~ 3h; The actual conditions of described drying is prior to 50 ~ 60 DEG C of drying 1 ~ 1.5h, then in 70 ~ 80 DEG C of drying 1.5 ~ 2h.
Generally, the curing mechanism of glyoxaline compound to epoxy resin comprises two parts: on the one hand, the secondary amine on imidazole ring can with epoxy group(ing) generation ring-opening reaction; On the other hand, the imine nitrogen atom on imidazole ring has very strong electron donation, can cause epoxy resin epoxy group and carry out ring-opening polymerization.
The active hydrogen of the present invention on acyl substituted imidazoles 1; secondary amine is not only allowed to lose the ability with epoxy resin generation ring-opening reaction; simultaneously because the strong sucting electronic effect of acyl group weakens the electron donation of imines; the energy barrier allowing itself and epoxy resin react improves; lose curing activity at normal temperatures, thus possess good latent.And when temperature be elevated to be enough to overcome energy barrier that imines and epoxy resin reacts time, acyl substituted imidazole curing agent can recover curing activity again.
In the present invention, acyl substituted imidazole curing agent mixes by a certain percentage with epoxy resin, and test by the following method: (1) adopts the dynamic exotherm of dsc (DSC) test system, and then analyzes its curing performance; (2) by curing system in storage in room temperature, observe the time that it loses flowability, to test its package stability; (3) system is allowed to solidify under constant temperature and record surface drying time, further its solidification effect of test.
Relative to prior art, tool of the present invention has the following advantages and beneficial effect:
(1) compared to existing imidazole curing agent, in the present invention, the package stability of acyl substituted imidazole curing agent is greatly improved, and latent period is 1 ~ 6 month, can be used for the preparation of single component epoxy coating, tackiness agent;
(2) acyl substituted imidazole curing agent and epoxy resin have good consistency, easily form homogeneous system, make cured product have more excellent mechanical property, and reduce technology difficulty;
(3) Dyhard RU 100 and organic hydrazides to the solidification value of epoxy resin all more than 170 DEG C, and in the present invention acyl substituted imidazole curing agent to the solidification value of epoxy resin between 120 ~ 160 DEG C, reduce because the too high infringement caused material of solidification value;
(4) be raw materials usedly marketable product, synthesis technique is simple, is easy to realize batch production.
Accompanying drawing explanation
The DSC curve of 1-ethanoyl-2-ethyl-4-methylimidazole that Fig. 1 is prepared for embodiment 1 and the curing system that epoxy resin is formed;
The DSC curve of 1-benzoyl-glyoxal ethyline that Fig. 2 is prepared for embodiment 2 and the curing system that epoxy resin is formed;
The DSC curve of the 1-propionyl-2-phenylimidazole that Fig. 3 is prepared for embodiment 3 and the curing system that epoxy resin is formed;
Fig. 4 is 1 of embodiment 4 preparation, the DSC curve of the curing system that 1 '-succinyl two-2-phenylimidazole and epoxy resin are formed;
Fig. 5 is 1 of embodiment 5 preparation, the DSC curve of the curing system that 1 '-adipyl diimidazole and epoxy resin are formed;
The DSC curve of benzenesulfonyl-2-ethyl-4-methylimidazole that Fig. 6 is prepared for embodiment 6 and the curing system that epoxy resin is formed;
The DSC curve of the p-toluenesulfonyl imidazoles that Fig. 7 is prepared for embodiment 7 and the curing system that epoxy resin is formed.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) synthesis of 1-ethanoyl-2-ethyl-4 Methylimidazole
(1-1) by 2-ethyl-4 Methylimidazole (5.02g, 0.05mol) and 50g tetrahydrofuran (THF) (THF) wiring solution-forming, add triethylamine (6.07g, 0.05mol), pass into N 2, at room temperature stirring (rotating speed of stirring is 300r/min) to dissolving, obtaining glyoxaline compound solution;
(1-2) Acetyl Chloride 98Min. (3.93g, 0.05mol) is dissolved in 50g THF, obtains acyl chloride compound solution, at N 2under condition, slowly be added drop-wise in the glyoxaline compound solution of step (1-1) with dropping funnel, time for adding is about 1h (speed of dropping is 20/min), drip relief system at room temperature to continue to react 8h, vacuum filtration is with the solid by-product generated except dereaction, and filtrate is spin-dried in Rotary Evaporators (condition of rotary evaporation is the temperature of rotary evaporation is 60 DEG C, rotating speed is 90r/min, vacuum tightness is 0.085MPa), then be the sherwood oil/n-butyl acetate mixed solvent washed product of 4:1 with mass ratio, to remove unreacted 2-ethyl-4 Methylimidazole, dry and (first at 50 DEG C, dry 1.5h, then at 80 DEG C, 1.5h is dried), obtain dark red solution and 1-ethanoyl-2-ethyl-4 methyl imidazole curing agent, triethylamine and solvent (THF) are with first carrying out molecular sieve dehydration before.
(2) application of solidifying agent and sign
Added in E-51 type epoxy resin by 1-ethanoyl-2-ethyl-4 Methylimidazole, stir (the time 10min of stirring, rotating speed is 200r/min), obtains curing system; By mass percentage, in curing system, 1-ethanoyl-2-ethyl-4 Methylimidazole content is 7%.
The performance of curing system is characterized: (1) adopts the dynamic exotherm of DSC test system, and temperature rise rate is 10 DEG C/min, and test curve as shown in Figure 1 by the following aspects; (2) by curing system in storage in room temperature, observe the time that it loses flowability; (3) allow system solidify under the constant temperature of 90 DEG C, 120 DEG C respectively, and record surface drying time, test result is as shown in table 1 ~ 2.
Embodiment 2
(1) synthesis of 1-benzoyl-glyoxal ethyline
(1-1) by glyoxal ethyline (4.11g, 0.05mol) and 50g butanone wiring solution-forming, add triethylamine (6.58g, 0.065mol), pass into N 2and be at room temperature stirred to dissolving (rotating speed of stirring is 300r/min), obtain glyoxaline compound solution;
(1-2) Benzoyl chloride (7.73g, 0.055mol) is dissolved in 50g acetone, obtains acyl chloride compound solution; At N 2under condition, be slowly added drop-wise in the glyoxaline compound solution of step (1-1) with dropping funnel, time for adding is about 1.2h (rate of addition is 20/min); Drip relief system at room temperature to continue to react 9h; vacuum filtration is with the solid by-product generated except dereaction; and filtrate is spin-dried in Rotary Evaporators (temperature of rotary evaporation is 70 DEG C; rotating speed is 90r/min; vacuum tightness is 0.09MPa); then use deionized water wash product, to remove unreacted glyoxal ethyline, dry (at 80 DEG C, drying 2h) and obtain weak yellow liquid and 1-benzoyl-glyoxal ethyline solidifying agent.
(2) application of solidifying agent and sign
Added in E-51 type epoxy resin by 1-benzoyl-glyoxal ethyline, stir (the time 10min of stirring, rotating speed is 200r/min), obtains curing system; By mass percentage, the content of 1-benzoyl-glyoxal ethyline is 8%.
The performance of curing system is characterized: (1) adopts the dynamic exotherm of DSC test system, and temperature rise rate is 10 DEG C/min, and test curve as shown in Figure 2 by the following aspects; (2) by curing system in storage in room temperature, observe the time that it loses flowability; (3) allow system solidify under the constant temperature of 90 DEG C, 120 DEG C respectively, and record surface drying time; Test result is as shown in table 1 ~ 2.
Embodiment 3
(1) synthesis of 1-propionyl-2-phenylimidazole
(1-1) by 2-phenylimidazole (7.21g, 0.05mol) and 100g THF wiring solution-forming, add triethylamine (6.07g, 0.06mol), pass into N 2, be at room temperature stirred to dissolving (rotating speed of stirring is 300r/min), obtain glyoxaline compound solution; Triethylamine and solvent molecular sieve dehydration before experiment;
(1-2) propionyl chloride (4.63g, 0.05mol) is dissolved in 50g THF, obtains acyl chloride compound solution; At N 2under condition, be slowly added drop-wise in the glyoxaline compound solution of step (1-1) with dropping funnel, time for adding is about 1h (rate of addition is 20/min); Drip relief system at room temperature to continue to react 8h; vacuum filtration is with the solid by-product generated except dereaction; and filtrate is spin-dried in Rotary Evaporators (temperature of rotary evaporation is 60 DEG C; rotating speed is 95r/min; vacuum tightness is 0.085MPa); then be the petrol ether/ethyl acetate mixed solvent washed product of 4:1 with mass ratio; to remove unreacted 2-phenylimidazole; dry and (first at 50 DEG C, dry 1.5h; then at 80 DEG C, 1.5h is dried), obtain weak yellow liquid and 1-propionyl-2-phenylimidazole solidifying agent.
(2) application of solidifying agent and sign
Added in E-51 type epoxy resin by 1-propionyl-2-phenylimidazole, stir (the time 10min of stirring, rotating speed is 200r/min), obtains curing system; By mass percentage, 1-propionyl-2-phenylimidazole content is 8%.
The performance of curing system is characterized: (1) adopts the dynamic exotherm of DSC test system, and temperature rise rate is 10 DEG C/min, and test curve as shown in Figure 3 by the following aspects; (2) curing system is observed its time lost flowability in storage in room temperature; (3) allow system solidify under the constant temperature of 90 DEG C, 120 DEG C respectively, and record surface drying time; Test result is as shown in table 1 ~ 2.
Embodiment 4
The synthesis of (1) 1,1 '-succinyl two-2-phenylimidazole
(1-1) first by 2-phenylimidazole (10.1g, 0.07mol), 60g CH 2cl 2with 60g ethylene dichloride wiring solution-forming, add triethylamine (10.12g, 0.1mol), pass into N 2and be at room temperature stirred to dissolving (rotating speed of stirring is 300r/min), obtain glyoxaline compound solution; Triethylamine and solvent molecular sieve dehydration before experiment;
(1-2) succinic chloride (5.42g, 0.035mol) is dissolved in 60g ethylene dichloride, obtains acyl chloride compound solution; At N 2under condition, be slowly added drop-wise in the glyoxaline compound solution of step (1-1) with dropping funnel, time for adding is about 1.5h (speed of dropping is 11/min); Drip relief system at room temperature to continue to react 8h; vacuum filtration is with the solid by-product generated except dereaction; and filtrate is spin-dried in Rotary Evaporators (temperature of rotary evaporation is 65 DEG C; rotating speed is 95r/min; vacuum tightness is 0.095MPa); then be the ether/toluene Mixed Solvent washed product of 3:1 with mass ratio; to remove unreacted 2-phenylimidazole; dry and (first at 50 DEG C, dry 1h; then at 80 DEG C, 2h is dried); obtain dark red solution i.e. 1,1 '-succinyl two-2-phenylimidazole solidifying agent.
(2) application of solidifying agent and sign
1,1 '-succinyl two-2-phenylimidazole adds in E-51 type epoxy resin, and stir (the time 10min of stirring, rotating speed is 200r/min), obtains curing system; By mass percentage, 1,1 '-succinyl two-2-phenylimidazole content is 6%.
The performance of curing system is characterized: (1) adopts the dynamic exotherm of DSC test system, and temperature rise rate is 10 DEG C/min, and test curve as shown in Figure 4 by the following aspects; (2) by curing system in storage in room temperature, observe the time that it loses flowability; (3) allow system solidify under the constant temperature of 90 DEG C, 120 DEG C respectively, and record surface drying time; Test result is as shown in table 1 ~ 2.
Embodiment 5
(1) 1, the synthesis of 1 '-adipyl diimidazole
(1-1) by imidazoles (5.45g, 0.08mol), 70g CH 2cl 2with 70g ethylene dichloride wiring solution-forming, add triethylamine (10.12g, 0.1mol), pass into N 2and be at room temperature stirred to dissolving (rotating speed of stirring is 300r/min), obtain glyoxaline compound solution; Triethylamine and solvent molecular sieve dehydration before experiment;
(1-2) Adipoyl Chloride (8.78g, 0.048mol) is dissolved in 70g THF, obtains acyl chloride compound solution; At N 2under condition, be slowly added drop-wise in the glyoxaline compound solution of step (1-1) with dropping funnel, time for adding is about 1.5h (20/min); Drip relief system at room temperature to continue to react 8h; vacuum filtration is with the solid by-product generated except dereaction; and filtrate is spin-dried in Rotary Evaporators (temperature of rotary evaporation is 70 DEG C; rotating speed is 100r/min; vacuum tightness is 0.09MPa); then be the ether/toluene Mixed Solvent washed product of 2:1 with mass ratio; to remove unreacted EMI; dry and (first at 50 DEG C, dry 1h; then at 80 DEG C, 2h is dried); obtain yellow liquid that is 1,1 '-adipyl diimidazole solidifying agent.
(2) application of solidifying agent and sign
1,1 '-adipyl diimidazole adds in E-51 type epoxy resin, and stir (the time 10min of stirring, rotating speed is 200r/min), obtains curing system; By mass percentage, in described curing system 1,1 '-adipyl diimidazole content is 7%.
Performance by the following aspects representation system: (1) adopts the dynamic exotherm of DSC test system, and temperature rise rate is 10 DEG C/min, and test curve as shown in Figure 5; (2) by curing system in storage in room temperature, observe the time that it loses flowability, (3) allow system solidify under the constant temperature of 90 DEG C, 120 DEG C respectively, and record surface drying time; Test result is as shown in table 1 ~ 2.
Embodiment 6
(1) synthesis of benzenesulfonyl-2-ethyl-4-methylimidazole
(1-1) by 2-ethyl-4-methylimidazole (5.02g, 0.05mol), 60g CH 2cl 2with 40 acetonitrile wiring solution-formings, add triethylamine (7.59g, 0.075mol), pass into N 2and be at room temperature stirred to dissolving (rotating speed of stirring is 300r/min), obtain glyoxaline compound solution;
(1-2) benzene sulfonyl chloride (10.60g, 0.06mol) is dissolved in 50g CH 2cl 2in, obtain acyl chloride compound solution; At N 2under condition, be slowly added drop-wise in the glyoxaline compound solution of step (1-1) with dropping funnel, time for adding is about 1h (speed of dropping is 15/min); Drip relief system at room temperature to continue to react 12h; vacuum filtration is with the solid by-product generated except dereaction; and filtrate is spin-dried in Rotary Evaporators (temperature of rotary evaporation is 65 DEG C; rotating speed is 90r/min; vacuum tightness is 0.095MPa); then be the solvent oil/n-butyl acetate mixed solvent washed product of 2:1 with mass ratio; to remove unreacted 2-ethyl-4 Methylimidazole; dry and (first at 50 DEG C, dry 1h; then at 80 DEG C, 1.5h is dried), obtain yellow crystals and benzenesulfonyl-2-ethyl-4-methylimidazole solidifying agent.
(2) application of solidifying agent and sign
Benzenesulfonyl-2-ethyl-4-methylimidazole is added in E-51 type epoxy resin, and Yong Nian Portland mills, make solidifying agent be dispersed in resin with Powdered, then at room temperature place 24h, crystal and resin-phase Rongcheng homogeneous system, obtain curing system; By mass percentage, benzenesulfonyl-2-ethyl-4-methylimidazole content is 15%.
Performance by the following aspects representation system: (1) adopts the dynamic exotherm of DSC test system, and temperature rise rate is 10 DEG C/min, and test curve as shown in Figure 6; (2) by curing system in storage in room temperature, observe the time that it loses flowability; (3) allow system solidify under the constant temperature of 140 DEG C, 165 DEG C respectively, and record surface drying time; Test result is as shown in table 1 ~ 2.
Embodiment 7
(1) synthesis of p-toluenesulfonyl imidazoles
(1-1) by imidazoles (4.08g, 0.06mol), 80g CH 2cl 2with 40g acetonitrile wiring solution-forming, add triethylamine (12.13g, 0.12mol), pass into N 2, be at room temperature stirred to dissolving (rotating speed of stirring is 300r/min), obtain glyoxaline compound solution;
(1-2) Tosyl chloride (17.16g, 0.09mol) is dissolved in 70g CH 2cl 2in, obtain acyl chloride compound solution, at N 2under condition, slowly be added drop-wise in the glyoxaline compound solution of step (1-1) with dropping funnel, time for adding is about 1.2h (rate of addition is 18/min), drip relief system at room temperature to continue to react 15h, vacuum filtration is with the solid by-product generated except dereaction, and filtrate is spin-dried in Rotary Evaporators (temperature of rotary evaporation is 60 DEG C, rotating speed is 95r/min, vacuum tightness is 0.095MPa), then be the solvent oil/n-butyl acetate mixed solvent washed product of 1:1 with mass ratio, to remove unreacted imidazoles, dry and (first at 50 DEG C, dry 1h, then at 80 DEG C, 1.5h is dried), obtain yellow crystals and p-toluenesulfonyl imidazole curing agent.
(2) application of solidifying agent and sign
P-toluenesulfonyl imidazoles adds in E-51 type epoxy resin, stirs, and mills with stone roller Portland, and solidifying agent is dispersed in resin with Powdered, then at room temperature places 24h, and crystal and resin-phase Rongcheng homogeneous system, obtain curing system; By mass percentage, in described curing system, p-toluenesulfonyl imidazole content is 15%.
Performance by the following aspects representation system: (1) adopts the dynamic exotherm of DSC test system, and temperature rise rate is 10 DEG C/min, and test curve as shown in Figure 7; (2) by curing system in storage in room temperature, observe the time that it loses flowability, (3) allow system solidify under the constant temperature of 140 DEG C, 165 DEG C respectively, and record surface drying time; Test result is as shown in table 1 ~ 2.
The parameter of the curing system DSC curve of each embodiment of table 1
Solidifying agent Start exothermic temperature (DEG C) Exothermic peak temperature (DEG C) ΔH tot(J/g)
1-ethanoyl-2-ethyl-4-methylimidazole 121.5 142.0 385
1-benzoyl-glyoxal ethyline 126.4 143.5 406
1-propionyl-2-phenylimidazole 128.8 146.7 394
1,1 '-succinyl two-2-phenylimidazole 134.3 150.9 371
1,1 '-adipyl diimidazole 131.7 149 378
Benzenesulfonyl-2-ethyl-4-methylimidazole 156.4 197.9 316
P-toluenesulfonyl imidazoles 149.0 188.2 321
The storage period of each embodiment curing system of table 2 and surface drying time
Above-described embodiment is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.All any amendments done within the spirit and principles in the present invention, equivalent to replace and improvement etc., within the protection domain that all should be included in the claims in the present invention.

Claims (10)

1. an acyl substituted imidazoles incubated epoxide curing agent, is characterized in that: its structure is such as formula shown in I, II or III:
R in formula 1for H, methyl, ethyl or phenyl, R 2for H or methyl, R 3for methyl, ethyl or phenyl, R 4for phenyl or p-methylphenyl, n=0,2 or 4.
2. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 1, is characterized in that: comprise the following steps:
(1) adopt solvent by glyoxaline compound wiring solution-forming, and add triethylamine in solution, pass into N 2, dissolve, obtain glyoxaline compound solution;
(2) adopt solvent by acyl chloride compound wiring solution-forming, obtain acyl chloride compound solution; At N 2under condition, acyl chloride compound solution is slowly added drop-wise in the glyoxaline compound solution of step (1), drips rear continuation reaction 5 ~ 15h;
(3) after having reacted, vacuum filtration, and filtrate is carried out rotary evaporation until evaporate to dryness at Rotary Evaporators;
(4) rotate the product of evaporate to dryness with solvent wash, be then placed in loft drier and carry out drying, obtain acyl substituted imidazoles incubated epoxide curing agent.
3. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 2, is characterized in that: described glyoxaline compound is such as formula shown in IV:
R in formula 1for H, methyl, ethyl or phenyl; R 2for H or methyl;
Described acyl chloride compound is such as formula shown in V, VI or VII:
(V); N=0 in formula, 2 or 4;
(VI); R in formula 3for methyl, ethyl or phenyl;
(VII); R in formula 4for phenyl or p-methylphenyl.
4. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 2; it is characterized in that: described glyoxaline compound is imidazoles, glyoxal ethyline or 2-ethyl-4-methylimidazole, now described acyl chloride compound is Adipoyl Chloride.
5. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 2; it is characterized in that: described glyoxaline compound is 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole or 2-phenylimidazole, now described acyl chloride compound is Acetyl Chloride 98Min. or Benzoyl chloride.
6. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 2; it is characterized in that: described glyoxaline compound is preferably imidazoles, glyoxal ethyline or 2-ethyl imidazol(e), now described acyl chloride compound is Tosyl chloride.
7. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 2, is characterized in that: solvent described in step (1) is more than one in tetrahydrofuran (THF), methylene dichloride, ethylene dichloride, acetonitrile, acetone or butanone; Described glyoxaline compound in the solution mass percent concentration is 2 ~ 13%;
Solvent described in step (2) is more than one in tetrahydrofuran (THF), methylene dichloride, ethylene dichloride, acetonitrile, acetone or butanone; Described acyl chloride compound mass percent concentration in acyl chloride compound solution is 5 ~ 20%;
The mol ratio of glyoxaline compound and triethylamine described in step (1) is (1:1) ~ (1:2);
Solvent described in step (4) be in polar solvent or non-polar solvent more than one; Described polar solvent is more than one in water, ethyl acetate or butylacetate; Non-polar solvent is more than one in sherwood oil, ether, solvent oil or toluene.
8. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 7, it is characterized in that: solvent described in step (4) is the composite of polar solvent and non-polar solvent, and described polar solvent and non-polar solvent mass ratio are (1:1) ~ (1:4); Described in step (4), the boiling range of sherwood oil is 60 ~ 90 DEG C; The boiling range of described solvent oil is 60 ~ 90 DEG C.
9. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 2, it is characterized in that: in step (2) when acyl chloride compound is single functionality acyl chloride compound, the mol ratio of described glyoxaline compound and single functionality acyl chloride compound is (1:1) ~ (1:1.5); When acyl chloride compound is difunctionality acyl chloride compound, the mol ratio of described glyoxaline compound and difunctionality acyl chloride compound is (1:0.5) ~ (1:0.75).
10. the preparation method of acyl substituted imidazoles incubated epoxide curing agent according to claim 2, is characterized in that: the speed dripped described in step (2) is 10 ~ 20/min; The temperature of described reaction is room temperature;
The condition of rotary evaporation described in step (3) is temperature is 60 ~ 70 DEG C, and rotating speed is 90 ~ 100r/min, and vacuum tightness is 0.085 ~ 0.095Mpa;
Temperature dry described in step (4) is 50 ~ 80 DEG C, and the dry time is 2 ~ 3h.
CN201510468673.4A 2015-07-31 2015-07-31 Acyl-substituted iminazole latent epoxy resin curing agent and preparation method thereof Pending CN104974094A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510468673.4A CN104974094A (en) 2015-07-31 2015-07-31 Acyl-substituted iminazole latent epoxy resin curing agent and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510468673.4A CN104974094A (en) 2015-07-31 2015-07-31 Acyl-substituted iminazole latent epoxy resin curing agent and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104974094A true CN104974094A (en) 2015-10-14

Family

ID=54271110

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510468673.4A Pending CN104974094A (en) 2015-07-31 2015-07-31 Acyl-substituted iminazole latent epoxy resin curing agent and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104974094A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111423347A (en) * 2020-04-30 2020-07-17 万华化学集团股份有限公司 Latent epoxy resin curing agent and preparation method and application thereof
CN115160229A (en) * 2022-05-31 2022-10-11 上海大学 Modified imidazole latent epoxy resin curing agent and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816324A (en) * 1967-09-18 1974-06-11 L Fine Bleaching compositions containing a n-acyl azole
US4343923A (en) * 1980-08-07 1982-08-10 Armstrong World Industries, Inc. Process for reducing the acid dye uptake of polyamide textile materials with N-acylimidazole compound
US6342545B1 (en) * 1998-11-23 2002-01-29 Loctite Corporation Radical-curable adhesive compositions, reaction products of which demonstrate superior resistance to thermal degradation
WO2014059089A1 (en) * 2012-10-10 2014-04-17 Luminescent MD, LLC Chemiluminescent aptasensors
CN104086751A (en) * 2014-06-25 2014-10-08 华南理工大学 DOPO-based symtriazine ring hydrogenated benzimidazole epoxy curing agent and preparation method thereof
CN104098555A (en) * 2014-07-15 2014-10-15 江西科技师范大学 Method for synthesizing ultrashort-wavelength photochromic diarylethene compound by using imidazole-thiophene aromatic heterocycle and application of compound

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816324A (en) * 1967-09-18 1974-06-11 L Fine Bleaching compositions containing a n-acyl azole
US4343923A (en) * 1980-08-07 1982-08-10 Armstrong World Industries, Inc. Process for reducing the acid dye uptake of polyamide textile materials with N-acylimidazole compound
US6342545B1 (en) * 1998-11-23 2002-01-29 Loctite Corporation Radical-curable adhesive compositions, reaction products of which demonstrate superior resistance to thermal degradation
WO2014059089A1 (en) * 2012-10-10 2014-04-17 Luminescent MD, LLC Chemiluminescent aptasensors
CN104086751A (en) * 2014-06-25 2014-10-08 华南理工大学 DOPO-based symtriazine ring hydrogenated benzimidazole epoxy curing agent and preparation method thereof
CN104098555A (en) * 2014-07-15 2014-10-15 江西科技师范大学 Method for synthesizing ultrashort-wavelength photochromic diarylethene compound by using imidazole-thiophene aromatic heterocycle and application of compound

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
AKIRA SUGIHARA: "Nitrofuran derivatives. VII. Synthesis of 2-[2-(5-nitro-2-furyl) vinyl]-2-imidazoline", 《YAKUGAKU ZASSHI》 *
AVIJIT BANERJI,等: "Effect of sodium naphthalenide, a key SET reagent, on trifluoroacetyl derivatives", 《TETRAHEDRON LETTERS》 *
DINGFENG LEI,等: "Preparation of 2-ethyl-4-methylimidazole derivatives as latent curing agents and their application in curing epoxy resin", 《JOURNAL OF APPLIED POLYMER SCIENCE》 *
KANDARPA PHUKAN: "REGIOSELECTIVE N-ACYLATION OF HETEROCYCLIC AMINES UNDER DRY CONDITIONS CATALYZED BY A NATURAL CLAY", 《INTERNATIONAL JOURNAL OF APPLIED BIOLOGY AND PHARMACEUTICAL TECHNOLOGY》 *
SAMY MOHAMADY,等: "Sulfonyl Imidazolium Salts as Reagents for the Rapid and Efficient Synthesis of Nucleoside Polyphosphates and Their Conjugates", 《ORG. LETT.》 *
SHAUL FREIREICH,等: "ACYLATION OF ACIDIC NITROGEN COMPOUNDS N-STANNYL DERIVATIVES", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 *
刘全文,等: "咪唑类环氧树脂固化剂研究进展", 《国外建材科技》 *
张宝华, 等: "改性咪唑环氧树脂中温固化剂的制备与性能", 《高分子材料科学与工程》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111423347A (en) * 2020-04-30 2020-07-17 万华化学集团股份有限公司 Latent epoxy resin curing agent and preparation method and application thereof
CN111423347B (en) * 2020-04-30 2022-04-19 万华化学集团股份有限公司 Latent epoxy resin curing agent and preparation method and application thereof
CN115160229A (en) * 2022-05-31 2022-10-11 上海大学 Modified imidazole latent epoxy resin curing agent and preparation method thereof

Similar Documents

Publication Publication Date Title
CN102471462B (en) Aluminum chelate-based latent curing agents and process for preparation thereof
CN104974094A (en) Acyl-substituted iminazole latent epoxy resin curing agent and preparation method thereof
CN107163301A (en) A kind of high hydroscopic resin and its preparation method and application
CN105237737A (en) Dicyandiamide type epoxy resin curing agent and preparation method and application thereof
CN102863275A (en) Sustained or controlled-release potash fertilizer and preparation method thereof
CN101583648A (en) Latent curing agent
CN107955133A (en) Imidazole Type Latent Curing Agent containing triazine ring structure and preparation method thereof
CN108003326A (en) Imidazole Type Latent Curing Agent containing maleimide structure and preparation method thereof
CN104530020A (en) Method for preparing maleimide-containing epoxy resin curing agent
CN104479136B (en) Nonionic epoxy emulsifier and preparation method thereof
CN109437658A (en) A kind of concrete water-retaining agent and preparation method thereof
CN102500255A (en) Carbon nano tube dispersing method
CN107840942B (en) Imidazole Type Latent Curing Agent of the ring structure containing triazinetrione and preparation method thereof
CN102190792B (en) Functionalized hyperbranched polyphenylene ether and method for preparing same
CN103589157A (en) Preparation method of addition-type liquid silicone rubber platinum complex with long storage life
CN106045886B (en) A kind of two ﹣ of compound (biguanides base is to phenyl) methane and its synthetic method, application
CN106243325A (en) A kind of heat-resisting incubated epoxide curing agent and preparation method thereof
CN103665324B (en) A kind of epoxy resin lalent solidifying agent and corresponding epoxypaint
CN115160229A (en) Modified imidazole latent epoxy resin curing agent and preparation method thereof
CN102559119A (en) One-component epoxy encapsulating adhesive with good rheological stability and preparation method thereof
CN103087295B (en) Latent hyperbranched polymer curing agent and its preparation method
CN103073919A (en) Solvent yellow 33
CN108192290A (en) A kind of environment protecting thermal insulating material used for building exterior wall and preparation method thereof
CN103242370A (en) Metal organic gel based on tetrazole compounds
CN103664834A (en) Thermal degradation epoxy resin monomer and preparation method and bottom fillers thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20151014