CN101624440A - Intermediate temperature latent thermal curing agents for epoxy resin - Google Patents
Intermediate temperature latent thermal curing agents for epoxy resin Download PDFInfo
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- CN101624440A CN101624440A CN200810116283A CN200810116283A CN101624440A CN 101624440 A CN101624440 A CN 101624440A CN 200810116283 A CN200810116283 A CN 200810116283A CN 200810116283 A CN200810116283 A CN 200810116283A CN 101624440 A CN101624440 A CN 101624440A
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Abstract
The invention discloses intermediate temperature latent thermal curing agents and a preparation method thereof. The compounds are characterized by having a cyclopentadienyl-iron-N-alkyl carbazole ferrocenium salt structure. The compounds are prepared from raw materials, namely ferrocene and N-alkyl substituted carbazole through ligand exchange reaction under the catalysis of Lewis acid. As the latent curing agents, the compounds can initiate ring opening polymerization of epoxy compounds at mild temperature, and have good thermal initiating activity and latent thermal performance. The solubility of the compounds in nonpolar resin is obviously strengthened due to the introduction of alkyl, and the compounds have wide study potential and application prospect in the field of epoxy resin application.
Description
Technical field
The present invention relates to the preparation and the application of warm latent thermal curing agents in the class, particularly a class is used for the preparation and the application of the thermofixation initiator of epoxy compounds.
Background technology
Resins, epoxy be a class have well cohere, the thermosetting polymer synthetic materials of performance such as corrosion-resistant, insulation, high strength, the aspects such as manufacturing that are widely used in the cohering of multiple metal and non-metallic material, corrosion resistant coating, electrical apparatus insulation material, glass reinforced plastic/matrix material, in electronics, electric, machinofacture, chemical anticorrosion and other many industrial circles, play an important role, become indispensable base mateiral in each industrial circle.
Epoxy curing systems commonly used is a bicomponent system, solidifying agent acid anhydrides commonly used and amine substance, and there is following shortcoming in bicomponent system: layoutprocedure is loaded down with trivial details; Batch mixes is inhomogeneous, and curing performance can fluctuate; Error in the metering is difficult to avoid or the like.
Latent curing agent is meant under the room temperature in Resins, epoxy can long-time stable existence, and can cause the compound system of curing reaction under effects such as heating rapidly.The Resins, epoxy latent curing agent is the raw material of preparation one-component epoxy resin system.The kind of the Resins, epoxy latent curing agent of having developed is a lot, mainly contain boron trifluoride complex, trimeric cyanamide and derivative thereof, imdazole derivatives and organic hydrazides class etc., but every type solidifying agent all has certain merits and demerits, up to the present, still do not find the latent curing agent that a kind of performance is good especially, very good.Good Resins, epoxy latent curing agent requirement has suitable use temperature, short set time, long usage period.Moreover, along with the raising of people to environmental protection consciousness, development of new low toxicity and the nontoxic environment-friendly epoxy resin latent curing agent trend that is inevitable.
Summary of the invention
The purpose of this invention is to provide warm latent thermal curing agents in the based epoxy resin, this compounds has the luxuriant molysite structure of cyclopentadiene-iron-N-alkyl carbazole, its chemical structure of general formula as shown in the formula:
R, R ', R " and R " ' be H, alkyl, thiazolinyl, phenyl ring, substituted benzene ring, naphthalene nucleus or replace naphthalene nucleus, R ', R " and R " ' substituent number n is 1-6, X
-For non-nucleophilicity negatively charged ion as SbF
4 -, AsF
6 -, PF
6 -, BF
4 -, CF
3SO
3 -Or CH
3SO
31
-
The present invention is an example with the luxuriant molysite compound of preparation N-alkyl substituted carbazole ligand, and its reaction equation is as follows:
The preparation method of the luxuriant molysite compound of N-alkyl substituted carbazole ligand of the present invention following (following all represent) with molar fraction:
(1) reacts under alkaline condition by carbazole, bromoalkane, phase-transfer catalyst and make the N-alkyl carbazole.Reaction conditions is: 1 part of carbazole, 1-1.5 part bromoalkane, 1-1.5 part sodium hydroxide and a small amount of phase-transfer catalyst are dissolved in the anhydrous tetrahydro furan of 10-15 part, after stirring, reaction mixture slowly is heated to 40 ℃ of backflows, keeps reaction 8-10 hour.
(2) make cyclopentadiene-iron-N-alkyl carbazole salt by N-alkyl carbazole and ferrocene, Lewis acid-respons.Reaction conditions is: with 1 part of ferrocene, 1-1.5 part N-alkyl carbazole, the anhydrous AlCl of 2-5 part
3, a small amount of Al powder and 10-20 part naphthenic hydrocarbon pours in the four-hole boiling flask N into
2Protection after stirring, is kept backflow 6-12h with the slow heating of reaction mixture.Promptly get product after adding NaMXn or KMXn after the hydrolysis.
The Resins, epoxy latent thermal curing agents that the present invention prepares can be used for the thermofixation of aliphatics and alicyclic epoxide compound, be particularly useful for alicyclic epoxide compound, as 3,4-epoxy group(ing) hexahydrobenzoic acid-3 ', 4 '-epoxy group(ing) cyclohexyl methyl esters (ERL4221) and 4,5-epoxy hexane-1,2-dioctyl phthalate 2-glycidyl ester (TDE85).
Description of drawings
Fig. 1 be the luxuriant molysite of N-alkyl substituted carbazole of 1% weight ratio as the latent heat initiator, epoxy compounds ERL4221 is carried out thermal initiation solidified differential thermal analysis curve.The luxuriant molysite of four kinds of N-alkyl substituted carbazole ligands is respectively [cyclopentadiene-iron-carbazole] hexafluorophosphate, [cyclopentadiene-iron-(N-ethyl) carbazole] hexafluorophosphate, [cyclopentadiene-iron-(N-butyl) carbazole] hexafluorophosphate, [cyclopentadiene-iron-(N-octyl group) carbazole] hexafluorophosphate.
Fig. 2 be the luxuriant molysite of N-alkyl substituted carbazole of 1% weight ratio as the latent heat initiator, epoxy compounds TDE85 is carried out thermal initiation solidified differential thermal analysis curve.The luxuriant molysite of four kinds of N-alkyl substituted carbazole ligands is respectively [cyclopentadiene-iron-carbazole] hexafluorophosphate, [cyclopentadiene-iron-(N-ethyl) carbazole] hexafluorophosphate, [cyclopentadiene-iron-(N-butyl) carbazole] hexafluorophosphate, [cyclopentadiene-iron-(N-octyl group) carbazole] hexafluorophosphate.
Embodiment
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1
Present embodiment is carried out as follows: get 0.038molN-butyl carbazole, 0.025mol ferrocene, the anhydrous AlCl of 0.075mol
3, 0.025mol Al powder and 50ml hexanaphthene drop in the there-necked flask, makes its stirring and dissolving, logical N
2Slowly be warming up to 84 ℃ then, keep reflux state 10h.The question response liquid cooling but to wherein pouring 10% methanol solution into, is stirred hydrolysis, filters, and separatory washes organic phase with water, after merging with water, uses the hexanaphthene repetitive scrubbing, adds excessive KPF then
6The aqueous solution promptly has the orange precipitation to separate out.With solid drying, promptly get product [cyclopentadiene-iron-N-butyl carbazole] hexafluorophosphate through the column chromatography purification.
Present embodiment is that the luxuriant molysite of N-alkyl substituted carbazole carries out thermal initiation curing as the latent heat initiator to epoxy compounds ERL4221: get the luxuriant molysite of 0.01 gram N-alkyl substituted carbazole and join among the epoxy compounds ERL4221 of 1 gram, fully stir and make its dissolving, get the 5-10 milligram and put into the DSC differential thermal analyzer and carry out the thermofixation analysis.Test condition is: heat-up rate be 10 the degree/minute; N
2Gas shiled; Temperature range is the 50-250 degree.Experiment data such as the table 1 surveyed.
Embodiment 3
Present embodiment is that the luxuriant molysite of N-alkyl substituted carbazole carries out thermal initiation curing as the latent heat initiator to epoxy compounds TDE85: get the luxuriant molysite of 0.01 gram N-alkyl substituted carbazole and join among the epoxy compounds TDE85 of 1 gram, fully stir and make its dissolving, get the 5-10 milligram and put into the DSC differential thermal analyzer and carry out the thermofixation analysis.Test condition is: heat-up rate be 10 the degree/minute; N
2Gas shiled; Temperature range is the 50-250 degree.Experiment data such as the table 2 surveyed.
The DSC data of the heat cured system that luxuriant molysite of table 11% carbazole and ERL4221 form
The DSC data of the heat cured system that luxuriant molysite of table 21% carbazole and TDE85 form
Claims (3)
- Warm latent thermal curing agents in 1 one based epoxy resins, this compounds have the luxuriant molysite structure of cyclopentadiene-iron-N-alkyl carbazole, its chemical structure of general formula as shown in the formula:
R, R ', R " and R ' " be H, alkyl, thiazolinyl, phenyl ring, substituted benzene ring, naphthalene nucleus or replace naphthalene nucleus, R ', R " and R ' " substituent number n is 1-6, X -For non-nucleophilicity negatively charged ion as SbF 4 -, AsF 6 -, PF 6 -, BF 4 -, CF 3SO 3 -Or CH 3SO 3 - - 2 preparation methods of compound according to claim 1 is characterized in that with N-alkyl carbazole and ferrocene be raw material, are catalyzer with Lewis acid and Al powder, react to make cyclopentadiene-iron-N-alkyl carbazole salt (II).Reaction conditions is: with 1 part of ferrocene, 1-1.5 part N-alkyl carbazole, the anhydrous AlCl of 2-5 part 3, a small amount of Al powder and 10-20 part non-reactive solvent, pour in the four-hole boiling flask N into 2Protection after stirring, is slowly heated reaction mixture, keeps backflow 6-12h.Promptly get product after adding NaX or KX after the hydrolysis.
- 3 according to claim 1 compound be used to cause the thermofixation of epoxy compounds, epoxy compounds comprises aliphatic epoxy compound and alicyclic epoxide compound.
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| CN200810116283A CN101624440A (en) | 2008-07-08 | 2008-07-08 | Intermediate temperature latent thermal curing agents for epoxy resin |
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|---|---|---|---|
| CN200810116283A CN101624440A (en) | 2008-07-08 | 2008-07-08 | Intermediate temperature latent thermal curing agents for epoxy resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273167A (en) * | 2014-06-19 | 2016-01-27 | 北京化工大学 | Applications of iron arene salt as sensitizer used for initiating photocuring of iodonium salt under visible light |
| CN114058306A (en) * | 2021-12-21 | 2022-02-18 | 韦尔通(厦门)科技股份有限公司 | Underfill adhesive and preparation method and application thereof |
-
2008
- 2008-07-08 CN CN200810116283A patent/CN101624440A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273167A (en) * | 2014-06-19 | 2016-01-27 | 北京化工大学 | Applications of iron arene salt as sensitizer used for initiating photocuring of iodonium salt under visible light |
| CN114058306A (en) * | 2021-12-21 | 2022-02-18 | 韦尔通(厦门)科技股份有限公司 | Underfill adhesive and preparation method and application thereof |
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Open date: 20100113 |