CN1154981A - Mannich base solidification agent - Google Patents
Mannich base solidification agent Download PDFInfo
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- CN1154981A CN1154981A CN 96121606 CN96121606A CN1154981A CN 1154981 A CN1154981 A CN 1154981A CN 96121606 CN96121606 CN 96121606 CN 96121606 A CN96121606 A CN 96121606A CN 1154981 A CN1154981 A CN 1154981A
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Abstract
A Mannich base curing agent is provided, prepared by reacting butyraldehyde, a phenolic compound and a primary or secondary amine. These curing agents are useful as sole curing agents or as co-curing agents for epoxy resin systems.
Description
The present invention relates to a kind of solidifying agent.On the one hand, the present invention relates to be used for the mannich base solidification agent of epoxy-resin systems.
About numerous various epoxy curing agents, the derivative of amine and amine is the most practical for cured epoxy resin.As a compounds, these are unique available such materials, and these materials at room temperature solidify the potentiality that provide enough for film and piece material.Aromatic amine curing agent is widely used.But, because toxicity has limited the use of aromatic amine substantially.Present solidifying agent based on amine mainly be aliphatic series or cyclic aliphatic, just for example be diethylenetriamine, isophorone diamine and 1 in nature, the 2-diamino-cyclohexane.
The hardener formula of many commodity is that these amine have been used the certain methods modification based on these aliphatic series and amine cyclic aliphatic, in order that improve the ratio of mixture with Resins, epoxy aspect processing characteristics, perhaps reduces the toxicity of these basic amines.Used most of commercial available amine is the quite little molecule with relatively a large amount of nitrogen.Low-molecular-weight amine is sufficiently volatile, and this causes in the air volume of sealing can run up to dangerous concentration.
As organic bases, amine easily and moisture and carbon dioxide reaction in the atmosphere form corresponding amine carbonate.This is enough to stop or suppress the reaction of amine and epoxide.This phenomenon is the most tangible in the curing of film.If the Resins, epoxy of coating and unmodified amine blended coating do not toast will keep a large amount of uncured.In addition, amine carbonate is insoluble in the base-material, and is retained in the surface of coating as the film that optical haze arranged, and is called " hazing ", " turning white " or " oozing out ".
Amine general with Resins, epoxy be such blended, consequently adopt each epoxy group(ing) to the unitary ratio of the hydrogen of an amine.When the epoxy hardener, the ethyleneamines of lower molecular weight has and forms the ability of cross-linked network closely.Yet at ambient temperature, curing speed slows down with the increase of polymer viscosity, unless consequently use promotor or elevated temperature for compensation, is incomplete otherwise solidify.In order to solidify at ambient temperature, must carry out modification to low-molecular-weight high functional amine in some way, so that carbonation reduces to minimum, improves curing performance and reduces volatility.
Mannich base is to make carbonation reduce to the example of the amine modification of minimum.The mannich base compound is based on the product of aldehyde (normally formaldehyde), phenolic compound and amine reaction.Commercial available mannich base is based on formaldehyde, and this formaldehyde is that the aqueous solution as gas uses, or use with the polymerized form of Paraformaldehyde 96.
High aldehyde helps making with liquid epoxies blended mannich base and possesses: (1) rapid curing under envrionment temperature and the temperature that reduced; (2) the general good chemical-resistant in excellent mechanical intensity and hardness performance and (3).But such high-content can make the viscosity of product be elevated to above the available scope.Concerning most of purposes of relevant this solidifying agent, what want is low viscosity.
According to the present invention, a kind of composition epoxy resin is provided, this composition contains:
(a) per molecule have at least 1.5 epoxy group(ing) Resins, epoxy and
(b) by (i) butyraldehyde, the (ii) phenolic compound and the (iii) mannich base of uncle or the prepared in reaction of secondary polyamine.
This composition is applicable to the purposes of tackiness agent, ground, sealing and coating.
Therefore shared for Resins, epoxy it is desirable to obtain such low viscosity mannich base solidification agent, and the viscosity of this solidifying agent generally is lower than 5000 centipoises in the time of 25 ℃, preferably is lower than 1000 centipoises.Have been found that epoxy-resin systems of the present invention has good use properties and low viscosity, this system contains by (i) butyraldehyde, the (ii) phenolic compound and the (iii) mannich base of uncle or the prepared in reaction of secondary polyamine.
Reaction by butyraldehyde, phenolic compound and uncle or secondary polyamine can prepare mannich base.The mol ratio of polyamines and phenolic compound was generally 1: 1 to 10: 1, was preferably 2: 1 to 4: 1.Based on equivalent, butyraldehyde should be less than or equal to whenever measuring amine nitrogen to 1 mole of butyraldehyde with the ratio of polyamines.Equally, butyraldehyde should be less than or equal to whenever measuring phenolic compound to 1 mole of butyraldehyde with the ratio of phenolic compound.
In general, polyamines and phenolic compound are put into a suitable container, mix fully.Add butyraldehyde then within a certain period of time continuously or incrementally.Reaction is spontaneous and is actual heat release.Need temperature control unit.Add fully after the aldehyde, remove the water that forms as by product by distillation.Can think that the chemical reaction between synthesis phase comprises that aldehyde and phenolic compound form the electrophilic addition of the phenol intermediate of alkane alcoholization.Further, produce the mannich reaction product with the amine condensation with except that anhydrating.These products are as the single curing agent of epoxy-resin systems or help solidifying agent to be used.
Phenolic compound can be any compound that contains at least one hydroxyl that is connected with at least one aromatic ring.As long as at least one carbon atom is unsubstituted in 2,4 or 6 for the carbon atom that has hydroxyl, above-mentioned aromatic ring then can have one or more substituting groups, for example alkyl.Preferred phenolic compound can be represented with following general formula:
R wherein
1And R
2Be hydrogen or C independently
1-C
12(preferred C
1-C
4) alkyl.R
1And R
2Can be straight chain, side chain or aromatics.The example of the phenolic compound that is fit to comprises phenol, nonyl phenol, butylphenol, ortho-cresol, meta-cresol, p-cresol, quinhydrones, p-phenyl phenol and 4-dodecylphenol.Polyamines can be any uncle or secondary polyamine.Preferred polyamines can be represented with following general formula:
H
2N-(R
3-NH-)
m-(R
4-)
n-NH
2R wherein
3And R
4Be the alkyl of divalence, preferably contain 2-20 carbon atom; M and n are the integers of 0-5, and condition is that m and n can not be 0 (m+n is 1 at least) simultaneously.As long as the amine that connects is aliphatic primary amine or secondary amine, above-mentioned alkyl can be alkylidene group side chain or straight chain, cyclic aliphatic base or can contain aryl.The example of polyamines comprises 2-methylpentane diamines, Triethylenetetramine (TETA), isophorone diamine, m-xylylene amine and 1,2-diamino-cyclohexane.
Mannich base solidification agent is to exist with the amount of cured epoxy resin effectively.The weight ratio of Resins, epoxy and mannich base solidification agent was generally 1: 1 to 5: 1, was preferably 2: 1 to 3: 1.
Generally do not need curing catalyst,, can use curing catalyst if still want to accelerate the solid speed of epoxy curing agent system.As long as curing catalyst can be dissolved in the mannich base solidification agent, can use the various curing catalysts compatible with amine.The example of available curing catalyst comprises 2,4,6-three (dimethylaminomethyl) phenol, N, N-diethylethanolamine, N, N-dimethyl benzyl amine etc.If exist, the general concentration of such curing catalyst can be preferably 1%-5% for the 0.1%-10% of mannich base solidification agent.
Resins, epoxy can be to use any Resins, epoxy of mannich base solidification agent solidified.In general, Resins, epoxy can be 1, the 2-epoxy equivalent (weight) greater than 1 and preferably per molecule on average contain any curable Resins, epoxy more than 1.5 epoxy group(ing).Resins, epoxy can be saturated or unsaturated, straight chain or side chain, aliphatic series, cyclic aliphatic, aromatics or heterocyclic, and can have the substituting group that hinders curing reaction indistinctively.Such substituting group can comprise bromine.Resins, epoxy can be monomeric or polymeric, liquid or solid, but preferably at room temperature be liquid.The Resins, epoxy that is fit to comprises glycidyl ether, it be by Epicholorohydrin with contain at least one, the best compound of two or more hydroxyls prepared in reaction of under basic reaction conditions, carrying out.The example that is applicable to Resins, epoxy of the present invention comprises the polyglycidyl ether, novolac epoxy resin of polyphenol or the similarly polyglycidyl ether of poly-phenol resins, alcohol, dibasic alcohol or the poly-dihydric alcohol of Racemic glycidolization and the poly epihydric alcohol base ester of poly carboxylic acid.
Preferred Resins, epoxy is based on the resin of the polyglycidyl ether of polyphenol.For example, by the reaction of Epicholorohydrin in the presence of alkali and polyphenol, can produce the polyglycidyl ether of polyphenol.The example of the polyphenol that is fit to comprises: 2, two (4-hydroxy phenyl) propane (bisphenol-A), 2 of 2-, two (4-hydroxyl-3-tert-butyl-phenyl) propane, 1 of 2-, two (4-hydroxy phenyl) ethane, 1 of 1-, two (4-hydroxy phenyl) Trimethylmethanes of 1-, two (2-hydroxyl-1-naphthyl) methane, 1,5-dihydroxy naphthlene, 1, two (4-hydroxyl-3-alkylbenzene) ethane of 1-etc.The polyphenol that is fit to also can obtain (bisphenol-f) by the reaction of phenol and aldehyde (for example formaldehyde).The polyglycidyl ether of these polyphenol and the phenolic compound for example molten product of bisphenol-A also are fit to as Resins, epoxy, for example those described in the U.S.P.3477990 and 4734468.The example of the commodity of preferred Resins, epoxy for example comprises the EPON resin 862,828,826,825 and 1001 (EPON is a trade mark) that obtains from ShellChemical Company.
These preferred Resins, epoxy can also be mixed with the glycidyl ether of alcohol, dibasic alcohol or the poly-dihydric alcohol of aliphatic series or aromatics or the glycidyl ester of monocarboxylic acid in case of necessity.Some examples comprise butylglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, 1,4-butanediol diglycidyl ether, neodecanoic acid glycidyl ester etc.In order to influence some performances, for example wettability, viscosity, flexibility, binding property or the like can make these glycidyl ethers mix with preferred Resins, epoxy with about 1% to about 50% concentration.EPON resin 815,813 and 8132 (sale of Shell chemical company) is the example that contains the preferred epoxy of such properties-correcting agent.
Preferred epoxy-resin systems of the present invention can contain one or more Resins, epoxy and contain the solidifying agent of mannich base.Can be under the situation that is lower than solidification value (generally being lower than 100 ℃), make Resins, epoxy with the solidifying agent fusion that contains mannich base or mix simultaneously or with any order.
Be used as when helping solidifying agent, can use Manny phase solidifying agent with other epoxy curing agent based on butyraldehyde.Such solidifying agent comprises the reaction product by the reaction formation of the monoglycidyl ether of excessive polyamines and monocarboxylic acid or poly carboxylic acid, Resins, epoxy, fatty alcohol or aromatic alcohol or monocarboxylic acid or polycarboxylic glycidyl ester.Such modified amine is well-known in this technology.
Can be under-40 ℃ to 150 ℃ (preferred-10 ℃ to 150 ℃) temperature, in the time of cured epoxy resin effectively, curable composition epoxy resin is solidified.For the ambient cure purposes of standard, said composition is preferably under 15 ℃ to 40 ℃ the envrionment temperature solidifies.
In addition, for the ease of the processing in various environment, application or use, can dilute solidifying agent or epoxy-resin systems with a spot of aliphatic hydrocrbon, aromatic hydrocarbons, alcohol or glycol ethers.
Decide with purposes, composition epoxy resin of the present invention can contain other additive, for example flowing regulator, defoamer or anti-sagging agent, and can contain the other additive, for example pigment, toughener, filler, elastomerics, stablizer, extender, softening agent or fire retardant.
This composition epoxy resin is applicable to tackiness agent, coating, ground, casting and sealing.
Can use curable composition epoxy resin by brushing, roller coat, spraying, blade coating or alternate manner, perhaps said composition be poured into or is injected in the suitable mould and make its curing.
When being used for tackiness agent, generally can be under the temperature of envrionment temperature or rising, with pure or with solvent cut curable composition epoxy resin be applied on the base material.Make solvent, if any, evaporation also forces together base material, and tackiness agent is solidified.
When being used for terrestrial applications, curable composition epoxy resin is mixed with sand, granulated glass sphere, powdery talc or aluminum oxide, metal-powder, filler, pigment etc., and be applied on the base material by brushing, trowelling, blade coating or other mode that is fit to.
When being used for the coating purposes, curable composition epoxy resin can contain all kinds of SOLVENTS, filler, flowing regulator, pigment and tinting material or softening agent.Can said composition be used for base material by brushing, spraying, roller coat, blade coating or any mode that other is fit to.
When being used for casting and sealing, curable composition epoxy resin also can contain various fillers, pigment, softening agent etc., can make this composition be incorporated on the goods or be incorporated in the suitable mould by cast, injection or other method, use this composition thus.
These curable composition epoxy resins form goods, for example tackiness agent, coating, tackiness agent, foundry goods and sealing agent during curing.
Following illustrative embodiment has been narrated method of the present invention, and these embodiments provide for illustrative purposes, and does not mean that limitation of the present invention.
Compare with the mannich base solidification agent for preparing with other aldehyde among Comparative Examples a, b, c, d and the e, embodiment 1,2,3,4,5,6 and 7 explanations have low viscosity with the mannich base solidification agent of butyraldehyde, phenolic compound and diamines preparation.Embodiment 8 has illustrated the epoxy-resin systems of the present invention that uses based on the mannich base solidification agent of butyraldehyde.
Purity is that 99% butyraldehyde obtains from Aldrich.Paraformaldehyde 96 and 37% water-containing acetal obtain from Janssen.
M-xylylene amine obtains from Mitsubishi Gas Chemical.Isophorone diamine is from Huls America, and Inc. obtains.Purity is that 99% 2-methyl pentamethylene diamine (Dytek A) and diamino-cyclohexane obtain from Dupont Chemicals.Triethylenetetramine (TETA) obtains from Dow Chemical Company.
Phenol obtains from Mallinckrodt.P-tert-butylphenol obtains from Schenectady.Nonyl phenol obtains from General Electric.
EPON Resin 828 (epoxy equivalent (weight) is the diglycidylether of the dihydroxyphenyl propane of 185-192) obtains from Shell Chemical Company.
Be higher than formaldehyde though have been found that the molecular weight of butyraldehyde,, using the result of butyraldehyde rather than formaldehyde or Paraformaldehyde 96 is that product unexpectedly shows low viscosity.In general, the increase of molecular weight is relevant with higher viscosity.Data point in table 1 and the table 2 provides the offset information that this phenomenon is described.Embodiment 1
In 1 liter of 3 neck flask that agitator, thermopair, condenser, distillation receptor and feed hopper are housed, add 272 gram (2 moles) m-xylylene amines (" MXDA ") and 94 gram (1 mole) phenol.With the nitrogen purging flask contents and be heated to 48 ℃.In 47-50 ℃ of insulation, in 60 minutes, in mixture, drip 144 gram (2 moles) butyraldehyde.Be warming up to 160 ℃ in insulation under 47-54 ℃ after other 60 minutes, in this temperature-rise period, collect all distillates.After 20 minutes, be warming up to 170 ℃ 160 ℃ of insulations.45 minutes postcooling flask contents and discharging.Product is the 465.8 gram light amber liquid that contain 11.8% titratable nitrogen, and the weight of this product per gallon is 8.65 pounds, and Brookfield viscosity is 181 centipoises in the time of 25 ℃.Embodiment 2
Repeat embodiment 1 except replacing the 94 gram phenol with 150 gram (1 mole) p-tert-butylphenols.Obtain containing 523.7 gram products of 10.44% titratable nitrogen, the weight of this product per gallon is 8.42 pounds, and viscosity is 194 centipoises in the time of 25 ℃.
Comparative Examples a
In 2 liter of 3 neck flask that stirring, thermopair, condenser and distillation susceptor are housed, add 188 gram (2 moles) phenol, 544 gram (4 moles) m-xylylene amines and 30 gram deionized waters.With the nitrogen purging flask contents and be heated to 45 ℃.In 47 ℃-52 ℃, add the 134 gram Paraformaldehyde 96s that concentration is 90%-92% in insulation with the speed of per 30 minutes 33.5 grams.After 60 minutes, in 40 minutes, flask contents is heated to 100 ℃.After 10 minutes, there is undissolved Paraformaldehyde 96 to exist 100 ℃ of insulations.Add other 30 gram deionized waters.When collecting all distillates, make flask contents be warming up to 160 ℃.After 230 minutes, there is undissolved material to exist.Flask contents cooling and jam-pack are spent the night.Second day, use the nitrogen purging flask contents, in 30 minutes, be warming up to 165 ℃, 163 ℃-165 ℃ insulations 515 minutes.Then, cooling flask contents and discharging.The synthetic product is the heavy-gravity liquid that contains 14.09% titratable nitrogen, and the weight of this product per gallon is 9.48 pounds, and Brookfield viscosity is 278000 centipoises in the time of 25 ℃.Comparative Examples b
96.5% concentration of adding 228 grams (1 mole) restrains (2 moles) m-xylylene amines to nonyl phenol and 272 in 2 liter of 3 neck flask that agitator, thermopair, condenser and distillation susceptor are housed.Use the nitrogen purging flask contents, in 20 minutes, be warming up to 65 ℃.With 162.2 gram (2 moles) concentration is that 37% water-containing acetal restrains the deionized water pre-mixings with 137.8, and they are joined in another feed hopper.In 64 ℃-65 ℃ of insulations, in 115 minutes, this drips of solution is added in the flask contents.Flask contents was mixed 60 minutes at 65 ℃.Be warmed up to 100 ℃, seethe with excitement in this temperature.Keep boiling 60 minutes.Remove all distillates then, make flask contents be warming up to 160 ℃, this temperature insulation 60 minutes.Cooling flask contents and discharging.The synthetic product is the thick liquid that contains 10.43% titratable nitrogen, and the weight of this product per gallon is 8.67 pounds, and Brookfield viscosity is 178000 centipoises in the time of 25 ℃.Embodiment 3
Except with 228 gram (1 mole) concentration be 96.5% nonyl phenol is replaced repeating embodiment 1 the 94 gram phenol.Obtain the product that 602.6 grams contain 9.10% titratable nitrogen, this product weight per gallon is 8.26 pounds, and Brookfield viscosity is 304 centipoises.
Embodiment 4
In 3 liter of 3 neck flask that agitator, thermopair, condenser and distillation susceptor are housed, add 300 gram (2 moles) p-tert-butylphenols and 342 gram (3 moles) diamino-cyclohexane (" DACH ").Use the nitrogen purging flask contents, be warming up to 49 ℃-51%.In 49 ℃-51 ℃ of insulations, in 120 minutes, in mixture, drip 216 gram (3 moles) butyraldehyde.Behind other 80 minutes, be warmed up to 170 ℃.In this temperature-rise period, collect all distillates.After 30 minutes, cool off flask contents and discharging 170 ℃ of insulations.Product is 795 gram amber color liquids, and this liquid Brookfield viscosity in the time of 25 ℃ is 354 centipoises, and the weight of per gallon is 8.05 pounds, and titratable nitrogen content is 10.33%.Comparative Examples C
In 3 liter of 3 neck flask that agitator, thermopair, condenser and distillation susceptor are housed, add 342 gram (3 moles) diamino-cyclohexane and 300 gram (2 moles) p-tert-butylphenols.Use the nitrogen purging flask contents, be warmed up to 50 ℃.Dripping 243 gram (3 moles) concentration is 37% water-containing acetal.Be warming up to 170 ℃ simultaneously at distillatory.After 60 minutes, cool off flask contents and discharging 170 ℃ of insulations.Product is 784.6 gram amber color liquids, and the Brookfield viscosity of this liquid is greater than 1000000 centipoises in the time of 25 ℃, and its titratable nitrogen content is 11.61%.Comparative Examples d
With the method for summarizing among the Comparative Examples b, the prescription that preparation is made up of the water-containing acetal and the 68.9 gram deionized waters of 340.6 gram (2 moles) isophorone diamines (" IPDA "), 150 gram (1 mole) p-tert-butylphenols, 81.1 gram (1 moles) 37%.The synthetic product is the heavy-gravity liquid that contains 10.81% titratable nitrogen content, and the weight of this liquid per gallon is 8.13 pounds, and viscosity is 15700 centipoises in the time of 25 ℃.Embodiment 5
Except replacing repeating Comparative Examples d the water-containing acetal of 81.1 grams 37% without deionized water with 72 gram (1 mole) butyraldehyde.The synthetic product is the amber color liquid that contains 9.97% titratable nitrogen content, and the weight of this liquid per gallon is 7.85 pounds, and viscosity is 262 centipoises in the time of 25 ℃.
Comparative Examples e
In 3 liter of 3 neck flask that agitator, thermopair, condenser and distillation susceptor are housed, add 584 gram (4 moles) Triethylenetetramine (TETA)s (" TETA ") and 514 gram (3.45 moles) p-tert-butylphenols.Use the nitrogen purging flask contents, in 20 minutes, make it be warming up to 65 ℃.In 65 ℃, in 60 minutes, in this mixture, drip the water-containing acetal of 243.2 gram (3 moles) 37% in insulation.After another 60 minutes, make temperature rise to 160 ℃.In this temperature-rise period, collect all distillates.After 45 minutes, make flask contents cooling and discharging 65 ℃ of insulations.Product is 1181.5 gram light amber liquid, and this liquid Brookfield viscosity in the time of 25 ℃ is 6200 centipoises, and the weight of per gallon is: 8.50 pounds, titratable nitrogen content is 18.18%.
Embodiment 6
Add 174 gram (3 moles) Dytek A in 1 liter of 3 neck flask that agitator, thermopair, condenser and distillation susceptor are housed, it is 2-methyl pentamethylene diamine (" the MPMDA ") preparation of commodity, and 150 gram (2 moles) p-tert-butylphenols.Use the nitrogen purging flask contents, be warming up to 73 ℃.After solution occurring, in 73 ℃, in 60 minutes, drip 108 gram (3 moles) butyraldehyde in insulation.Insulation 73 ℃ after 60 minutes, make flask contents be warming up to 163 ℃ simultaneously at distillatory.Insulation after 15 minutes, makes flask contents cooling and discharging 170 ℃ of mistakes.Product is 408.5 gram amber color liquids, and the Brookfield viscosity of this liquid in the time of 25 ℃ is 69 centipoises, and the weight of per gallon is 7.69 pounds, and titratable nitrogen content is 10.07%.
Embodiment 7
In 1 liter of 3 neck flask that agitator, thermopair, condenser, distillation susceptor and feed hopper are housed, add 136 gram (1 mole) m-xylylene amines and 220 grams to nonylphenol.With the nitrogen purging flask contents and make its mixing.During mixing, make temperature be raised to 34 ℃.In 50 minutes, in mixture, drip 72 gram (1 mole) butyraldehyde, make temperature rise to 49 ℃ simultaneously.Insulation is warming up to 100 ℃ at 47 ℃-49 ℃ after other excessively 10 minutes.Between this temperature raising period, collect all distillates., vacuumize and steam volatile matter after 120 minutes 100 ℃ of insulations.Reclaim sample and test its viscosity down at 40 ℃.This moment, viscosity was 175 centipoises.JP-A-48-78254 has enumerated the prescription based on Gong the comparison of formaldehyde, and this dispensing viscosity is 4700 centipoises in the time of 40 ℃.
Embodiment 8
Test implementation example 1 and the embodiment 2 synthetic products performance during as the solidifying agent of EPON 828.To per 100 parts of EPON 828, with the ratio of mixture of 42.1 parts and 47.1 parts, the composition of embodiment 1 and embodiment 2 is mixed with EPON 828 respectively.Solidified 16 hours with the mixture injection glass mold of formation and at 75 °F, under 200 °F, in baking oven, toasted 2 hours then.From glass mold, take out the 1/8 inch thick sheet material that forms, carry out machining with this sheet material and form suitable test sample, and test its tensile property and chemical resistant properties.The data of the acquisition of listing in the table 1 show that the product that makes according to the present invention is suitable for use as solidifying agent.
Table 1
| Embodiment/Comparative Examples | ????1 | ?????2 | ????a |
| The kind of amine | ????MXDA | ????MXDA | ????MXDA |
| The kind of aldehyde | ????B 1 | ?????B 1 | ????P 1 |
| The kind of phenol | Phenol | Butylphenol | Phenol |
| Mol ratio: amine/aldehyde/phenol | ????2/2/1 | ????2/2/1 | ????2/2/1 |
| The titratable nitrogen content of weight (pound/gallon) (%) of physical constant viscosity (centipoise) per gallon | ????181 ????8.65 ????11.8 | ?????194 ?????8.42 ????10.44 | ????278000 ????9.48 ????14.09 |
| Ratio of mixture (phr) with EPON Resin 828 2 | ????42.1 | ?????47.1 | |
| Use properties tensile strength (pound/inch 2) tensile modulus (* 10 6) weightening finish (%) of elongation (%) in following material 3: the dimethylbenzene/IPA of the acetate 50/50 of deionized water 5% | ????12270 ????0.52 ????7.7 ????0.11 ????0.11 ????0.05 | ????12530 ?????0.53 ?????5.2 ?????0.11 ?????0.11 ?????0.58 |
B
1=butyraldehyde; P
1=Paraformaldehyde 96.
The sheet material casting spare that the 2:1/8 inch is thick solidified 16 hours at 75 ℃ of F, solidified 2 hours at 200 °F then.
3: soaked 24 hours.
Table 2
The water-containing acetal of 1:F=37%; The B=butyraldehyde; The P=Paraformaldehyde 96.
| Embodiment/Comparative Examples | ????b | ????3 | ????4 | ????c |
| The kind of amine | ????MXDA | ????MXDA | ????DACH | ????DACH |
| The kind of aldehyde | ????F 1 | ????B 1 | ????B 1 | ????F 3 |
| The kind of phenol | Nonyl phenol | Nonyl phenol | Butylphenol | Butylphenol |
| Mol ratio: amine/aldehyde/phenol | ????2/2/1 | ????2/2/1 | ????3/2/2 | ????3/2/2 |
| The titratable nitrogen content of weight (pound/gallon) (%) of physical constant viscosity (centipoise) per gallon | ????178000 ????8.67 ????10.43 | ????304 ????8.26 ????9.10 | ????354 ????8.05 ????10.33 | ????＞1000000 ????----- ????11.61 |
Table 2 (continuing)
| Embodiment/Comparative Examples | ????d | ????5 | ????e | ????6 | ????7 |
| The kind of amine | ????IPDA | ????IPDA | ????TETA | ????MPMDA | ????MXDA |
| The kind of aldehyde | ????F 1 | ????B 1 | ????F 1 | ????B 3 | ????B 1 |
| The kind of phenol | Butylphenol | Butylphenol | Butylphenol | Butylphenol | Nonyl phenol |
| Mol ratio: amine/aldehyde/phenol | ????2/2/1 | ????2/2/1 | ????4/3/3.45 | ????3/3/2 | ????1/1/0.965 |
| The titratable nitrogen content of weight (pound/gallon) (%) of physical constant viscosity (centipoise) per gallon | ????15700 ????8.13 ????10.81 | ????262 ????7.85 ????9.97 | ????6200 ????8.26 ????16.58 | ????69 ????7.69 ????10.07 | ????1752 ????8.17 ????6.86 |
The water-containing acetal of 1:F=37%; The B=butyraldehyde; The P=Paraformaldehyde 96.
2: in the time of 40 ℃, record.
Claims (10)
1. curable composition, said composition contains:
(a) per molecule have at least 1.5 epoxy group(ing) Resins, epoxy and
(b) by (i) butyraldehyde, the (ii) phenolic compound and the (iii) mannich base of uncle or the prepared in reaction of secondary polyamine.
2. the composition of claim 1, phenolic compound wherein can be represented with following general formula:
R wherein
1And R
2Be hydrogen or C independently
1-C
12Alkyl.
3. claim 1 and 2 composition, polyamines wherein can be represented with following general formula:
H
2N-(-R
3-NH-)
m-(-R
4-)
n-NH
2
R wherein
3And R
4Be C
2-C
20The alkyl of divalence, m and n are the integers of 0-5, condition is that m+n is at least 1.
4. the composition of claim 3, polyamines wherein is selected from 2 methyl pentamethylenediamine, Triethylenetetramine (TETA), isophorone diamine, m-xylylene amine and 1,2-diamino-cyclohexane.
5. the composition of claim 1-4, Resins, epoxy wherein is the polyglycidyl ether of polyphenol.
6. the composition of claim 1, wherein the weight ratio of Resins, epoxy and mannich base is 1: 1-5: 1, preferred 2: 1-3: 1.
7. the composition of claim 1-6, said composition also contains (c) and the different curing agent for epoxy resin of component (b).
8. the composition of solidified claim 7.
9. use the curable composition epoxy resin substrates coated of claim 1-7.
10. goods comprise the moulded products that has the surface and be applied to the binder composition on the above-mentioned part surface at least, and above-mentioned binder composition contains the composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96121606 CN1154981A (en) | 1995-12-13 | 1996-12-11 | Mannich base solidification agent |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US572,199 | 1984-01-19 | ||
| CN 96121606 CN1154981A (en) | 1995-12-13 | 1996-12-11 | Mannich base solidification agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1154981A true CN1154981A (en) | 1997-07-23 |
Family
ID=5126953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96121606 Pending CN1154981A (en) | 1995-12-13 | 1996-12-11 | Mannich base solidification agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1154981A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348563B (en) * | 2008-09-17 | 2010-11-10 | 中昊晨光化工研究院 | Tough mannich base curing agent and preparation thereof |
| CN102803367A (en) * | 2009-06-04 | 2012-11-28 | 阿肯马法国公司 | Use of molecules having associative groups as hardeners for thermosetting resins |
| CN105542129A (en) * | 2016-02-25 | 2016-05-04 | 武汉理工大学 | High-toughness hydrophobic epoxy hardener and preparation method thereof |
| WO2022160584A1 (en) * | 2021-01-26 | 2022-08-04 | 江苏凯伦建材股份有限公司 | Polyurethane waterproof coating, preparation method therefor and use thereof |
-
1996
- 1996-12-11 CN CN 96121606 patent/CN1154981A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348563B (en) * | 2008-09-17 | 2010-11-10 | 中昊晨光化工研究院 | Tough mannich base curing agent and preparation thereof |
| CN102803367A (en) * | 2009-06-04 | 2012-11-28 | 阿肯马法国公司 | Use of molecules having associative groups as hardeners for thermosetting resins |
| CN105542129A (en) * | 2016-02-25 | 2016-05-04 | 武汉理工大学 | High-toughness hydrophobic epoxy hardener and preparation method thereof |
| WO2022160584A1 (en) * | 2021-01-26 | 2022-08-04 | 江苏凯伦建材股份有限公司 | Polyurethane waterproof coating, preparation method therefor and use thereof |
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