CN101370846B - Curing agents for epoxy-functional compounds - Google Patents
Curing agents for epoxy-functional compounds Download PDFInfo
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- CN101370846B CN101370846B CN2007800024860A CN200780002486A CN101370846B CN 101370846 B CN101370846 B CN 101370846B CN 2007800024860 A CN2007800024860 A CN 2007800024860A CN 200780002486 A CN200780002486 A CN 200780002486A CN 101370846 B CN101370846 B CN 101370846B
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- 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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
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Abstract
The present invention relates to compounds suitable to use as curing agents for epoxy systems which can be obtained by reacting an amine-functional compound with an alpha-beta unsaturated acid and/or ester and a mono-functional epoxy compound. The invention further relates to coating compositions comprising these curing agents.
Description
The present invention relates to a kind of amine functional group solidifying agent that is used for epoxy-functional compounds.In this article, amine functional group represent to comprise-NH or-NH
2One or more of group.The invention still further relates to the application of this amine-epoxy systems in coating composition and the matrix that is coated with this coating composition.
Some amine functional compounds that can be used for the cured epoxy functional compounds is with healthy relevant with environmental problem.For example, they can be sensitization of skin agent (skin sensitiser).In addition, in the curing of the system that contains epoxy-functional compounds, amine functional compounds may be to general envrionment conditions sensitivity, for example humidity and carbonic acid gas.
When curing comprised the coating composition of epoxy-functional compounds and amine functional compounds, the problem that often runs into was to form so-called " amine frosting ".The possible explanation that forms for the amine frosting is when film forms, the amine functional group solidifying agent can with water and CO
2Form carbaminate.These carbaminates are usually incompatible with the coated membrane body and be exuded to the surface.Therefore form grease-like layer (" amine frosting ") on the surface of solidified coating, it has adverse influence to outward appearance and external coating (EC).Amine functional group solidifying agent and water and CO
2The another one consequence of reaction is its reaction that stops amine and epoxide.Therefore, have only seldom amine functional group and epoxy-functional to react.This is influential for the network that forms in film, and therefore influences the character of film.When taking place under being solidificated in low temperature and high humidity, the amine frosting is the most general.
In 40 years, there is the people to make great efforts to make amine-epoxide reaction to handle the risk of these materials for envrionment conditions of curing reaction more insensitive, more stable (robust) and reduction in the past.Generally, can accomplish these by the pre-reaction of amine functional compounds.Reaction product has the free amine molecule of less amount and therefore more stable to envrionment conditions in solidification process.In addition, reaction product is generally the molecule bigger than unreacted amine functional compounds.When fully big, the use of molecule will be safer.A reason of this situation is that abundant big molecule can not enter human skin and meeting therefore can not be as the skin sensitization agent.The amine hardener that can suppose the EU definition of satisfying polymkeric substance more safely uses than ungratified.
For example, well-known, amine functional compounds and aliphatic glycidyl ether reaction are to obtain being used for the amine functional compounds of cured epoxy functional compounds.Yet this mode still has shortcoming.If polyamines and the reaction of aliphatics bifunctional glycidyl ether, the amine functional compounds that obtains may be difficult to store.In the storage, not really stable and possibility " separating out " (the seed out) of this amine functional compounds, promptly solid particulate may be deposited to the hold-up vessel bottom.Possible explanation to this problem is that most of aliphatic glycidyl ethers contain high-caliber relatively hydrolyzable chlorine.In the storage, hydrolyzable chlorine can experience reaction and the formation ammonium salt with amine functional compounds.Another shortcoming of polyamines and aliphatics bifunctional glycidyl ether reaction product is, when product had fully high molecular weight with safer use, it also had very high viscosity.Therefore, need a large amount of relatively solvents to obtain having the curing agent solution of the suitable viscosity of using by conventional art.When this reaction product was used in coating composition, it will introduce a large amount of relatively volatile organic compound, and it improves the VOC (organic volatile component) of composition.
WO 02/074832 discloses the adduction of polyalkenyl alcohol monoglycidyl ether and amine functional compounds.The document has stated that the adducts that obtains has low relatively viscosity.Although the reaction by oxygen functionalized compound of monocycle and polyamines can obtain low molecular weight substance, the system that contains this reaction product has shortcoming.At first, because molecular size and they can the polymeric facts, these materials are probably for bioactive and may therefore cause health and environmental problem.If have only the reaction of small amount of epoxy and polyamines, can obtain high relatively free amine content.The free amine content of indication is the quantity of unreacted amine functional compounds in system in this manual.When keeping high relatively free amine content, system for the reaction sensitivity of water and carbonic acid gas, and may form carbaminate, show as so-called lip-deep as explained above " amine frosting " effect.If the epoxide of sufficient quantity and polyamines reaction can only be had the lower molecular weight adducts of low relatively functionality to avoid the amine frosting.After comprising system's curing of this adducts, the network that obtains may be unsatisfactory.Cross-linking density may too lowly can not obtain having acceptable hardness, toughness, amount of deflection, anti-chemical or any other depend on the cured layer of the full-blown coating performance of network.
The well-known other example that obtains the amine hardener of part amine functional group pre-reaction is amine functional compounds and vinylformic acid or acrylate reactions.At US 3,247, described amine-acrylate adducts and used these adducts cure polyepoxides in 163.JP 2000281759 discloses the solidifying agent that the additional polycondensation by (methyl) alkyl acrylate and aliphatie diamine obtains.DE 1 072 805 discloses the solidifying agent that is used for epoxy system by aliphatic polyamine and vinylformic acid or acrylate reactions preparation.
Verifiedly in practice when the reaction of polyamines and vinylformic acid, be difficult to preparation and have the good solidifying agent of low-molecular-weight performance.When the vinylformic acid of relatively small amount and polyamines reaction, can obtain low-molecular-weight compound.These materials usually have a low viscous while and also have high free amine content, when when low temperature and high relative humidity are solidified, make them be easy to form the amine frosting.In addition, the lower molecular weight of these materials and high free amine content also can make their danger and be difficult to handle.To such an extent as to when acrylic acid amount of using in reaction is enough high when obtaining having the solidifying agent of the low free amine content that anti-amine frosting forms, solidifying agent will have high viscosity.Therefore, select polyamines and molar ratio such as acrylic acid so that obtain the solidifying agent of anti-amine frosting formation, and have abundant low molecular weight so that guarantee not need or only need a small amount of organic solvent to obtain having abundant low viscous solidifying agent, be a problem.
But EP 0 709 418 A disclose the amine hardener of the self-emulsifying of using in water-bearing media coating.This solidifying agent can be amine, epoxy-functional polyethers and hydrophobic epoxy group(ing) and randomly acrylate or acrylic acid reaction product.In this system, amine reacts with the acrylic compound with two keys, rather than reacts with the acid function group of the higher processing thermotonus of needs condition.The existence of polyether chain has adverse influence to film and dipping property in the paint film that obtains.
When room temperature condition is a low temperature and when having high relatively humidity, solidifying agent fully solidifies.Generally, these are by unit molecule phenol, formaldehyde and the polyamines poly-Mannich base of ethylene diamine prepared in reaction for example.Although these materials can be very effective low temperature curing agent, they fade very soon in the sun when exposing.
The invention provides the solution of the relevant shortcoming of a kind of above-mentioned prior art.Especially, the present invention has paid close attention to anti-amine frosting and forms with the possibility of use high solid solidifying agent and combine.Another object of the present invention provides the solidifying agent that is used for epoxy system with good colour stability; That is to say that the cured epoxy system after the curing should have good colour stability.For colour stability, its meaning is, when exposing in the sun, system can be with than changing color with the slower speed of traditional high solid low temperature solidifying agent solidified epoxy film.The another one purpose provides the solidifying agent with high relatively curing speed cured epoxy system.The another one purpose provides low viscosity high solids amine-functional solidifying agent that can be used for cured epoxy system at low temperatures and the cure system that can obtain having good color stability.
Target of the present invention can be by the solidifying agent realization of mono-functional epoxy compound and acid amides prepared in reaction by using, acid amides can by have 2 or more a plurality of-NH or-NH
2The amine functional compounds of group with have the reaction of one or more alpha-beta unsaturated acid and/or one or more alpha-beta unsaturated ester or obtain by other any preparation method that can obtain identical final product.Usually, acid amides is being higher than 160 ℃ by amine functional compounds and acid and/or ester, and for example the reaction of 180 ℃ or higher temperature forms.Solidifying agent may have one or more amide functional groups.
Randomly other compound can add reaction.Have 2 or more a plurality of-NH or-NH
2The amine functional compounds of group is also referred to as " polyamines ".The compound that contains an epoxy-functional is also referred to as " mono-functional epoxy compound ".
Compound exhibits of the present invention wish the advantage obtain.They can be with acting on the solidifying agent that epoxy-functional compounds and being used to comprises the system of epoxy-functional compounds.Have been found that when under the condition of low temperature and high humidity, solidifying the anti-amine frosting of solidifying agent according to the present invention forms.When solidifying agent according to the present invention is used to comprise the cure system of epoxy-functional compounds, can prepare when surpassing 60% in 10 ℃ or lower temperature and relative humidity when solidifying, system does not show perceptible amine frosting.Solidifying agent has fully low molecular weight to guarantee not needing or only need a small amount of organic solvent to obtain having abundant low viscous solidifying agent.Another one advantage according to compound of the present invention is can prepare to comprise one or more high-solid coating compositions according to solidifying agent of the present invention and one or more epoxy-functional compounds, when 10 ℃ or lower temperature with when surpassing 60% relative humidity and solidifying, it does not have the amine frosting yet.
When solidifying agent according to the present invention was used to solidify the system that comprises the epoxy-functional component, when exposing in the sun, cured epoxy system generally demonstrated good colour stability.For example, can prepare such epoxy system, with present high solid, low temperature solidifying agent, for example compare as above-mentioned poly-Mannich base, it demonstrates the flavescence that significantly weakens after solidifying.And when being used for cured epoxy system, solidifying agent according to the present invention demonstrates high relatively curing speed.This solidifying agent can be as at room temperature, for example in from 5 to 30 ℃ the temperature range, also can be at elevated temperatures, and cured epoxy system.The major advantage of The compounds of this invention is that they can be used to prepare at low temperatures the solidified high solids epoxy system and demonstrate good colour stability.
The example that is suitable for the amine functional compounds of preparation solidifying agent according to the present invention has: ethylene diamine, 1,3 propanediamine, 2,2-dimethyl-1, the 3-propanediamine, 1,4-butane diamines, 1, the 6-hexamethylene-diamine, 2,2, the 4-trimethylhexamethylenediamine, 1,3-pentane-diamines, the 2-methyl isophthalic acid, the 5-pentane diamine, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, piperazine, aminoethyl piperazine, m-xylene base diamines, 1,3-two-(aminomethyl) cyclo-hexylamine, isophorone diamine, 4,4 '-methylene radical dicyclohexylamine.Preferred diamines is 2,2-dimethyl 1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, 2-methyl isophthalic acid, 5-pentane diamine, m-xylene base diamines and 1,3-two-(aminomethyl) cyclo-hexylamine.Very Shi Yi polyamines is a fatty amine, for example trimethylhexamethylenediamine and 3-methyl isophthalic acid, 5-pentane diamine.Optimum polyamines is the diamines that contains ring, for example, and m-xylene base diamines and 1,3-diaminomethyl hexanaphthene.
As the suitable alpha-beta unsaturated acid and the example of ester, following compound may be mentioned: vinylformic acid, methacrylic acid, methyl methacrylate or similar methacrylic ester, methyl acrylate or similar acrylate, toxilic acid or acid anhydrides, maleic acid ester, fumaric acid or fumarate and Ba Dousuan or crotonate.
As the example of suitable mono-functional epoxy compound, following compound may be mentioned: mono-functional glycidyl ethers, for example butyl glycidyl ester, hexyl glycidyl ester, cyclohexyl glycidyl ether, 2-ethylhexyl glycidyl ether, C
12-C
14Alkyl glycidyl ester (epoxide 8), gresyl glycidyl ester and phenyl glycidyl ester.
When amine functional compounds and unsaturated acid or ester cpds react at elevated temperatures, amine functional group not only and two keys also form amide group with acid groups.Because at room temperature the reaction of amine and activity double key is very fast, the reaction of amine and carboxylic acid or ester group slowly much and generally need be above 160 ℃, for example carry out under 180 ℃ or the higher temperature, or carry out having under other means of same effect.Like this, unsaturated acid or ester are as bifunctional compound, rather than the simple function group compound, as shown in the EP 0 709 418.
For example mono-functional epoxy adds simultaneously or it can add before or after polyamines and unsaturated acid and/or ester reaction, for example after the reaction mixture of amine and unsaturated acid and/or ester is cooled to below 100 ℃ the temperature, for example 75-85 ℃, for example about 80 ℃.
According to amine functional compounds of the present invention, it is suitable for the cured epoxy functional compounds, polyamines and the alpha-beta unsaturated acid of 7.5 to 17.5 weight % and/or the mono-functional epoxy compound prepared in reaction of ester and 10 to 50 weight % that can be by 50% to 80 weight %, wherein wt % 100 multiply by the gross weight of the weight of given component divided by material in initially feeding.Preferably, reactant ratio is polyamines and the alpha-beta unsaturated acid of 10 to 16 weight % and/or the mono-functional epoxy compound of ester and 20 to 40 weight % of 60 to 75 weight %, and wherein wt % is the gross weights of 100 weight that multiply by given component divided by material in initial charging.More preferably, the ratio of reactant is polyamines and the alpha-beta unsaturated acid of 12 to 15 weight % and/or the mono-functional epoxy compound of ester and 25 to 35 weight % of 65 to 70 weight %, and wherein wt % is the gross weights of 100 weight that multiply by given component divided by material in initial charging.
According to amine functional compounds of the present invention can be by 40-90 mole % polyamines and the alpha-beta unsaturated acid of 5-50 mole % and/or the mono-functional epoxy compound prepared in reaction of ester and 5-55 mole %, wherein mole % 100 multiply by the total mole number of the mole number of given component divided by material in initially feeding.Preferably, the ratio of reactant is polyamines and the alpha-beta unsaturated acid of 10-40 mole % and/or the mono-functional epoxy compound of ester and 10-40 mole % of 45-75 mole %, and wherein mole % is the total mole numbers of 100 mole numbers that multiply by given component divided by material in initial charging.Most preferably, the ratio of reactant is polyamines and the alpha-beta unsaturated acid of 15-30 mole % and/or the mono-functional epoxy compound of ester and 15-25 mole % of 50-65 mole %, and wherein mole % is the total mole numbers of 100 mole numbers that multiply by given component divided by material in initial charging.
The number-average molecular weight (Mn) that is suitable for the amine functional compounds of cured epoxy functional compounds according to the present invention can be 200-1000, and is preferably 300-500.For example, number-average molecular weight can calculate the described theoretical numerical value that calculates number-average molecular weight by simplifying the Stockmeyer distribution function.
The nitrogen equivalent weight (nitrogen equivalent weight) that is suitable for the amine functional compounds of cured epoxy functional compounds according to the present invention is generally in 50 to 250g/mol scope, preferably 75-225g/mol, more preferably 100-200g/mol.The nitrogen equivalent weight can be determined by volumetry.Nitrogen equivalent weight scope and the titratable nitrogen-atoms pointed out above have relation.
According to the present invention, when one or more amine functional compounds are used to prepare can be with the preparation curative system of the solidifying agent that acts on epoxy system the time, curative system generally comprises:
-according to one or more amine functional compounds of the present invention
-organic solvent and/or water and
-optional catalyzer
According to the preferred 10-100 pool at room temperature of the viscosity of the not amine functional compounds of preparation of the present invention.Polyamines with viscosity of 10-100 pool scope can be prepared at an easy rate solidifying agent is had at room temperature＜viscosity of 10 pools, and it can be used for the coating that preparation has solids content in volume＞75%.These viscosity datas are determined as the shear viscosity that records with awl-plate viscometer.For example, shear viscosity can have 10,000-12,000s according to ASTM D 4,287 00 usefulness
-1The shear viscosity meter of velocity of shear is measured.
Randomly, curative system according to the present invention comprises catalyzer.The embodiment of suitable catalyzer may mention nonylphenol, Whitfield's ointment, three (dimethyl)-aminomethyl phenol, diazabicyclooctane, diazabicylo undecylene, water, ammonium thiocyanate, LiBF4, potassium sulfocyanate, sodium tetrafluoroborate, lithium benzoate, lithium lactate, lithium hydroxide, acetylacetonate lithium, nitrocalcite, lithium perchlorate, lithium formate, lithium thiocyanate, potassium tetrafluoroborate.Preferred catalyzer is sodium tetrafluoroborate, potassium sulfocyanate, lithium lactate, lithium hydroxide, lithium benzoate, He Shui.
Coating composition can be produced, and it comprises according to amine functional group solidifying agent of the present invention or curative system and one or more epoxy-functional compounds.
Can or contain solvent medium and may comprise water and organic solvent for water-bearing media according to coating composition of the present invention.Preferably, coating composition comprises one or more organic solvents; More preferably coating composition is a high solids compositions, it comprise based on total coating composition be no more than or only up to the organic solvent of 20 weight %.Coating composition of the present invention preferably includes every liter of organic solvent and is less than 430 gram volatile organic matters (VOC).More preferably, coating composition comprise every liter be less than 340 the gram VOC, even more preferably every liter be less than 250 the gram VOC.Solids content according to composition of the present invention preferably is higher than 60% by weight based on total coating composition, more preferably is higher than 70% by weight, even more preferably by weight 80%.
May comprise catalyzer according to coating composition of the present invention.This catalyzer can be the part of the curative system of coating composition.On this basis or additionally, catalyzer can be used as the part preparation of coating base.
Coating composition of the present invention may comprise one or more other components.They may comprise one or more pigment, and for example for example yellow or red iron oxide or phthalocyanine pigment and/or one or more are strengthened for example iron mica or silica crystal and/or one or more anticorrosive pigment for example barite, talcum or lime carbonate of metallic zinc, zinc phosphate, wollastonite or chromic salt, molybdate or phosphoric acid salt and/or weighting agent pigment for example of pigment for titanium dioxide (white pigments), coloured pigment.Said composition may comprise denseization agent for example fine-particle silica, wilkinite, hydrogenated castor oil or polyamide wax.Said composition can contain softening agent, pigment dispersing agent, stablizer, glidant or diluting solvent.
Coating composition of the present invention generally at room temperature solidifies, and for example therefore temperature suits to be applied to for the unpractical macrostructure that is heating and curing at from 0 to 30 ℃ even in 50 ℃ scope.In addition, coating composition of the present invention can solidify at elevated temperatures, for example from 30 or 50 ℃ to 80 ℃ even up to 100 ℃ or 130 ℃, solidifies quickening.
General coating composition of the present invention can be used as topcoating (finish coating) and/or priming paint.This coating composition can be used as priming paint/topcoating and is directly used in the preparation carbon steel, and promptly said composition can be used for the supercoat of the unique type on matrix.
Coating composition preferably of the present invention is as the protectiveness primer coating, particularly on the steel surface, and for example bridge, pipeline, industrial plant or building, oil or gas facility or ship.It generally uses anticorrosive pigment coloring for this purposes.For example it can be painted with zinc powder; Coating according to the present invention has similar corrosion resistance for well-known zinc silicate coating, and is not easy to mud crack and can be coated with in the above at an easy rate, uses urethane or polysiloxane for example according to topcoating surface treatment of the present invention especially.Can be used for safeguarding or repairing not really ideal top coat according to primer composition of the present invention, for example the steel of aging infringement or " ginger " (steel that has damaged or got rusty), the aging steel of manual preparation and aging coating with point.
Preferably, combine as so-called two-component composition (two-pack composition) according to the component of coating composition of the present invention.A kind of component comprises one or more according to solidifying agent of the present invention, and other component comprises one or more epoxy-functional compounds.
The present invention will use following embodiment with reference to explanation.These be used for illustration the present invention but should not be construed as and limit its scope in any form.In these embodiments, pbw means weight part.
Embodiment
Embodiment 1
Amine functional compounds produced according to the present invention
By diamines and vinylformic acid and mono-functional glycidyl ethers prepared in reaction amine functional compounds.
M-xylenedimaine (MXDA) (656.9g, 4.83mol) agitator, condenser, Dean ﹠amp are equipped with in adding; Stark separator, thermopair and N
2In the 700ml reaction flask of injector.With keep speed that temperature in the flask is lower than 30 ℃ add vinylformic acid (AA) (72.0g, 1.00mol).In case all vinylformic acid adds, temperature of reaction is raised to 180 ℃ to evict water of condensation from.Temperature of reaction keeps 180 ℃ of acid numbers up to intermediate to be lower than 5.Reaction mixture is cooled to 80 ℃ and added butylglycidyl ether (BGE) in 2 hour time (434.2g, 3.34mol), and temperature of reaction remains on 80 ℃.In case all butylglycidyl ethers add, temperature of reaction was kept 2 hours at 80 ℃ again, and reaction product is cooled to 40 ℃ and emit then.This product is the fluxion of clarifying low viscosity (25 ℃, 8.2 pools).
Comparative example 1
Preparation is amine functional compounds relatively
By diamines and bifunctional glycidyl ether and mono-functional glycidyl ethers prepared in reaction amine functional compounds.
M-xylenedimaine (MXDA) (656.9g, 4.83mol) agitator, condenser, Dean ﹠amp are equipped with in adding; Stark separator, thermopair and N
2In the 700ml reaction flask of injector, and temperature is raised to 80 ℃.With keep the flask temperature 80 ℃ speed add hexanediol diglycidyl ether (230.0g, 1.00mol).In case all hexanediol diglycidyl ether add, temperature of reaction was kept 2 hours at 80 ℃ again.In 2 hour time, added butylglycidyl ether and temperature of reaction maintains 80 ℃.In case all butylglycidyl ethers add, temperature of reaction was kept other 2 hours at 80 ℃ again, and reaction product is cooled to 40 ℃ and emit then.
The physical properties of the amine functional compounds of preparation in embodiment 1 and the comparative example 1
During the physical properties of the amine functional compounds of preparation is listed in the table below in embodiment 1 and the comparative example 1.
| ? | Amine value [mg.KOH.g -1] | Theoretical amine value [mg.KOH.g -1] | Viscosity [pool, 25 ℃] | NVC 1[weight %] | Acid number [mg.KOH.g -1] |
| Embodiment 1 | 420 | 424 | 8.2 | 85.3 | 3.5 |
| Comparative example 1 | 373 | 387 | 55.2 | 88.6 | 3.2 |
1NVC is a non-volatilization component
Find out obviously that from the physical properties of determining amine functional compounds prepared in accordance with the present invention has lower viscosity than amine functional compounds frequently, although two kinds of materials all have the polymerization degree and similar molecular weight of equal value.
Embodiment 2 to 6
Several types used according to the invention have 2 or more a plurality of-NH or-NH
2The amine functional compounds of group prepares amine functional compounds
According to the present invention by amine functional compounds and vinylformic acid and the mono-functional glycidyl ethers prepared in reaction amine functional compounds of in following table, listing.The physical properties of the amine functional compounds of preparation is listed in the following same table.
1BGE represents butylglycidyl ether
2MXDA represents m-xylene diamine
3Dytek EP is 1, the commerce product of 3-pentane diamine
4TMD represents 2,2,4 trimethylhexane diamine
51,3 BAC represents 1,3-(diaminomethyl) hexanaphthene
6Dytek A is the 2-methyl isophthalic acid, the commerce product of 5-pentane diamine
7Unless otherwise noted, all viscosity record under 25 ℃.
8NVC is non-volatile component.
For the amine functional compounds of this invention of the identity basis purposes as solidifying agent, every kind of compound mixes so that each amine hardener has 1 corresponding each Resins, epoxy of active H that 1 epoxide group is arranged with certain weight ratio with liquid epoxies (DER331 ex DowChemicals).Curing speed records according to ASTM 5895 usefulness " the dry track record instrument of BK " (" BK Dry Track Recorder ").
The result show according to amine functional compounds of the present invention can be frequently than compound cured epoxy resin quickly.
Embodiment 7 to 25
The reactive component of different ratios used according to the invention prepares amine functional compounds
The following examples show that the ratio of amine functional compounds and alpha-beta unsaturated acid and/or ester and mono-functional epoxy compound can be easy to change the solidifying agent that has special properties with preparation.And it also proves and may change mono-functional epoxy compound and to obtain for example further raising of viscosity of special property.
| ? | 1，3BAC 1[weight (g)] | AA 2[weight (g)] | BGE 3[weight (g)] | Epoxide 8 4[weight (g)] | Amine value [mgKOH.g -1] | NVC [weight %] | Viscosity [pool, 55 ℃] |
| Embodiment 7 | 56 | 10 | 34 | ? | 378.8 | 87.48 | 4.78 |
| Embodiment 8 | 55 | 11 | 34 | ? | 361.9 | 90.23 | 10.08 |
| Embodiment 9 | 60 | 15 | 25 | ? | 377.3 | 89.36 | 25.89 |
| Embodiment 10 | 70 | 15 | 15 | ? | 458.9 | 78.87 | 5.69 |
| Embodiment 11 | 50 | 15 | 35 | ? | 296.0 | 96.25 | 78.5 |
| Embodiment 12 | 60 | 13 | 28 | ? | 388.8 | 87.08 | 11.67 |
| Embodiment 13 | 50 | 10 | 40 | ? | 327.1 | 91.75 | 11.77 |
| Embodiment 14 | 65 | 14 | 21 | ? | 422.4 | 84.21 | 10.56 |
| Embodiment 15 | 70 | 15 | 15 | ? | 455.9 | 78.17 | 5.73 |
| Embodiment 16 | 62 | 12 | 27 | ? | 405.3 | 82.93 | 5.38 |
| Embodiment 17 | 50 | 35 | 15 | ? | 293.5 | 72.93 | 76.7 |
| Embodiment 18 | 67 | 13 | 20 | ? | 450.2 | 77.81 | 3.98 |
| Embodiment 19 | 70 | 14 | 16 | ? | 465.1 | 76.20 | 4.21 |
| Embodiment 20 | 50 | 10 | 40 | ? | 330.3 | 91.32 | 10.87 |
| Embodiment 21 | 50 | 15 | ? | 35 | 285.8 | 92.51 | 52.1 |
| Embodiment 22 | 50 | 10 | ? | 40 | 348.2 | 80.53 | 2.36 |
| Embodiment 23 | 70 | 15 | ? | 15 | 442.3 | 77.36 | 5.89 |
| Embodiment 24 | 60 | 13 | ? | 27 | 387.0 | 81.22 | 5.58 |
| Embodiment 25 | 55 | 11 | ? | 34 | 354.5 | 83.70 | 5.23 |
11,3BAC represents 1,3-(diaminomethyl) hexanaphthene
2AA represents vinylformic acid
3BGE represents butylglycidyl ether
4Epoxide 8 is C
12-C
14Alkyl glycidyl ether
Claims (7)
1. amide compound, it is suitable for the solidifying agent as epoxy-functional compounds, can one or more compounds that contain an epoxy-functional and the reaction of one or more acid amides by 5 to 55 moles of % obtain, acid amides by 40 to 90 moles of % have 2 or more a plurality of-NH-or-NH
2The one or more alpha-beta unsaturated acid of one or more amine functional compounds of group and 5 to 50 moles of % and/or the reaction of one or more alpha-beta unsaturated ester obtain, and wherein mole % is the total mole numbers of 100 mole numbers that multiply by given component divided by material in initial charging.
2. compound according to claim 1 has 200 to 1000 number-average molecular weight Mn.
3. compound according to claim 1 has 50 to 250g/mo1 nitrogen equivalent weight.
4. cure system, it comprises:
-compound according to claim 1
-organic solvent and/or water and
-catalyzer randomly.
5. the purposes of compound according to claim 1 as solidifying agent, is used to comprise the system of one or more epoxy-functional compounds.
6. coating composition, it comprises compound according to claim 1 and one or more epoxy-functional compounds.
7. matrix with coating composition as claimed in claim 6 coating.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06100450 | 2006-01-17 | ||
| EP06100450.3 | 2006-01-17 | ||
| US76518006P | 2006-02-06 | 2006-02-06 | |
| US60/765,180 | 2006-02-06 | ||
| PCT/EP2007/050313 WO2007082853A1 (en) | 2006-01-17 | 2007-01-15 | Curing agents for epoxy-functional compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101370846A CN101370846A (en) | 2009-02-18 |
| CN101370846B true CN101370846B (en) | 2011-08-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800024860A Active CN101370846B (en) | 2006-01-17 | 2007-01-15 | Curing agents for epoxy-functional compounds |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN101370846B (en) |
| BR (1) | BRPI0706555B1 (en) |
| MY (1) | MY148433A (en) |
| UA (1) | UA102215C2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN2014DN08701A (en) * | 2012-04-27 | 2015-05-22 | Mitsubishi Gas Chemical Co | |
| JP6241674B2 (en) * | 2012-04-27 | 2017-12-06 | 三菱瓦斯化学株式会社 | Epoxy resin curing agent, epoxy resin composition, gas barrier adhesive, and gas barrier laminate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3449278A (en) * | 1966-04-15 | 1969-06-10 | Ciba Ltd | Epoxide resin compositions |
| EP0709418A2 (en) * | 1994-10-28 | 1996-05-01 | Mitsubishi Gas Chemical Company, Inc. | Aqueous self-emulsifiable epoxy resin curing agent |
| CN1481421A (en) * | 2000-11-16 | 2004-03-10 | ���¡�D��ϯ���� | Hardoner for epoxy of polyols and n-contg hardener |
| CN1637039A (en) * | 2003-12-19 | 2005-07-13 | 气体产品与化学公司 | Method of preparation of a water based epoxy curing agent |
-
2007
- 2007-01-15 UA UAA200810450A patent/UA102215C2/en unknown
- 2007-01-15 BR BRPI0706555-8A patent/BRPI0706555B1/en active IP Right Grant
- 2007-01-15 CN CN2007800024860A patent/CN101370846B/en active Active
- 2007-01-15 MY MYPI20082615 patent/MY148433A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3449278A (en) * | 1966-04-15 | 1969-06-10 | Ciba Ltd | Epoxide resin compositions |
| EP0709418A2 (en) * | 1994-10-28 | 1996-05-01 | Mitsubishi Gas Chemical Company, Inc. | Aqueous self-emulsifiable epoxy resin curing agent |
| CN1481421A (en) * | 2000-11-16 | 2004-03-10 | ���¡�D��ϯ���� | Hardoner for epoxy of polyols and n-contg hardener |
| CN1637039A (en) * | 2003-12-19 | 2005-07-13 | 气体产品与化学公司 | Method of preparation of a water based epoxy curing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| MY148433A (en) | 2013-04-30 |
| BRPI0706555B1 (en) | 2018-07-31 |
| CN101370846A (en) | 2009-02-18 |
| BRPI0706555A2 (en) | 2011-03-29 |
| UA102215C2 (en) | 2013-06-25 |
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