TW201641531A - Hardener composition - Google Patents

Abstract

Cold curing hardener compositions comprise: component A, at least one adduct of a first amine compound and at least one polyfunctional epoxy compound; component B, at least one adduct of a second amine compound and at least one monofunctional epoxy compound; component C, at least one adduct of a third amine compound based on a polyalkylene oxide; on a cycloaliphatic, aliphatic or araliphatic amine, and a modifier; wherein the hardener compositions has a low VOC, a low free amine content, and a low viscosity. Curable compositions include (a) at least one epoxy resin and (b) at least one of the above cold curing hardener composition. Processes for preparing the hardener compositions and the curable compositions will be presented.

Description

Hardener composition

The present invention generally relates to a hardener composition, a method of preparing the hardener composition, a curable composition comprising the hardener composition, and a curable composition comprising the hardener composition. Curing the product.

Epoxy resins are widely used in a variety of applications including coating compositions. Those coating compositions are used for a variety of end uses, such as metal and concrete substrate protection; flooring, infusion, packaging applications; and other similar end uses.

Many known amine adduct hardener compositions are used in epoxy resin curable compositions to provide a curable coating composition. In these compositions, the amine adduct hardener composition contains up to 50% (%) of the monomolecular structure amine. In addition to acting as a hardener, the monomolecular structural amine also reduces the viscosity of the hardener composition.

One or more volatile organic compounds (VOCs) are known to be used in the hardener composition. Benzyl alcohol is added to the hardener composition to reduce the compositional viscosity and improve the surface appearance of the curable system made from the curable composition. Non-reactive materials or modifiers are also used in the hardener composition in amounts up to 75%. These non-reactive materials, such as nonylphenol, reduce the viscosity of the hardener composition and enhance the flexural properties of the curing system. However, these non-reactive materials have a detrimental effect on the mechanical properties of the curing system.

The VOC-free composition is conventional and is mainly used in aqueous hardener compositions. Examples of VOC-free compositions are described in EP 0 995 767 and EP 1 136 509. The composition of EP 0 995 767 and EP 1 136 509 requires a polyolefin oxide portion to achieve homogeneity of the composition in water. However, after evaporation of the water from the composition, the polyolefin oxide portion will exist in a sequence to weaken the polymer matrix. Moreover, these weakened polymer matrices reduce the chemical resistance of the coatings made from the composition. WO2011059500 also discloses curable coating compositions that do not contain VOCs. The compositions comprise an epoxy resin component, a Mannich base; and (1) an epoxy compound and (2) an amine adduct as a hardener. In addition, WO2011059500 discloses coated articles made from the aforementioned curable coating compositions. In general, Mannich base is a conversion product of an (alkyl) phenol with an amine and formaldehyde. These conversion products can achieve a certain degree of chemical resistance. However, due to the (alkyl) phenols present in the coating composition, these Mannich bases are indicated as the exposure hazard of the designated "risk phrase R 62", which corresponds to "damaged fertility. Danger". Accordingly, it would be advantageous to provide a curable coating composition that does not use Mannich base as disclosed in WO2011059500 and to provide reduced exposure hazard and improved chemical resistance.

Adducts, distillate adducts, and the foregoing modifiers are also well known in the art. The m-xylylenediamine (MXDA)-adduct is disclosed in Vandezande et al., "Epoxy Hardeners for 2K Systems", 30th (2nd episode) FATIPEC Congress ( 2010), pp. 620-629; disclosed in Marks et al., ACS Applied Materials & Interfaces (2009), 1(4), pp. 921-926; and disclosed in Girish Mirchandani "Using Differential Scanning Thermal Analyzers to Evaluate Relative Reactivity and Various Polyamine Kinetics, and Assessment of Relative Reactivities and Kinetics of Various Polyamines, And Polyamide Hardeners with Epoxy Resins for Designing High Performance Epoxy Coatings Using Differential Scanning Calorimetry), Indian Coatings Show (2007), 57(6), 69-70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92 pages. The above documents do not disclose curable coating compositions having desirable properties such as monomolecular structure amine content less than [<] 20%, low VOC content, flexibility, surface appearance, and chemical resistance.

EP 1213312 B1 discloses an adduct of isolated (e.g. distilled) phenyl glycidyl ether (Ph-GE) and tri-ethyltetramine (TETA), wherein the resulting adduct has a viscosity greater than 10,000 mPa s. EP 1213312 B1 does not teach the use of toluene glycidyl ether (CGE) or 2-methylpentamethylenediamine (MPMD) in such adducts. The process disclosed in EP 1213312 B1 fails to complete an adduct having a low viscosity in the range of less than 10,000 mPa s, preferably in the range of 6,000 to 7,000 mPa s or less.

Despite the developments in the art of making hardener compositions for coating compositions and coating end uses, there is still a need for a hardener composition in the industry where the composition of the hardener is included, but not limited to, (1) a low VOC content (for example, about 0-5 g/L; a substance having a temperature lower than [<] 250 ° C is regarded as a VOC according to a boiling point [bp]); (2) a low free amine content (for example, <20 weight) Percent [wt%]); (3) low viscosity (for example, <1,500 mPa s at 25 ° C); (4) a combination of beneficial chemical properties required for improved chemical resistance and the like. In addition, a hardener composition having such characteristics can be used in the preparation of a curable epoxy resin composition or composition.

The present invention discloses low volatile organic compounds (VOC), low temperature curing hardener compositions, and methods of making the same. Further, a curable composition using the low temperature curing hardener composition, preparing the composition and curing the article The method of these compositions.

In one aspect, a low VOC, low temperature curing hardener composition comprising four components is present: an adduct of a first amine compound and a polyfunctional epoxy compound (component A), an adduct of a second amine compound And a monofunctional epoxy compound (component B), an adduct (component C) based on a polyolefin oxide, a third amine compound based on a cycloaliphatic amine, an aliphatic amine or an aryl lipid amine, and a A modifier wherein the composition has a low viscosity and a monomolecular structural amine content of less than 20% by weight.

In another aspect, the present disclosure is a curable composition comprising at least one epoxy compound and at least one low temperature curing hardener, wherein the curable composition has a low VOC content.

In still another aspect, a method of preparing a low temperature curing hardener composition comprises admixing four components: component A, component B, component C, and a modifier. Other additives known to those skilled in the art may also be added.

In still another aspect, a method of preparing a curable composition comprising at least one low temperature curing hardener and at least one epoxy compound is presented.

In still another aspect, the present disclosure is a cured product made by curing the low viscosity, low VOC curable composition.

Other features and retelling of the invention are described in more detail below.

Non-limiting specific examples of the invention are illustrated in the following figures, in which: Figure 1 is an illustration showing the chemical resistance of a curing system comprising a combination of a hardener (composition #11) and an epoxy resin DERTM 3531 of the invention. Sex test.

Figure 2 is a graphical representation showing the chemical resistance test of a curing system comprising a combination of another hardener (composition #12) and epoxy resin D.E.R. 3531 of the present invention.

Figure 3 is a graphical illustration showing the chemical resistance test of a curing system comprising a combination of a hardener other than the present invention (composition #1) and epoxy resin D.E.R. 3531.

Figure 4 is a graphical representation showing the results of the Flexibility Test (E-modulus {E(b) [GPa]}) of one embodiment of the present invention (Composition #11): Composition 11.

As previously stated, the present disclosure is a low temperature curing hardener composition comprising four components: component A, component B, component C and a modifier. Component A comprises at least one adduct comprising a first amine and at least one polyfunctional epoxy compound having a monomolecular structural amine content of less than 20% by weight. Component B comprises at least one adduct comprising a second amine and a monofunctional epoxy compound having a monomolecular structural amine content of less than 20% by weight. Component C comprises an adduct of a third amine based on a polyolefin oxide. The low temperature curing hardener composition and at least one epoxy resin compound provide a curable composition. After the curable composition is coated and cured, the resulting coating or thermoset has many beneficial aspects, such as low volatile organic compounds (VOC), improved flexibility, gloss, no distortion, and a smooth appearance. , improved chemical resistance, and E modulus below 2.5 MPa.

(I) low temperature curing hardener composition

In one aspect, the low temperature curing hardener composition comprises four components. In general, the low temperature curing composition has a monomolecular structure amine content of less than 20% by weight.

(a) Component A: First amine adduct

In one aspect, component A in the low temperature curing hardener composition comprises (a) at least one first amine compound; and (b) at least one multifunctional epoxy compound, wherein the adduct has less than about 20% by weight Monomolecular structure amine content.

(i) first amine compound

The first amine compound used in component A may include, for example, m-xylylenediamine (MXDA), isophoronediamine (IPDA), di-ethyltriamine (DETA), tri-ethylidene Amine (TETA), trimethylpentamethylenediamine (TMD), and mixtures thereof. In a preferred embodiment, the first amine compound can be MXDA. MXDA may be blushing and may produce a good chemical resistant coating.

In general, the concentration of the first amine compound can generally range from 10 wt% to about 90 wt%. In various embodiments, the concentration of the first amine compound can range from 10 wt% to about 90 wt%, 20 wt% to about 80 wt%, 25 wt% to about 75 wt%, or 30 wt% to about 70 wt%. If the concentration of the amine compound is less than about 10% by weight, the viscosity of the hardener composition may be too high. If the concentration of the amine compound is higher than about 90% by weight, blushing may increase due to the reaction of the monomolecular structure amine with CO2/water from air during the hardening reaction.

(ii) Polyfunctional epoxy compounds

The polyfunctional epoxy compound in component A may include, for example, an adduct of liquid epoxy resin (LER). Liquid epoxy compounds may include, for example, bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE), low (eg, <500-800 g/mole) molecular weight (MW) novolac, and Its mixture. In a preferred embodiment, the adduct hardener composition can include BADGE such as D.E.R. 331 and D.E.R. 330 (which is commercially available from The Dow Chemical Company). In another preferred embodiment, the adduct hardener composition can be based on DER 331 because the polyfunctional epoxy compound exhibits a higher viscosity than a higher epoxy equivalent (EEW) (eg, compared At DER 330), but due to less epoxy groups by weight, some slightly low viscosity adducts are formed (e.g., at a fixed epoxy/amine ratio).

In general, the concentration of the polyfunctional epoxy compound can generally range from 10 wt% to about 90 wt%. In various embodiments, the concentration of the polyfunctional epoxy compound used in component A may range from 10 wt% to 90 wt%, 20 wt% to 80 wt%, 25 wt% to 75 wt%, or 30 wt% to 70 wt%. If the concentration of the polyfunctional epoxy compound used is less than about 10% by weight, it results in the use of a larger amount of amine, which in turn increases the whitening of the resulting coating; if the concentration of the polyfunctional epoxy compound used is greater than about 90% by weight, The resulting composition will exhibit a high viscosity (eg, at 25 ° C, 50,000 mPa s).

(b) Component B: second amine adduct

Component B of the low temperature curing hardener composition comprises a second amine compound and a monofunctional epoxy compound, wherein the adduct has a monomolecular structural amine content of less than about 20% by weight.

(i) second amine compound

The second amine compound used in component B may include any of the same amines as described above with reference to the first amine. Furthermore, all distillable amines known in the art (for example amines which are distillable under mild conditions of 200 ° C and 5 mbar). In a preferred embodiment, the second amine compound can be methyl pentamethylenediamine (MPMD). MPMD produces low viscosity adducts (eg, at a given epoxy to amine ratio).

In general, the concentration of the second amine compound can generally range from 10 wt% to about 90 wt%. In various embodiments, the concentration of the first amine compound may range from 10 wt% to about 90 wt%, 20 wt% to about 80 wt%, 25 wt% to about 75 wt%, or 30 wt%, based on the total weight of the components in the hardener composition. Up to about 70% by weight.

(ii) monofunctional epoxy compounds

The monofunctional epoxy compound may include any glycidyl ether (GE). Non-limiting examples of glycidyl ethers may be o-toluene glycidyl ether (CGE), p-tert-butylphenyl glycidyl ether, glycidyl ether mixtures, such as (i) 1-dodecanol (C12 alkyl) shrinkage a mixture of glyceryl ether and (ii) 1-tetradecanol (C14 alkyl) glycidyl ether (C12/C14 alkyl GE mixture), 1,4-butanediol glycidyl ether (BDDGE), 1,6-hex Glycol glycidyl ether (HDDGE), C12 to C14-alkyl glycidyl ether, 2-ethylhexyl glycidyl ether, and mixtures thereof. In a preferred embodiment, the monofunctional epoxy compound can be, for example, CGE. CGE is monofunctional and, therefore, CGE produces an essentially lower viscosity adduct (e.g., as compared to D.E.R. 331 or other epoxy resin compounds). In addition, CGE has an aromatic backbone (e.g., similar to D.E.R. 331) and, therefore, can increase the chemical resistance of coatings cured with CGE-containing adducts.

In general, the concentration of the monofunctional epoxy compound can generally range from 10 wt% to about 90 wt%. In various embodiments, the concentration of the first amine compound may range from 10 wt% to about 90 wt%, 20 wt% to about 80 wt%, 25 wt% to about 75 wt%, or 30 wt%, based on the total weight of the components in the hardener composition. % to about 70% by weight.

In a preferred embodiment, the reaction mixture is targeted to provide a 1:1 molar: molar addition of the second amine compound to the monofunctional epoxy compound. Thus, 2 moles of amine was reacted with 1 mole of monofunctional epoxy compound. Then, an excess of 0.2 to 1 mole of the second amine is removed by distillation, while the residual monomolecular structure amine content in the composition is less than about 2% by weight. If the reaction mixture contains a molar ratio of less than 1:1, more undesirable higher (CGE) x-(MPMD) 1 (x>1) type adducts are formed. If the reaction mixture contains a molar ratio above 1:1, the amount of amine that needs to be distilled from the reaction mixture increases undesirably.

(c) Component C: third amine adduct

The third amine adduct, component C, can be based on a polyolefin oxide, a cycloaliphatic amine, an aliphatic amine or an arylamine, or a combination thereof. A non-limiting example of component C can be a polyalkylene alkylamine such as Jeffamine D-230 and Jeffamine D-400, which are commercially available from Huntman. These polyoxyalkylene amines help to improve the flexibility and surface appearance of the cured product.

In general, the concentration of component C (third amine adduct) used in the low temperature curing hardener composition may generally range from 1 wt% to about 20 wt%. In various embodiments, the concentration of component C may range from 1 wt% to about 20 wt%, from 1 wt% to about 15 wt%, from 1 wt% to about 10 wt%, and from 2 wt% to the total weight of the components of the hardener composition. It is in the range of about 5 wt%. When component C is used in excess of 20% by weight, the chemical resistance of the coating made using the hardener is lowered. On the other hand, when component C is used in an amount of less than 1% by weight, the composition exhibits a high viscosity.

(d) modifier compound

On the other hand, the low-temperature curing hardener composition may use a high boiling point modifier (b.p. > 250 ° C, no VOC) compatible with the epoxy resin and the amine mixture. Non-limiting examples of high boiling point modifiers can include styrenated phenol, diisopropylnaphthalene (DI), and mixtures thereof. In a preferred embodiment, the high boiling point modifier compound can be DI because DI is compatible with amines, amine adducts, epoxy resins, and curing systems.

In general, the concentration of the high-boiling modifier compound used in the low-temperature curing hardener composition may range from 1% by weight to about 50% by weight based on the total weight of the components in the hardener composition. In various embodiments, the concentration of the high boiling point modifier can range from 1 wt% to 50 wt%, from 5 wt% to about 40 wt%, from 10 wt% to about 30 wt%, from 15 wt% to about 25 wt%. If the high-boiling modifier compound is used in an amount of more than 50% by weight, the mechanical properties of the coating obtained by using the modifier are lowered. Conversely, if the modifier is used at less than 1% by weight, the composition exhibits a high viscosity.

(e) Additives as appropriate

On the other hand, an optional additive may be added to the low-temperature curing hardener composition. Non-limiting examples of optional additives may be accelerators such as salicylic acid, 2,4,6-tris(N,N-dimethylamino)phenol (eg, DMP-30), and mixtures thereof.

Generally, the additive concentration may be in the range of from 0 wt% to about 5 wt%, as appropriate. In various embodiments, the additive concentration may be in the range of 0 wt% to 5 wt%, 0.1 wt% to about 2.5 wt%, and 0.1 wt% to about 1 wt%, as appropriate.

(f) Properties of low temperature curing hardener compositions

In general, the low temperature curing hardener composition can be a liquid prior to curing. The viscosity of the low temperature curing hardener composition may range from 100 mPa s to about 1500 mPa s at 25 °C. In various embodiments, the low temperature curing hardener composition may have a viscosity at 25 ° C of from 100 mPa s to about 1500 mPa s, from 200 mPa s to about 1,400 mPa s, from 300 mPa s to about 1,300 mPa s and from 400 mPa s to about 1,200 mPa. Within the scope of s.

The low temperature curing hardener composition advantageously has no VOC content or has a low VOC content (as defined by a boiling point of >250 ° C). Further, the content of the non-reactive material in the low-temperature curing composition may be in the range of 1% by weight to about 50% by weight. In various embodiments, the amount of non-reactive material can range from 1 wt% to about 50 wt%, from about 5 wt% to about 40 wt%, and from about 10 wt% to about 30 wt%.

The content of free amine in the low temperature curing hardener composition may range from 1 wt% to about 20 wt%. In various embodiments, the free amine content can range from 1 wt% to 20 wt%, from 5 wt% to about 20 wt%, and from about 10 wt% to about 20 wt%.

(II) curable composition

Another aspect of the present invention provides a curable composition comprising (I) at least one epoxy resin and (II) the aforementioned low temperature curing hardener. Other optional additives may be added to the curable composition.

(a) epoxy resin compound (I)

The curable composition using the low temperature curing hardener composition includes at least one epoxy resin compound. The epoxy resin compound, component (I), can be any conventional epoxy resin compound. The epoxy resin may be a single epoxy resin compound or a mixture of two or more epoxy compounds used in combination, that is, a group of the curable epoxy resin coating composition of the present invention which is cured to form a coating material. Sub-portion A comprises at least one epoxy resin. Non-limiting examples of the at least one epoxy resin may include aliphatic epoxy resin, cycloaliphatic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, Phenolic novolac epoxy resin, biphenyl epoxy resin, polyfunctional epoxy resin, naphthalene epoxy resin, divinylbenzene dioxide, 2-glycidylphenyl glycidyl ether, dicyclopentadiene ring An oxyresin, a phosphorus-containing epoxy resin, a polyaromatic resin type epoxy resin, and a mixture thereof. Other non-limiting examples of the at least one epoxy resin may include trimethylpropane epoxide, cyclohexane dimethanol diglycidyl ether, cyclohexane-1,2-dicarboxylic acid diglycidyl ester, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcinol diglycidyl ether, p-aminophenol triglycidyl ether, halogen-containing (eg chlorine or bromine) epoxy resin such as tetrabromobisphenol A Glycidyl ether, epoxidized phenol novolac resin, epoxidized bisphenol A novolac, Oxazolidinone modified epoxy resin, epoxy terminated polycondensation Oxazolidinones, and mixtures thereof.

Suitable commercially available epoxy resin compounds may include the DERTM 300 series, DENTM 400 series, DERTM 500 series, DERTM 600 series, and DERTM 700 series epoxy commercially available from The Dow Chemical Company. Resin. Epoxy resin Non-limiting examples thereof may include liquid epoxy resins (LERs) such as DER 331 (bisphenol A diglycidyl ether, BADGE), DER 354 (bisphenol F diglycidyl ether), DER 324 (diluent modified ring) Oxygen resins), other low viscosity epoxy resin blends, and other well known epoxy resins and blends or mixtures of the foregoing known epoxy resins. D.E.R. 324, D.E.R. 330, D.E.R. 331, D.E.R. 332 and D.E.R. 354 are epoxy resins commercially available from The Dow Chemical Company. Other commercially available epoxy resin compounds may include, for example, BADGE having a MW < 700. As an illustration, at least one epoxy resin compound which is advantageous for the present invention may comprise a liquid epoxy resin such as bisphenol A condensed water having an epoxy equivalent weight of from about 170 to about 190, a viscosity of about 10 Pa-s, and a density of 1.2 g/cc. Glycerol ether (DGEBPA) DER331.

Lee, H. and Neville, K, "Handbook of Epoxy Resins", incorporated in the present invention by reference, McGraw-Hill Books, New York, 1967, Chapter 2, pp. 257- Epoxy resins which are advantageous for the extended list of the invention are found in 307. The preparation of epoxy compounds which are advantageous in the present invention is described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Vol. 9, pp. 267-289, incorporated herein by reference. Other suitable epoxy resins as component (I) are described, for example, in U.S. Patent Nos. 3,018,262, 7,163,973, 6,887,574, 6,632,893, 6,242,083, 7,037,958, 6,572,971, 6,153,719, 5,137,990, 6,451,898, 5,405,688, 7,655,174, 7,871,556, 7,923,073, and 8,048,819. The invention is incorporated by reference.

(b) Low-temperature curing hardener composition (II)

The low temperature curing hardener composition, component (II), (also referred to as curing agent or crosslinking agent) may be selected from one or more of the aforementioned low temperature curing hardener compositions.

In general, the epoxy resin compound (I) and the hardener composition (II) The amount ratio is sufficient to form a coating or thermoset. The equivalent ratio of the epoxy resin (I) to the hardener composition (II) is such that the epoxy/hardener ratio is an epoxy equivalent ratio to one amine equivalent. In various embodiments, the ratio of epoxy equivalent to amine equivalent can generally range from about 1:1 to about 1:0.9, or from about 1:1 to about 1:1.1. Using a concentration outside the above range may weaken the formed network structure.

(c) Additives as appropriate (III)

Other optional additives may be added to the coating composition. Non-limiting examples of other optional compounds or additives may include dispersant additives, antifoam additives, flow additives, catalysts, solvents, fillers, dyes, toughening agents, softeners, processing aids, flow modifiers, Adhesion promoter, diluent, stabilizer, plasticizer, catalyst deactivator, flame retardant, aromatic hydrocarbon resin, coal tar pitch, petroleum pitch, carbon nanotube, graphene, carbon black, carbon fiber, or Its mixture.

The amount of the compound or additive as the case may be generally from 0% by weight to about 5% by weight. In various embodiments, the amount of the compound or additive may be from 0 wt% to about 5 wt%, from 0.1 wt% to about 2.5 wt%, and from 0.1 wt% to about 1 wt%, as appropriate.

(d) Properties of the curable composition

The curable composition exhibits a low viscosity sufficient to make it easy to process and handle with conventional formulation equipment. In general, the curable composition prepared using the foregoing procedure advantageously exhibits a low viscosity of less than or equal to about 5,000 mPa s at 25 °C. In various embodiments, the viscosity of the curable composition can be from 500 mPa s to about 5,000 mPa s, from 1,000 mPa s to about 4,000 mPa s, and from 2,000 mPa s to about 2,500 mPa s at 25 °C. A curable composition having a viscosity greater than about 5,000 mPa s results in poor outgassing, which in turn results in the formation of bubbles in the composition.

Other beneficial properties included in the curable composition are that the curable composition is capable of At temperatures below room temperature, i.e., about 10 ° C to 25 ° C, low temperature curing forms a thermoset; and the curable composition is capable of curing at an efficient cure rate (eg, the curable composition is at room temperature and at 13 ° C for several hours) Internal curing).

In general, the curing temperature of the curable composition can range from 0 °C to about 50 °C. In various embodiments, the curing temperature can range from 0 °C to about 50 °C, from 5 °C to about 40 °C, and from 10 °C to about 30 °C. If the curing temperature is lower than about 0 ° C, the curing speed may be too slow, and if the curing temperature is higher than 50 ° C, the curing speed may be too alkyne for the control of the reaction.

A specific example includes curing the curable composition discussed above to form a cured product such as a coating or thermoset. For example, curing of the curable composition can be carried out at a predetermined temperature and for a predetermined time sufficient to cure the composition to form a cured coating material.

(III) Method for preparing a low temperature curing hardener composition

In general, the method for preparing the aforementioned low-temperature curing hardener composition generally includes a preparation step of each component; the preparation of component A is followed by distillation to remove excess monomolecular structural amine, and the preparation of component B is then removed by distillation. Excess monomolecular structural amine, and component C. These components A, B and C are mixed (mixed) with the modifier and optionally the additives.

Component A is prepared by mixing the first amine compound (a) (i) and the polyfunctional epoxy compound (a) (ii) at a temperature of from 70 ° C to about 90 ° C. Excess monomolecular amines are removed from the reaction mixture by vacuum distillation (for example at 200 ° C and 5 mbar).

Component B is prepared by mixing the second amine compound (b) (i) and the monofunctional epoxy compound (b) (ii). Excess monomolecular amines are removed from the reaction mixture by vacuum distillation (for example at 200 ° C and 5 mbar).

The curable composition comprising components A, B and C can be from about 20 ° C to about 100 ° C Mix with modifiers and other optional additives as appropriate.

For example, the curable composition of the present invention can be prepared by blending a first amine adduct (component), a second amine adduct (component B), and a third amine in a known mixing apparatus. The adduct (component C) and the modifier are used. These components can be mixed in one order, randomly or sequentially. Any of the foregoing optional additives may be added to the composition to form a curable composition between or after mixing.

All of the compounds used to prepare the curable composition are typically blended and dispersed at a temperature that will help form a curable composition having an effective balance to the desired properties for a particular application. For example, the temperature at which all components are mixed can generally range from about 20 °C to about 100 °C. In various embodiments, the temperature at the time of mixing may range from 20 ° C to about 100 ° C, from 30 ° C to about 90 ° C, from 40 ° C to about 80 ° C, or from 50 ° C to about 70 ° C.

The preparation of the low temperature curing hardener composition and/or any of its steps can be batch or continuous. The mixing equipment used in the process can be any container and auxiliary equipment well known to those skilled in the art.

(IV) Method for preparing a curable composition

In general, the curable composition is first prepared by mixing, blending or mixing: (I) the foregoing epoxy resin and (II) at least one of the aforementioned low temperature curing hardener compounds; The mixture is heated at a temperature at which the curable coating composition is produced, which is subsequently cured by heating. Optionally, the curable composition can include any desired and one or more of the foregoing additives as appropriate.

For example, the composition may be prepared by blending (I) at least one epoxy resin in a known mixing apparatus; and (II) at least one of the aforementioned low temperature curing hardener compounds; (III) any other required additives to complete. Any of the foregoing optional additives may be added to the composition between mixing or prior to mixing to form a curable composition.

All of the compounds of the composition are typically mixed and dispersed at a temperature that will help form a curable composition that is effective for balancing the desired properties for a particular application. For example, in one embodiment, the temperature at which all components are mixed may generally range from about 0 ° C to about 50 ° C, and in another embodiment, from 0 ° C to about 30 ° C.

The preparation of the curable composition and/or any of its steps can be batch or continuous. The mixing equipment used in the process can be any container and auxiliary equipment well known to those skilled in the art.

(VI) Method of curing a curable composition

Another aspect of the invention provides a method of making a cured composition. The method comprises providing a curable composition as detailed above, exposing the curable composition to heat to form a cured coating. Generally, at least a portion of the surface of the article to be coated is coated with a curable composition prior to heat curing.

(a) curable composition

Suitable curable compositions are as previously described.

(b) items

The invention further encompasses an article comprising a cured or uncured curable composition adhered to at least a portion of the surface. The article can be broadly defined as a material in which the curable composition is initially coated and adhered to at least a portion of at least one surface of the substrate. The curable epoxy resin composition can be cured by exposing the composition to heat, which forms a thermoset or cured composition to bond the coating to the substrate. The item can be any that can withstand curing temperatures A material that forms a cured coating.

In various embodiments, the article can be a metal. The article, as defined herein, may be a single metal or an alloy of different metals. Non-limiting examples of such metals include cast iron, aluminum, tin, brass, steel, copper, zinc aluminum alloy, nickel, or combinations thereof.

In other embodiments, the substrate can be a cellulosic product. Non-limiting examples of cellulosic products can be paper, cardboard, paper cards, cardboard, and wood.

In yet another embodiment, the substrate can be a plastic. Non-limiting examples of plastics may be bakelite, polyester, polyethylene terephthalate, polyethylene, high density polyethylene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polystyrene, polyfluorene. Amine (nylon), acrylonitrile-butadiene-styrene, polycarbonate, polyurethane, and combinations thereof.

In a further embodiment, the item can be a stone. Non-limiting examples of stones can be granite, brick, limestone, concrete, and combinations thereof.

In another embodiment, the item can be a floor. Non-limiting examples of flooring may be cement, acrylic flooring, vinyl flooring, laminate flooring, wood flooring, ceramic tiles, and varnish.

In different specific examples, the item can have a different configuration. Non-limiting examples of configurations may be reels, coils, plates, sheets, tubes, bricks, slabs, boulders, or tubing. The configuration of the item can be of various sizes, shapes, thicknesses and weights.

(c) coating a curable composition

The method further includes applying a curable composition to a portion of at least one surface of the article. Suitable items have been detailed above. The coating of the curable coating composition can be applied by different means. For example, the coating composition can use a drawdown bar, Rolls, knives, paint brushes, sprays, dip coatings or the like are applied in a manner known to those skilled in the art. As detailed above, the curable coating composition can be applied to one or more surfaces of the article to be coated.

(d) curing curable composition

The method further includes curing the curable epoxy resin composition to a portion of at least one surface of the article. The curable composition, as detailed in the present invention, can be formed by exposing the composition to heat to form a cured composition or thermoset.

In general, the method of making the cured coating material involves performing a curing reaction under processing conditions to enable the preparation of an effective cured material (particularly to form a coated product) having a balance of properties desired for particular applications. The temperature of the curable curable composition may range from -10 ° C to about 50 ° C. In various embodiments, the curing temperature can range from -10 ° C to about 50 ° C, from -5 ° C to about 50 ° C, from 0 ° C to about 45 ° C, from 5 ° C to about 40 ° C.

In general, the curing time can also vary. In various embodiments, the curing time can range from 0.1 hours to about 7 days, from 0.5 hours to about 1 day, and from 1 hour to about 6 hours.

The preparation of the cured coating material and/or any of its steps can be batch or continuous. The equipment used to carry out the reaction includes equipment known to those skilled in the art.

Curing product characteristics

Another aspect includes the end use of the cured product. Non-limiting examples of end use products for curing compositions can include coatings, paintings, infusions, packaging applications, flooring, thermosets, and primers.

Yet another aspect includes the properties of the cured product or thermoset. Curing the above The cured thermoset product prepared from the curable composition of the hardener composition exhibits unexpected and unique characteristics. For example, cured thermoset products, such as coatings, exhibit improved flexibility; when cured at room temperature, they exhibit a glossy, non-twisted, smooth surface, and are visually inspected at 13 ° C. May be slightly dull, slightly distorted, not smooth"; exhibits at least moderate chemical resistance with a cured thermoset product from a composition containing a hardener (3 day cotton pad test); and an E modulus below 2.5 MPa .

Cured coatings (i.e., crosslinked coating products made from curable compositions) exhibit several improved and advantageous performance characteristics over conventional cured coating products made from conventional curable compositions containing conventional curing agents. In general, the cured composition may exhibit enhanced flexibility. In general, cured coatings may exhibit flexural properties generally between 1 and 2.5. In various embodiments, the flexibility properties may range from 1 to about 2.5, from 1.2 to about 2.2, and from 1.5 to about 2. The flexural properties of the cured coating material can be determined according to ATSM D 790 using a three point bend test.

The cured coating can also advantageously exhibit a good surface appearance. In general, the cured coating may exhibit surface appearance characteristics that are generally good to good, good to moderate, and moderate to about acceptable. The surface characteristics of the cured coating material can be judged by visual inspection.

The cured coating may also advantageously exhibit chemical resistance of at least "moderate" (3 day cotton pad test, "good" for 7 days). In general, the cured coatings of the present invention exhibit chemical resistance from "moderate to good". The chemical resistance of the cured coating material can be determined using a cotton pad test method.

The cured product may also exhibit improved chemical resistance relative to other cured products that do not use a low temperature curing hardener composition. In homogenizing two components (the hardener of the invention or comparison After 2 minutes of the hardener and D.E.R. 3531 epoxy resin, the liquid mixture was poured into a mold so that the film thickness was 3 mm and cured at room temperature for 7 days.

These films were tested by exposing them to different solutions for 7 days (168 hours) by placing a cotton pad soaked in the solution on the sample and covering the pad to the sample. The samples were measured for Shore D hardness after 1 day (24 hours) exposure, 2 days (48 hours) exposure, and 7 days (168 hours) exposure. The Xiao's D hardness measurement results are shown in Figures 1 and 2.

The percent change in Shore D hardness (shown as percentage Δ (% A)) was determined using the initial hardness and the final hardness after exposure to the solution for 168 hours. The percentage change in the D hardness of Xiao is calculated as (1-(final hardness/initial hardness))*100, wherein the negative hardness percentage change value indicates that the value of the initial hardness is larger than the value of the final hardness.

definition

The articles "a" and "the/said" are intended to mean one or more elements. The words "comprising", "including" and "having" are intended to include additional elements that are not intended to be in the

The term "elongation" or "tensile elongation" as used in the present invention refers to a mechanical property in which a polymer deforms or changes shape under tensile stress. When the polymer sample is deformed by stretching, it becomes longer. Elongation is typically expressed as percent elongation (%) which is the length (L) of the polymer sample after stretching divided by the initial length of the sample (L0) and multiplied by 100. Elongation at yield is the point at which stress increases without causing an increase in length. "Elongation at break" corresponds to the breaking point.

"glass transition temperature" is the polymer The hard, vitreous material transforms into a soft, rubbery material.

"Cold crystallization temperature" is the temperature at which the polymer crystallizes.

The term "tensile modulus" or "Young's modulus" refers to the rigidity of a material and is used to describe the elastic properties of a material. The tensile modulus is defined as the ratio of the axial stress (force per unit area) to the axial strain (initial length deformation ratio).

The term "tensile strength at break" refers to the tensile stress at which the test specimen breaks. Tensile strength is the force placed on the test sample divided by the cross-sectional area of the sample.

The phrase "low volatile organic compounds (VOC) content" means a composition having a VOC content of 0 to 5 g/L in the hardener composition.

The phrase "low free amine content" means a composition having less than 20% by weight of free amine in the hardener composition.

The term "low viscosity" means a composition having a viscosity of the hardener composition of less than 1,500 mPa s at 25 °C.

The term "low temperature curing" means that the curing temperature is in the range of from about 0 ° C to about 50 ° C.

The term "good surface appearance" means a composite having a shiny, glossy, non-twisted, pale yellow, non-whitened or whitened/blurred composite surface.

The term "fair surface appearance" means a composite having a slight distortion and some whitish, concomitant surface of the composite.

The term "medium chemical resistance" refers to a cured material (thermoset) or composite that can withstand at least 3 days of cotton pad chemical testing without degradation.

By "flexibility" is meant a complex having a composite E modulus of less than about 2.5 GPa.

As used herein, the term "alkyl" is used to describe a saturated hydrocarbon group containing from 1 to 30 carbon atoms, more preferably from 1 to 20 carbon atoms, and most preferably from 1 to 10 carbon atoms. They may be linear, branched or cyclic and may be substituted by the definitions including methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl, octyl, decyl and the like.

As used herein, the term "alkenyl" is used to describe a hydrocarbon group containing at least one carbon-carbon double bond and having from 1 to 30 carbon atoms. They may be linear, branched or cyclic and may be substituted by the definitions including vinyl, propenyl, isopropenyl, butenyl, isobutenyl, hexenyl and the like.

The term "alkoxide" or "alkoxy" as used in the present invention is a conjugate base of an alcohol. The alcohol may be linear, branched or cyclic and comprises an aryloxy compound.

As used herein, the term "alkynyl" is used to describe a hydrocarbon group containing at least one carbon-carbon triple bond and having from 1 to 30 carbon atoms. They may be linear, branched or cyclic and may be substituted by the definitions including ethynyl, propynyl, butynyl, isobutynyl, hexynyl and the like.

As used herein, the term "aromatic", alone or as part of another group, refers to a conjugated planar ring or ring system containing a homocyclic or heterocyclic group of a non-localized electron, as appropriate. . These aromatic groups preferably have 5 to 14 carbon atoms in the ring portion. Monocyclic (eg, furan or benzene), bicyclic, or tricyclic groups. The term "aromatic" includes the "aryl" as defined below.

As used herein, the term "aromatic" as used alone or as part of another group refers to a homocyclic aromatic group which is optionally substituted, preferably a monomer having from 6 to 10 carbon atoms in the ring portion. a cyclic or bicyclic group such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl, wherein the "substituted" substituent includes a carbon chain atom or a carbon atom such as A moiety substituted with a hetero atom of nitrogen, oxygen, helium, phosphorus, boron or a halogen atom, and a portion of the carbon chain containing an additional substituent. These substituents include alkyl, alkoxy, decyl, decyloxy, alkenyl, alkenyloxy, aryl, aryloxy, amine, decylamino, acetal, amine, mercapto, carbocyclic , cyano, ester, ether, halogen, heterocyclic, hydroxy, keto, ketal, diphosphoryl, nitro and thio.

The term "hydrocarbon" or "hydrocarbyl" as used in the present invention refers to an organic compound or group consisting only of carbon and hydrogen. These moieties include alkyl, alkenyl, alkynyl and aryl moieties. These moieties also include alkyl, alkenyl, alkynyl and aryl moieties substituted with other aliphatic or cyclo or cyclic hydrocarbyl groups such as alkaryl, alkaryl and alkynyl. They can be linear, branched or circular. Unless otherwise indicated, these moieties preferably contain from 1 to 20 carbon atoms.

As used herein, the term "substituted hydrocarbyl" refers to a hydrocarbyl moiety substituted with at least one atom other than carbon or hydrogen, including a carbon chain atom such as nitrogen, oxygen, helium, phosphorus, boron or a halogen atom. A moiety substituted with a hetero atom and a portion of the carbon chain containing an additional substituent. These substituents include alkyl, alkoxy, decyl, decyloxy, alkenyl, alkenyloxy, aryl, aryloxy, amine, decylamino, acetal, amine, mercapto, carbocyclic , cyano, ester, Ether, halogen, heterocyclic, hydroxy, keto, ketal, diphosphoryl, nitro and thio groups.

It has been described in detail in the present invention that modifications and variations are possible without departing from the scope of the appended claims.

Example

The following examples and comparative examples illustrate the invention in further detail, but are not to be construed as limiting the scope of the claims.

The different materials, terms, and codes used in the following examples are, for example, the original materials listed in List 1 below:

Example 1: Preparation of (BADGE/MXDA Additive)

In this Example 1, the preparation of the MXDA adduct is generally described as 4,4'-isopropylidenediphenol and 1-chloro-2,3-epoxypropane according to the general procedure below. Widow The reaction product of the polymerization product and m-phenylene bis(methylamine):

Part A: Small scale

On a small laboratory scale, 1 gram (g) of a mixture of MXDA and bisphenol A diglycidyl ether (D.E.R. 331) (4 moles: 1 mole) was prepared at room temperature (about 25 ° C). A drop of the mixture was then transferred to a helium of a Differential Scanning Thermal Analyzer (DSC) and heated to 80 °C. The heat flux of the heated mixture is measured. After 25 minutes (min) the reaction was considered to be over.

Part B: Larger scale

On a larger laboratory scale, 600 g of amine (MXDA) was placed in a flask with a heating mantle, the amine was stirred, and the amine was heated to 80 ° C while stirring. Then, 400 g of an epoxy compound (D.E.R. 331) was added to the above flask. The epoxy compound is added to the flask at an addition rate sufficient to maintain the temperature at about 80 to 90 °C. The flask was cooled by removing the heating mantle as needed. After the addition of the epoxy compound, a post-reaction was carried out at a reaction temperature of 80 ° C for at least 25 minutes.

Example 2: Preparation of CEG-MPMD adduct

Part A: Small scale

1 g of a mixture of MPMD and o-tolyl glycidyl ether (DER723) (2 mol: 1 mol) was prepared at room temperature and a drop of the mixture was transferred to a crucible of a differential scanning calorimeter (DSC). Heat to 80 ° C and measure the heat flux. After 25 minutes (min) the reaction was considered to be over.

Part B: Larger scale

On a larger scale, the amine is placed in a flask with a heating mantle and heated. The epoxy compound was then added to the aforementioned flask at a rate at which the temperature was maintained. The flask was cooled by removing the heating mantle as needed. After the addition, the reaction is carried out at the reaction temperature for at least 25 minutes. (post-reaction). After the reaction, the molar excess of MPMD was removed by vacuum distillation.

Example 3: Preparation of cured sample

Mixing hardener with DER3531, diluted epoxy resin (bisphenol A epoxy resin, bisphenol F epoxy resin and a mixture of dodecyl alcohol and tetradecanol monoglycidyl ether as reactive diluent) The compound was mixed at room temperature in an epoxy equivalent ratio of 1 amine equivalent to produce a curable composition. The aforementioned hardener/epoxy curable composition was then cured at a curing temperature of 13 ° C and 23 ° C.

In an embodiment: the use of standard analytical equipment and method measurements includes, for example, the following properties:

Flexibility (E modulus)

Flexibility is defined by a three point bend test according to the procedure described in ATSM D 790.

Early water stain test

The water drop test was carried out as follows: a drop of water was placed on the surface of the thermoset substrate that had not yet fully cured, and the water evaporated to leave a white urethane on the surface of the thermoset. If the water evaporates without leaving a white urethane on the surface of the thermoset that has not yet fully cured, it means that the hardener is not sensitive to water droplets, which is desirable.

Chemical resistance comparison

After homogenizing the hardener of the present invention with DER3531 epoxy resin or comparative hardener and DER3531 epoxy resin for 2 minutes, the liquid mixture is poured into a mold to form a film so that after the liquid mixture is cured, the film thickness is about 3 mm. (mm); the liquid mixture was then cured at room temperature for 7 days (168 hours [hr]).

These films were tested by exposing them to different test liquid solutions for 7 days (168 hours) by placing a cotton pad soaked in the solution on the sample and covering the pad with the sample with a plastic cover. The Xiao's D hardness of each sample was measured according to the procedure described in ASTM D2240 after 1 day (24 hours) exposure, 2 days (48 hours) exposure, and 7 days (168 hours) exposure. The Xiao's D hardness measurement results are shown in Figures 1 and 2, and the percentage change in Xiao's D hardness (shown as percentage Δ(% A)) by measuring the initial hardness and the final hardness after exposure to the solution for 168 hours. To determine. The percentage change value of the Shore D hardness is calculated using the following formula: (1-[Final Hardness/Initial Hardness])*100, wherein the negative hardness percent change value indicates that the value of the initial hardness is larger than the value of the final hardness.

The test liquids used for chemical resistance comparison were acetic acid, sulfuric acid, sodium hydroxide, gasoline, Bau-und Prüfgrundsätze Gruppe 5b (B.P.G.5b), xylene and methyl isobutyl ketone (MIBK). Specific compounds used for testing include the following: acetic acid, sulfuric acid, and sodium hydroxide are of analytical grade and are commercially available from the Merck Group.

DIBT's Bau-und Prüfgrundsätze Gruppe 5b (Policy for Construction and Testing Group 5b of the German Institute for Construction Technique) (hereinafter referred to as "BPG5b") is 48 A mixture of volume percent methanol, 48 volume percent isopropanol, and 4 volume percent water. The methanol and isopropanol used were of analytical grade and were commercially available from the Merck Group.

The gasoline used for testing is commercially available from Esso (Exxon).

The xylene, ethanol and methyl isobutyl ketone (MIBK) used for the test were of analytical grade and were commercially available from the Merck Group.

Examples 5-12 and Comparative Examples 1-4

The hardener was prepared by (physical) mixing/blending at 23 °C. The components used in the compositions of Inventive Examples 5-12 (Composition #5-#12) and Comparative Examples 1-4 (#1-#4) are described in Table II.

Table II describes the compositions (compositions #4 to #12) of the present invention and comparative compositions (compositions #0 to #3). As shown in Table II, Composition #11 was the most effective composition.

Claims (20)

A low temperature curing hardener composition comprising component A, component B and component C, wherein: a. component A comprises: i. an adduct of at least one first amine compound; ii at least one multifunctional epoxy resin And iii a modifier; wherein component A has from 0 g/L to about 5 g/L of volatile organic compound, from about 1 to about less than about 20% by weight of free amine, and from about 150 mPa s to less than about a viscosity of 1,500 mPa s; b. component B, comprising: i. an adduct of at least one second amine compound; ii. at least one monofunctional epoxy resin; and iii. a high boiling point modifier; B has a volatile organic compound content of less than about 5 g/L, a free amine content of less than about 20 weight percent, and a viscosity of less than about 1,500 mPa s at 25 ° C; and c. component C, comprising at least one based a polyolefin oxide; a third amine adduct based on a cycloaliphatic amine, an aliphatic amine or an arylamine; or a combination thereof; wherein component C has a volatile organic compound content of less than about 5 g/L, low The free amine content is about 20 weight percent, and the viscosity is less than about 1,500 mPa s at 25°. The hardener composition of claim 1, wherein the at least one first amine compound adduct is m-xylylenediamine. The hardener composition of claim 1, wherein the at least one first amine compound The concentration of the adduct is from about 20 weight percent to about 50 weight percent. The hardener composition of claim 1, wherein the at least one multifunctional epoxy resin is at least one bisphenol A diglycidyl ether. The hardener composition of claim 1, wherein the concentration of the modifier in component A is from about 5 weight percent to about 50 weight percent. The hardener composition of claim 1, wherein the at least one second amine compound adduct is methyl pentamethylenediamine. The hardener composition of claim 1, wherein the concentration of the at least one second amine compound adduct is from about 20 weight percent to about 50 weight percent. The hardener composition of claim 1, wherein the at least one monofunctional epoxy resin is tolyl glycidyl ether. The hardener composition of claim 1, wherein the concentration of the modifier in component B is from about 5 weight percent to about 50 weight percent. The hardener composition of claim 1, wherein the at least one third amine adduct is an amine selected from the group consisting of polyoxyalkyleneamines, trimethylpentamethylenediamine, and mixtures thereof. . The hardener composition of claim 1, wherein the concentration of the at least one third amine adduct is from about 0.1 weight percent to about 10 weight percent. A method of preparing a low temperature curing hardener composition comprising mixing: a. component A; b. component B; and c. component C. A method of preparing component A of a low temperature curing hardener composition comprising mixing: a. an adduct of at least one first amine compound; b. at least one multifunctional epoxy resin; and c. a high boiling point modifier Wherein the hardener composition has a volatile organic compound content of less than about 5 g/L, a free amine content of less than about 20 weight percent, and a viscosity of less than about 1,500 mPa s at 25 °C. A method of preparing component B of a low temperature curing hardener composition, comprising: mixing: a. an adduct of at least one second amine compound; b. at least one monofunctional epoxy resin; and c. a high boiling point modifier Wherein the hardener composition has a volatile organic compound content of less than about 5 g/L, a free amine content of less than about 20 weight percent, and a viscosity of less than about 1,500 mPa s at 25 °C. A method of preparing component C of a low temperature curing hardener composition comprising at least one third amine adduct based on a polyolefin oxide, or a cycloaliphatic amine or an aliphatic amine or an arylamine or a combination thereof One or more additive blends; wherein the hardener composition has a volatile organic compound content of less than about 5 g/L, a free amine content of less than about 20 weight percent, and a lower than about 1,500 mPa s at 25 °C Viscosity. A curable coating composition comprising: A. at least one epoxy resin; wherein the at least one epoxy resin is a bisphenol A epoxy resin, a bisphenol F epoxy resin a blend of a mixture of dodecyl alcohol and tetradecanol monoglycidyl ether as a reactive diluent; and B. at least one of the low temperature curing hardener compositions of claim 1; wherein the hardener is composed The composition has a volatile organic compound content of less than about 5 g/L, a free amine content of less than about 20 weight percent, and a viscosity of less than about 1,500 mPa s at 25 °C. The curable coating composition of claim 16, wherein the concentration of the at least one epoxy resin and the at least one hardener composition is about one amine equivalent to one epoxy equivalent. The curable coating composition of claim 16, which further comprises a filler, a modifier, a second thermosettable resin or a mixture thereof. A method of preparing a curable coating composition comprising: mixing: A. at least one epoxy resin compound; and B. at least one low temperature curing hardener composition as in claim 1; wherein the hardener composition It has a volatile organic compound content of less than 5, about 5 g/L, a free amine content of less than about 20 weight percent, and a viscosity of less than about 1,500 mPa s at 25 °C. A cured coating product obtained by curing a curable composition as claimed in claim 16 of the patent application.