TW201533179A - Coating method for surfaces in chemical installations - Google Patents

Abstract

The invention pertains to a method for providing a metallic or concrete surface of a chemical installation with a coating, which comprises the steps of - providing a coating composition comprising epoxy-functional resin, and amine curing agent for the epoxy-functional resin, wherein the coating composition comprises an organic silicon-containing compound selected from the group of organosilanes and organosiloxanes, with the molar ratio between the silicon atoms of the organic silicon-containing compound and the epoxy-groups in the coating composition being in the range of 0.20-0.75:1.00, - applying the coating composition to a metallic or concrete surface of a chemical installation to form a coating layer, and - allowing the coating layer to cure at a temperature in the range of 0 to 50 DEG C.

Description

Coating method for the surface of chemical equipment

This invention relates to a method for providing a coating to a metal or concrete surface of a chemical plant. The invention is also directed to compositions suitable for use as coatings for metal or concrete surfaces of chemical equipment and chemical equipment having such coatings.

In chemical equipment, metal and concrete surfaces are in contact with numerous chemical compounds. These surfaces typically have a coating that serves two purposes. First, the coating is intended to protect the surface from the chemicals. Second, the coating is designed to protect the chemical from contamination (eg, by corrosion) on the surface of the device (eg, a sump). For broad applicability, coatings for this application should be able to handle interactions with numerous chemical compounds. In addition, the coating should be able to withstand high temperature and high pressure conditions.

There is another problem with contacting the surface of more than one chemical in sequence. This is the case, for example, in storage or transport tanks for storing or transporting liquid bulk chemicals on land or in the sea. The important characteristics of coatings that come into contact with different classes of chemicals are the interaction with various chemicals, with the aim of avoiding contamination of subsequent chemicals. Thus, on the one hand, bulk chemicals can be adsorbed upon contact with the surface and this adsorption should be minimized. On the other hand, if the coating adsorbs chemicals, the chemicals should be easily removed by conventional cleaning methods. This can be described as a coating with high chemical resistance, where the term chemical resistance refers to the tendency of the coating to adsorb chemicals and subsequently release chemicals while maintaining film integrity.

WO 2012/119968 describes a coating composition comprising an epoxy resin mixture, A curing agent, accelerator or accelerator mixture and one or more fillers or pigments, wherein the epoxy resin mixture comprises 60 to 80% by weight of RDGE epoxy resin and 20 to 40% by weight of epoxy novolac resin. The coating composition is referred to as a sump liner composition.

Although the coating composition described in this reference exhibits good properties when used as a lining coating for a sump, there is still a need to provide a coating on a metal or concrete surface of a chemical device, and has a wide range of applications and high chemical resistance. Alternative coating compositions. By broad application range, we mean that the coating composition can be applied and cured across a range of temperatures (eg, 5 ° C to 35 ° C), and the coating will deliver good coating properties (good adhesion, good film integrity) ) and chemical resistance.

The present invention provides such a coating composition. The invention also provides a method for providing a cured coating to a concrete or metal surface of a chemical device, and a surface having such a layer.

In one embodiment, the present invention is directed to a method for providing a coating to a metal or concrete surface of a chemical device, comprising the steps of: - providing a coating composition comprising an epoxy functional group-containing resin and An amine curing agent for an epoxy functional group-containing resin, wherein the coating composition comprises an organic cerium-containing compound selected from the group consisting of organic decane and an organic decane, wherein the cerium atom of the organic cerium-containing compound is combined with the coating The molar ratio between the epoxy groups is in the range of 0.20 to 0.75:1.00, applying the coating composition to the metal or concrete surface of the chemical equipment to form a coating, and - causing the coating to Curing at temperatures ranging from 0 to 50 °C.

In one example, the molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition is in the range of 0.25 to 0.75:1.00.

In another embodiment, the present invention is directed to a chemical apparatus comprising a metal or concrete surface having a lining of a cured coating composition, wherein the cured coating composition is a coating composition derived from a resin comprising an epoxy functional group-containing resin and an amine curing agent for the epoxy functional group-containing resin, wherein the coating composition comprises an organic group selected from the group consisting of organic germanes and organic germanium oxides. The cerium-containing compound wherein the molar ratio between the cerium atom of the organic cerium-containing compound and the epoxy group in the coating composition is in the range of 0.20 to 0.75:1.00.

In one example, the molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition is in the range of 0.25 to 0.75:1.00.

In another embodiment, the present invention is directed to a coating composition suitable for use in providing a coating to a metal or concrete surface of a chemical device, wherein the coating composition comprises an epoxy functional group-containing resin and is used in the ring An amine functional curing agent for an oxygen functional group, wherein the coating composition comprises an organic cerium-containing compound selected from the group consisting of organic decane and an organic decane, wherein the cerium atom of the organic cerium-containing compound is in the coating composition The molar ratio between the epoxy groups is in the range of 0.20 to 0.75:1.00.

In one example, the molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition is in the range of 0.25 to 0.75:1.00.

Compositions comprising a ruthenium containing compound and an epoxy functional group-containing resin are known, for example, from US 2013/0224496, WO 2013/110046, WO 2004/033570, and US 2013/0237638.

All of the compositions disclosed in US 2013/0224496, WO 2004/033570, and US 2013/0237638 have a molar ratio of the ruthenium atom of the organic ruthenium containing compound to the epoxy group of the coating composition of greater than 0.75:1.00. WO 2013/110046 does not provide guidance on the molar ratio of the ruthenium atom of the organic ruthenium containing compound to the epoxy group of the coating composition. There is no suggestion in these documents that the molar ratio of the epoxy group between the ruthenium atom of the organic ruthenium containing compound and the coating composition is as claimed herein (e.g., 0.20 to 0.75: 1.00), and such coating combinations The article will have improved chemical resistance and other advantageous properties, such as better recoatability.

The invention will be described in more detail below.

In the present invention, the coating composition comprises an epoxy functional group-containing resin, an amine curing agent for the epoxy functional group-containing resin, and an organic cerium-containing compound selected from the group consisting of organodecane and organic decane. The organic cerium-containing compound may be one or more selected from the group consisting of decane and decane containing epoxy functional groups, decane and decane containing amino functional groups, and organic decane or organic oxirane having no epoxy or amine functionality. a compound of the group of alkanes. The coating composition may comprise a ruthenium containing epoxy resin (ie, an epoxy functional decane and a decane) and a non-ruthenium epoxy resin, and a guanamine containing curing agent (ie, an amine functional group-containing decane and A buffer of a decylamine and a hydrazine-free curing agent. Additionally, as indicated above, the coating composition can comprise an organodecane or an organodecane having no epoxy or amine functionality. The coating composition may also contain other components such as fillers and pigments.

In the following, the various components of the coating composition will first be discussed. The composition itself will then be discussed.

Epoxy and decane containing epoxy functional groups

In one embodiment of the invention, the coating composition comprises at least one epoxy-functional decane or decane. Within the scope of the present description, the term epoxide containing an epoxy functional group means a monoglycidyl alkoxy decane, and the oxyalkylene containing an epoxy functional group is meant to comprise any at least one -Si-O-Si- Single and polyglycidyl polyoxymethane compositions of the components of the bonded composition.

An epoxy functional group-containing decane and an epoxy functional group-containing oxirane suitable for use in the present invention include those having the formula 1, Formula 1: QR ¹ -Si-(OR ² ) _n (R ³ ) _{2 -n} -O[-(QR ¹ )Si(OR ² ) _n-1 (R ³ ) _2-n -O-] _m R ²

Wherein Q represents glycidyloxy ( And R ¹ represents an aliphatic alkyl group having 1 to 6 carbon atoms, R ² represents an aliphatic monovalent C1-C6 alkyl group, and R ³ represents an aliphatic monovalent C1-C6 alkyl group or a monovalent C6 aromatic group, n Is 1 or 2, and m is an integer greater than or equal to zero.

R ¹ preferably has 2 to 4 carbon atoms, more preferably 3. R ^{2 is} preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group. R ^{3 is} preferably an aliphatic C1-C6 alkyl group, more specifically a methyl group, an ethyl group or a propyl group, more preferably a methyl group, or a monovalent C6 aromatic group, preferably a phenyl group.

When n = 2, R ³ does not exist. When m = 0, the formula describes a decane containing an epoxy functional group. When m > 0, the formula describes a oxirane containing an epoxy functional group. In the case of epoxy oxiranes, m can vary over a wide range. The m of the epoxy functional group-containing decane used in the present invention generally preferably has a number average of up to 10. Suitable epoxy functional decane or decane compounds are known in the art.

In one embodiment, an oxirane containing an epoxy functional group of formula 1 wherein R ¹ = -CH ₂ CH ₂ CH ₂ -, R ² = CH ₃ , R ³ is absent, n = 2 and m = 0 is used. The compound has the following chemical formula

This material is glycidoxypropyltrimethoxydecane (GOPTMS) and is available, for example, from Evonik (under the trade name Dynasylan GLYMO).

In another embodiment, an epoxy functional oxyalkylene oligomer having a -(Si-O)-backbone and a pendant epoxy group is used. In one embodiment, such an oxirane oligomer having an epoxy functional group of the above formula 1 is used, wherein R ¹ = -CH ₂ CH ₂ CH ₂ -, R ² = CH ₃ , and R ³ is absent. , n=2 and m has a number average of 2 to 8, in particular in the range of 3 to 5, for example about 4. This material is manufactured by Momentive Performance Chemicals and sold under the trade name Momentive MP200.

There are many other suitable compounds that can be used, including glycidoxypropyltriethoxydecane (a compound of formula 1 wherein R ¹ =-CH ₂ CH ₂ CH ₂ -, R ² =CH ₂ CH ₃ , R ^{3 is} not Exist, n=2 and m=0), Silres HP1000 from Wacker (compound of formula 1 wherein m=2, n=1, R ² =CH ₃ , R ³ =phenyl), glycidoxypropyl di Methyl ethoxy decane (compound of formula 1 wherein R ¹ =-CH ₂ CH ₂ CH ₂ -, R ² =CH ₂ CH ₃ , R ³ =CH ₃ , n=0 and m=0), 3-shrinkage Glyceroxypropylmethyldimethoxydecane (compound of formula 1 wherein R ¹ =-CH ₂ CH ₂ CH ₂ -, R ² =CH ₃ , R ³ =CH ₃ , n=1 and m=0) 3-glycidoxypropylmethyldiethoxydecane (compound of formula 1 wherein R ¹ =-CH ₂ CH ₂ CH ₂ -, R ² =CH ₂ CH ₃ , R ³ =CH ₃ , n= 1 and m=0).

In one embodiment, one or more of the following epoxy functional group-containing decane and epoxy functional group-containing oxirane are used, wherein R ⁴ is glycidyloxy group, and the e value is from 0.1 to 0.5, f value. It is from 0.1 to 0.5 and has a g value of from 0.5 to 0.9: an oxime-containing material containing the following units: (R ⁴ (CH ₃ ) ₂ SiO _1/2 ) _e and (C ₆ H ₅ SiO _3/2 ) _g

An oxime-containing material comprising the following units: (R ⁴ (CH ₃ ) ₂ SiO _1/2 ) _e , ((CH ₃ ) ₂ SiO _2/2 ) _f and (C ₆ H ₅ SiO _3/2 ) _g

An oxime-containing material comprising the following units: ((CH ₃ ) ₃ SiO _1/2 ) _e , (R ⁴ (CH ₃ )SiO _2/2 ) _f and (C ₆ H ₅ SiO _3/2 ) _g

An oxime-containing material comprising the following units: (R ⁴ (CH ₃ )SiO _2/2 ) _f and (C ₆ H ₅ SiO _3/2 ) _g

An oxime-containing material comprising the following units: (R ⁴ (CH ₃ ) ₂ SiO _1/2 ) _e and (CH ₃ SiO _3/2 ) _g

An oxime-containing material comprising the following units: (R ⁴ (CH ₃ ) ₂ SiO _1/2 ) _e , ((CH ₃ ) ₂ SiO _2/2 ) _f and (CH ₃ SiO _3/2 ) _g

An oxime-containing material comprising the following units: ((CH ₃ ) ₃ SiO _1/2 ) _e , (R ⁴ (CH ₃ )SiO _2/2 ) _f and (CH ₃ SiO _3/2 ) _g

An oxime-containing material comprising the following units: (R ⁴ (CH ₃ )SiO _2/2 ) _f and (CH ₃ SiO _3/2 ) _g

An oxime-containing material comprising the following units: ((CH ₃ ) ₂ SiO _2/2 ) _f and (R ⁴ SiO _3/2 ) _g .

Alkane-containing decane and decane

In one embodiment of the invention, the coating composition comprises at least one decane or decane having an amine functional group. The amine functional group-containing decane or decane can be used as the sole amine curing agent for the epoxy functional group-containing resin, or it can be used in combination with a decylamine-free curing agent. Suitable amine-containing functional decanes or decanes are known in the art.

The alkane-containing functional group-containing decane and the amino group-containing functional group-containing oxirane which are suitable for use in the present invention include those having the formula 2: Formula 2: Q'-NH-R' ¹ -Si-(OR' ² _n' (R' ³ ) _2-n' -O[-(Q-NH-R' ¹ )Si(OR' ² ) _n'-1 (R' ³ ) _2-n' -O-] _m' R' ²

Wherein Q' represents a residue -(CH ₂ CH ₂ NH) _z' -H or an aminoaryl group, R' ¹ represents an aliphatic alkyl group having 1 to 6 carbon atoms, and R' ² represents an aliphatic monovalent C1- C6 alkyl group, R ^'3 represents a monovalent aliphatic C1-C6 alkyl or C6 monovalent aromatic radical, n' is 1 or 2, and m 'an integer greater than or equal to zero the system. In Formula 2, the z' value is 0, 1, or 2.

R' ¹ preferably has 2 to 4 carbon atoms, more preferably 3. R' ^{2 is} preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group. R' ^{3 is} preferably an aliphatic C1-C6 alkyl group, more specifically a methyl group, an ethyl group or a propyl group, more preferably a methyl group, or a monovalent C6 aromatic group, preferably a phenyl group.

When n 'time = 2, R' ³ is absent. When m' = 0, the formula describes a decane containing an amine functional group. When m'> 0, the formula describes a oxane having an amine functional group. In the case of a halogenated alkane having an amino functional group, m' can vary over a wide range. The m' of the decyl group containing an amino group functional group used in the present invention usually preferably has a number average of up to 10. Suitable amide or decane compounds containing amino functional groups are known in the art.

Examples of suitable decane or decane having an amino functional group include aminopropyltriethoxydecane (in Formula 2, Q'=-H, R' ¹ = -CH ₂ CH ₂ CH ₂ -, R ' ² =-CH ₂ CH ₃ , R' ³ is absent, and m'=0), aminopropyltrimethoxydecane (in formula 2, Q'=-H, R' ¹ =-CH ₂ CH ₂ CH ₂ -, R' ² = -CH ₃ , R' ³ is absent and m' = 0), aminophenyl trimethoxy decane (in formula 2, Q' = -C ₆ H ₄ NH ₂ , R' ¹ is absent, R' ² = -CH ₃ , R' ³ is absent and m' = 0), N-(2-aminoethyl)-3-aminopropyltriethoxydecane In Formula 2, Q'=-NHCH ₂ CH ₂ NH ₂ , R' ¹ =-CH ₂ CH ₂ CH ₂ -, R' ² =-CH ₂ CH ₃ , R' ³ is absent and m'=0), N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane (in the formula 2, Q'=-(CH ₂ CH ₂ NH)-H, that is, z'=1, in the formula 2, R' ¹ = -CH ₂ CH ₂ CH ₂ -, R' ² = -CH ₃ , R' ³ is absent and m' = 0) and (3-trimethoxymercaptopropyl) dibenz a triamine (in the formula 2, Q'=-(CH ₂ CH ₂ NH) ₂ -H, that is, z'=2, in the formula 2, R' ¹ = -CH ₂ CH ₂ CH ₂ -, R ' ² = -CH ₃ , R' ³ does not exist and m' = 0).

There are many other suitable compounds may be used of, comprising of from Wacker Silres HP2000 (compound of formula 2, where m '= 2, n' = 1, R '2 = CH 3, R' 3 = phenyl). An example of this is an amine oxane. Amines having alkoxydecane units in accordance with the present invention also include aminoalkylalkyldialkoxydecanes, aminoalkyldialkyldialkoxydecanes, and precondensed aminoalkylalkoxydecanes.

Organic decane and organic oxirane without epoxy or amine functionality

In one embodiment of the invention, the coating composition comprises at least one organodecane or organodecane having no epoxy or amine functionality. In the present specification, such compounds may also be referred to as non-functional organodecane or organodecane. The phrase non-functional means that the compound does not contain an epoxy or amine group which can react with the amine or epoxy group present in the composition, respectively. Suitable non-functional organodecanes and organodecanes are known in the art.

Organodecane and organooxane which are suitable for use in the present invention without epoxy or amine functionality include those having the formula 3: Formula 3: R" ¹ -Si-(OR" ² ) _n" (R" ³ ) _2-n" -O[-(R" ¹ )Si(OR" ² ) _n"-1 (R" ³ ) _2-n" -O-] _m" R" ²

Wherein R" ¹ represents a saturated or unsaturated aliphatic alkyl group having 1 to 6 carbon atoms or a monovalent C6 aromatic group, R" ² represents an aliphatic monovalent C1-C6 alkyl group, and R" ³ represents an aliphatic monovalent C1 a -C6 alkyl group or a monovalent C6 aromatic group, n" is 1 or 2, and m" is an integer greater than or equal to zero.

When R" ¹ is non-aromatic, it preferably has from 1 to 4 carbon atoms, more preferably from 1 to 3, preferably methyl, ethyl, vinyl, propyl or allyl. R" ² It is preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group. R" ^{3 is} preferably an aliphatic C1-C6 alkyl group, more specifically a methyl group, an ethyl group or a propyl group, more preferably a methyl group, or a monovalent C6 aromatic group, preferably a phenyl group.

Examples of suitable organodecane or organooxanes which are free of epoxy or amine functionality are phenyltriethoxydecane, methyltriethoxydecane, phenyltrimethoxydecane and methyltrimethoxydecane. Other examples include vinyl triethoxy decane, vinyl trimethoxy decane, n-propyl triethoxy decane, n-propyl trimethoxy decane, allyl trimethoxy decane, and allyl triethoxy Decane. Phenyltriethoxydecane may be considered to be preferred.

Innocent epoxy resin

In one embodiment of the invention, the coating composition comprises at least one non-ruthenium epoxy resin (also referred to as "no epoxy resin-containing resin").

Within the scope of the present specification, an indigo-free epoxy resin is meant to mean a resin or resin mixture comprising an epoxy group and free of a decane or a decoxyalkyl group as described above. Suitable non-ruthenium epoxy resins are known in the art. It covers, for example, phenol novolac epoxy resins, bisphenol F epoxy resins, and resorcinol diglycidyl ether (RDGE) epoxy resins. Other suitable epoxy resins include bisphenol A diglycidyl ether, hydrogenated bisphenol A, or bisphenol S, condensation or extended glycidyl ether of any of the above bisphenols, hydrogenated condensation glycidyl ether of bisphenol, polyols Polyglycidyl ether (such as trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol polyglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether Ether, hexanediol diglycidyl ether and sorbitol glycidyl ether), epoxidised oil, epoxy compounds (such as diepoxyoctane and epoxidized polybutadiene).

In one embodiment, the epoxy-free epoxy resin comprises an aromatic epoxy resin, specifically a phenol novolac epoxy resin. Suitable phenol novolac epoxy resins are well known in the art and need not be further elucidated. Examples of phenol novolac epoxy resins useful in the compositions of the present invention include DEN 425, DEN 431 and DEN 438 (from DOW Chemicals), Epon 154, Epon 160, Epon 161 and Epon 162 (from Momentive Performance Chemicals) and Epalloy 8250 (from Emerald Chemical Co.). The epoxy equivalent of these epoxy compounds is in the range of 165 to 185 g/eq. The epoxy equivalent is the weight of the epoxy resin required to obtain one mole (one equivalent) of epoxy functional groups. Other epoxy resins that can be used include cresol novolac epoxy resins (such as Epon 164 and Epon 165 (from Momentive Performance Chemicals)) or bisphenol A epoxy novolac resins (such as Epon SU series resins).

In an embodiment, the bismuth-free epoxy resin comprises an RDGE epoxy resin. The RDGE epoxy resins useful in the compositions of the present invention are typically low viscosity epoxy compounds having an epoxy equivalent weight of from 110 to 140 g/eq, more preferably from 120 to 135 g/eq.

Although RDGE epoxy resins are attractive for the manufacture of coatings with very high chemical resistance, it is sometimes preferred to use RDGE for dispensing because of the extremely harsh sensitizing properties of the epoxy resins. Thus, in one embodiment, the coating composition comprises less than 50% by weight RDGE epoxy resin, preferably less than 20% by weight, more preferably less than 10% by weight RDGE, based on the total amount of the non-antimony epoxy resin. Specifically, less than 5% by weight RDGE, for example less than 2% by weight RDGE. The coating composition is preferably substantially free of RDGE, meaning that no RDGE is intentionally added to the composition.

A particular feature of the present invention, and the unexpected discovery, is that compositions containing relatively small amounts of RDGE as described above can be prepared, or such compositions are substantially free of RDGE while still exhibiting excellent chemical resistance.

Any of the above non-ruthenium epoxy resin blends may be used in combination with each other, but a phenol novolak epoxy resin is preferred when extremely high chemical resistance is required. Therefore, the phenol novolac epoxy resin preferably constitutes at least 50% of the non-ruthenium epoxy resin based on the total amount of epoxy groups provided by the non-ruthenium epoxy resin. More preferably, the phenol novolac epoxy resin constitutes at least 70%, more specifically at least 80%, of the non-ruthenium epoxy resin based on the total amount of epoxy groups provided by the non-ruthenium epoxy resin.

In particular, a solvent for any coating formulation comprising the non-ruthenium epoxy resin The minimum content, phenol novolac epoxy resin (if used) preferably has a low solvent content, for example less than 20% by weight, preferably less than 10% by weight, based on the weight of the phenol novolac epoxy resin. Phenolic novolac epoxy resins are preferably free of solvents.

Melamine-free curing agent

The coating composition comprises an epoxy functional group-containing resin (also referred to simply as "epoxy resin") and an amine curing agent. The amine curing agent may be a non-amine amine curing agent, a guanamine containing curing agent, or a combination of the two. The guanamine-containing curing agent is discussed above in the section on amine functional decane and decane. In this section, a flawless curing agent will be discussed.

Because epoxy resins are inherently electrophilic, they typically react with nucleophiles. The curing agent used in the present invention contains a nucleophilic functional group reactive with an epoxy group, in this case an amine group. During the ring opening reaction of the epoxide with the nucleophile (nucleophilic functional group), a hydrogen atom is transferred from the nucleophile to the oxygen atom of the epoxide. The transferred hydrogen atom is referred to as "active hydrogen". The reaction is described below:

Therefore, the equivalent weight of the nucleophilic material is often described in terms of the active hydrogen equivalent. This simply results in the weight of a nucleophile required to transfer a mole (or an "equivalent") to the hydrogen atom of the ring-opened epoxy group. Thus, in the case of an amine curing agent, the active hydrogen equivalent of the amine curing agent is the weight of the amine curing agent giving one mole (or one "equivalent") N-H group. For example, a primary amine curing agent will have two active hydrogens because it can react with two epoxy groups.

The amine-free curing agent used in the present invention is a polyamine because it contains at least two amine groups. The amine group can be a primary and/or secondary amine group.

The coating composition of the present invention comprises an amine curing agent. The amine curing agent may comprise, according to other components, at least one of the above-described amine functional group-containing decane or decane, at least one amine-free curing agent as described in this section, or at least one amine-containing functional group. Base decane or hydrazine a combination of oxyalkylene and at least one non-amine amine curing agent.

In one embodiment of the invention, the coating composition comprises at least one amine-free curing agent. Within the scope of the present specification, an amine-free curing agent is indicated to mean an amine curing agent which does not contain a decane or a decoxyalkyl group as described above. Suitable amine-free curing agents are known in the art.

Examples of suitable non-ruthenium polyamine curing agents are ethylenediamine, N-(2-hydroxyethyl)ethylenediamine, di-extension ethyltriamine, tri-extension ethyltetramine, tetra-extension ethylpentamine, and often The curing agent prepared by reacting the polyamine curing agent with a fatty acid and a dimerized fatty acid to obtain a guanamine amine and an amine functional polyamine curing agent is obtained. Examples of such curing agents are described in "Protective Coatings, Fundamentals of Chemistry and Composition" (ISBN 0-938477-90-0) by Clive H. Hare, published by the Society for Protective Coatings. This is incorporated herein by reference. Other polyamine curing agents are dicyandiamide, isophorone diamine, m-xylene diamine, m-phenylenediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-amino ring) Hexyl)methane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, two Aminodiphenyl hydrazine and Mannich base curing agent. Any commercial grade quality curing agent in such polyamines can be used, such as Ancamine 2264 (from Air Products), a commercial quality primarily comprising bis(4-aminocyclohexyl)methane curing agent. Examples of amine curing agents are described in "Protective Coatings, Fundamentals of Chemistry and Composition" (ISBN 0-938477-90-0) by Clive H. Hare, published by the American Protective Coatings Association, by H Lee and K Neville Author, published by LLC "Epoxy Resins" (ISBN 978-1258243180), edited by D Stoye and W Freitag, published by Hanser, "Resins for Coatings" (ISBN 978-1569902097), etc. Into this article.

Any of these amine adducts can also be used. These adducts can be prepared by the reaction of an amine with a suitable reactive compound such as a non-fluorene epoxy resin or a reactive diluent containing an epoxy functional group such as butyl glycidyl ether. This will reduce the free amine content of the curing agent, from It is more suitable for use under low temperature and / or high humidity conditions. Other examples of reactive functional diluents containing epoxy functional groups are described in "Protective Coatings, Fundamentals of Chemistry and Composition" by Icicle Clive H. Hare, published by the American Protective Coatings Association (ISBN 0-938477-90-0 Among them, they are incorporated herein by reference. Any of these amine adducts may also be supported by an amine with a suitable reactive compound such as an acrylate, maleate, fumarate, methacrylate or even an electrophilic vinyl compound such as acrylonitrile. The reaction was made.

It has been found that cycloaliphatic amines impart good chemical resistance in the compositions of the present invention. Examples of suitable cycloaliphatic amine curing agents include bis(4-aminocyclohexyl)methane and isophorone diamine as shown below.

A mixture of amine curing agents can also be used, including a mixture of a non-amine amine curing agent and an amine functional group-containing decane and a decane.

Other components

In one embodiment, the coating composition comprises an accelerator that accelerates the curing reaction between the epoxy group of the epoxy functional group-containing resin and the amine group of the amine curing agent. Although the amine group of the curing agent, whether in its unreacted or reacted form, will accelerate the alkoxypurine groups present on the organodecane or organooxane used in the present invention as described above. Hydrolysis and condensation reactions, but the addition of accelerators which also accelerate the process is also advantageous. Some of these promoters may also promote anionic polymerization of epoxy groups. An accelerator which accelerates the hydrolysis and condensation reaction of the alkoxyfluorene group but does not significantly affect the reaction between the amine group and the epoxy group or the anionic polymerization of the epoxy group may be added. Examples of such promoters are dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, neodymium neodecanoate, titanium tetrabutoxide, titanium tetraisopropoxide, poly(n-titanate) Ester) and the like.

An example of an accelerator known to accelerate the curing reaction between an epoxy resin and an amine curing agent The following materials are included: alcohols, phenols, carboxylic acids, sulfonic acids, salts and tertiary amines: alcohols: examples of suitable alcohols include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, Tributyl alcohol, benzyl alcohol, decyl alcohol, and other alkanols, propylene glycol, butanediol, glycerin and other polyols, triethanolamine, triisopropanolamine, dimethylaminoethanol, and other β-hydroxy tertiary amines.

Phenol: Examples of suitable phenols include phenol, 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 4-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrate Phenolic, 4-cyanophenol, o-cresol, m-cresol, p-cresol, 4-ethylphenol, 4-isopropylphenol, 2,4-dimethylphenol, 3,5-dimethyl Phenolic, nonylphenol, eugenol, isoeugenol, cardanol and other alkylated phenols, 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 4,4'-dihydroxy Biphenol, bisphenol A, bisphenol F, catechol, 4-t-butyl catechol, resorcinol, 4-hexyl resorcinol, lichenol, hydroquinone, naphthalenediol, bismuth Phenols, biphenols and other substituted dihydric phenols, phloroglucinol, phloroglucide, calixarene, poly(4-vinylphenol) and other polyphenols.

Carboxylic acid: Examples of suitable carboxylic acids include acetic acid, propionic acid, butyric acid, lactic acid, phenylacetic acid, and other alkyl carboxylic acids, malonic acid, oxalic acid, maleic acid, fumaric acid, and other dibasic acids or singles thereof. Ester, benzoic acid, 4-tert-butylbenzoic acid, salicylic acid, 3,5-dichlorosalicylic acid, 4-nitrobenzoic acid and other aromatic acids.

Sulfonic acid: Examples of suitable sulfonic acids include methanesulfonic acid and other alkylsulfonic acids, p-toluenesulfonic acid, 4-dodecylbenzenesulfonic acid, and other aromatic sulfonic acids, naphthalene disulfonic acids, and dinonylnaphthalenes. Disulfonic acid and other polysulfonic acids.

Salt: Examples of suitable salts include calcium nitrate, calcium naphthenate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, imidazolinium thiocyanate, lithium tetrafluoroborate, lithium bromide, lithium trifluoroacetate, chlorine Calcium, barium triflate, lithium perchlorate, zinc triflate, lithium nitrate. For all such salts, the cation can be exchanged with lithium, sodium or potassium.

In the coating composition of the present invention, an epoxy group may also undergo anionic polymerization. In a real In the examples, the anionic polymerization of the epoxy group is accelerated by including a promoter in the composition. Examples of suitable anionic polymerization promoters are tertiary amines such as 1,8-diaza-bicyclo[5.4.0]undec-7-ene, tri-ethylidene diamine (diazabicyclooctane) Benzyl dimethylamine, dimethylaminopropylamine, diethylaminopropylamine, N-methylmorpholine, 3-morpholinylpropylamine, triethanolamine, dimethylaminoethanol , 2-dimethylaminomethylphenol, 4-dimethylaminomethylphenol, 2,4-bis(dimethylaminomethyl)phenol, 2,6-bis(dimethylamino) Methyl)phenol and 2,4,6-gin(dimethylaminomethyl)phenol; imidazoles such as 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4 -methylimidazole, 2-ethyl-4-methylimidazole and 2-heptadecylimidazole. These accelerators also accelerate the curing between the epoxy group of the epoxy resin and the functional group of the curing agent having active hydrogen.

Preferred promoters within the scope of the present application include tertiary amines such as 1,8-diaza-bicyclo[5.4.0]undec-7-ene, tri-ethylethylamine (diazepine) Heterobicyclooctane), benzyldimethylamine, triethanolamine, dimethylaminoethanol, and 2,4,6-para-(dimethylaminomethyl)phenol; imidazoles, such as 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-heptadecylimidazole, as appropriate, in other catalysts One or more combinations.

These tertiary amine accelerators also serve as a catalyst for the hydrolysis and condensation reaction of the alkoxyfluorene groups of the above organic decane or organomethoxyalkane used in the present invention.

The promoter (if present) is suitably used in an amount of from 0.1 to 5.0 parts by weight, preferably from 0.5 to 5.0 parts by weight, per 100 parts by weight of the epoxy resin mixture, relative to 100 parts by weight of the epoxy resin mixture.

As will be discussed in more detail below, the coating compositions of the present invention are two-pack compositions. The (etc.) promoter, if present, should be present in the package containing the amine curing agent. It is not recommended that the (etc.) accelerator be present in the package containing the epoxy resin mixture as this will reduce the shelf life of the package.

In one embodiment, the coating composition of the present invention comprises one or more pigments and/or fillers Agent. The one or more pigments may be colored pigments such as titanium dioxide (white pigment), color pigments (such as yellow or red iron oxide) or phthalocyanine pigments. The one or more pigments may be reinforced pigments such as micaceous iron oxide and crystalline cerium oxide and apatite. The one or more pigments may be corrosion resistant pigments such as zinc phosphate, molybdate or phosphonate. The one or more pigments may be a filler pigment such as barite, talc, feldspar or calcium carbonate.

The composition may comprise one or more other ingredients such as a thickening agent or a thixotrope such as particulate ceria, bentonite, hydrogenated castor oil or polyamide wax. The composition may also contain a plasticizer, a pigment dispersant, a stabilizer, a glidant, a wetting agent, an antifoaming agent, an adhesion promoter or a thinning solvent. In one embodiment, the coating composition used in the present invention has a solvent content of up to 250 g/l, in particular up to 200 g/l, more specifically up to 150 g/l, and in particular up to 100 g/l. The solvent content is preferably at most 50 g/l. In one embodiment, the composition is free of additional solvents.

The solvent content can be determined as follows: the solvent content includes those which are liquid at 0 to 50 ° C, and are not reacted with the epoxy resin, the amine curing agent, and the organic decane and the organic decane which are used in the present invention as described above, and A component having a vapor pressure at 25 ° C of greater than 0.01 kPa or a boiling point of less than 250 ° C at 1 atm. For clarity, volatile materials produced by hydrolysis of an epoxy functional decane or an epoxy functional oxane or any other alkoxy decane present in the coating composition (as defined above) ) is not included in the solvent content.

Coating - application and use

The coating composition of the present invention at least partially cures the epoxy functional group-containing resin at a temperature in the range of 0 to 50 °C. If this requirement is not met, the composition is less suitable for coating metal or concrete surfaces of chemical equipment. One of the features of the process according to the invention is that the coating is cured in the first step at a temperature in the range from 0 to 50 ° C, for example from 10 to 30 ° C, more specifically from 15 to 25 ° C. In this step, the curing should be carried out at least to the extent that water can subsequently be sprayed onto the coating or the coating can be physically treated without causing the coating surface to rupture. This step will be further referred to as an environmental curing step. The environmental curing step can be, for example, advanced Lines 1 to 24 hours, specifically 3 to 10 hours, where higher temperatures will reduce the required cure time, and where lower temperatures will increase the required cure time.

The environmental curing step is preferably carried out in a relative humidity range of 0 to 100%, more preferably in the range of 20 to 80%, and most preferably in the range of 40 to 60%. When the surface to be coated is relatively closed, such as when it is part of a sump, it is common practice to control the relative humidity during the coating operation to ensure that film formation occurs to obtain a complete coating without significant defects.

In general, in order to obtain a coating having optimum chemical resistance properties, the coating composition is advantageously further cured in a second step, in particular in which the coating will be extremely aggressive in contact with the coating. Chemicals. In this second step (also referred to as the post-cure step), the coating is heated to a temperature above 50 ° C for a given period of time, for example, for a period of, for example, 1 to 24 hours, in particular 3 Up to 16 hours. In general, post curing can be carried out at a temperature of at least 50 ° C, for example from 50 to 150 ° C. In an embodiment, the post cure will be carried out at a temperature of from 50 to 100 ° C, for example from 50 to 80 ° C. In another embodiment, the post cure will be carried out at a temperature of from 100 to 150 °C.

How to achieve post-cure will depend on the nature of the surface to be coated and will be apparent to those skilled in the art. For example, curing can be achieved by heating the surface with hot air or hot water (eg, by spraying). When the chemical equipment is a sump, heating can also be achieved by, for example, contacting the coated surface with the hot cargo, utilizing heat from the cargo to effect additional curing, or filling the sump with hot water. The performance of the post-cure step at a temperature of at least 50 ° C is a preferred embodiment of the invention.

The coating composition can be applied to the surface to be coated by methods known in the art. Examples of suitable methods include roll coating, spray coating, and brush coating. It is preferably applied by spraying because it effectively deposits a homogeneous coating. One feature of the present invention is that the coating composition can be formulated to have a sprayable viscosity without relying on a large amount of solvent. The composition can be applied, for example, via a single feed airless spray technique or via a plurality of component application techniques.

Each of the coatings applied in the present invention may have, for example, 50 to 350 microns after curing. Specifically, the thickness is 75 to 200 microns. This thickness is suitable for each layer, whether it is cured separately or simultaneously after application.

This invention relates to the coating of metal or concrete surfaces of chemical equipment. Within the scope of this specification, "chemical equipment" means buildings, man-made structures and/or devices used to produce and/or store and/or transport liquid or gaseous bulk chemicals. Specific examples of chemical equipment include buildings and man-made structures for the introduction of new chemical equipment for the marine or marine industry, the oil and gas industry, the chemical processing industry, the power industry, the wastewater and aquaculture industries, the transportation industry, and the mining and metallurgical industries. And / or equipment.

Bulk chemicals are chemicals that are present in large quantities (ie, at least 10 m ^{3 in} volume). Bulk chemicals vary from completely harmless to extremely aggressive to steel, concrete and/or other materials. Liquid bulk chemicals can be broadly classified into edible and non-edible goods. Examples of edible liquid bulk chemical cargoes are juice, milk and vegetable oils. Examples of non-edible bulk chemicals include chemical solvents, reactive chemical intermediates (such as vinyl acetate), petroleum, acid, alkali and liquefied natural gas (LNG). ).

The metal or concrete surface may include a storage tank, a storage container, its associated piping, or other piping in general, the inner and outer surfaces of the flue and containment areas. In addition to liquid or gaseous chemicals, the surface of such metal or concrete of chemical equipment can be exposed to high temperatures (whether static or cyclic) and high pressure (whether static or cyclic).

In one embodiment, the coated chemical equipment of the present invention is a chimney, pipe or sump, such as a cargo tank or storage tank.

It has been found that the coating compositions of the present invention exhibit particularly good results when used as a sump lining composition, which combines low absorbency and good washability against a wide variety of chemicals, resulting in the coating composition being resistant to cyclic loading. Bulk chemicals. It has also been found that the coating composition has good thermal stability at elevated temperatures which makes it suitable for use in high temperature problematic land storage tanks. The invention has particular utility in cargo tanks, but can also be used in other storage tanks (such as land storage tanks for various chemicals and crude oil or hydrocarbon-water mixtures) and such storage tanks The secondary receiving area.

The coating composition can be applied directly to the surface as a primer and/or finish, i.e., the composition can be used as the only type of protective coating on the surface.

The coating composition of the present invention can also be applied as a primer, that is, the coating of the present invention is first applied to a surface to form a first coating layer, and the coating is cured at a temperature of 0 to 50 ° C to the first coating. Another coating is provided on the layer to form a second coating and to cure the second coating. Other coatings may also be applied to provide three or more layers of the coating compositions of the present invention. Usually no more than three layers are required, the exact number depends on the thickness of each layer. For the post-cure step, this step is preferably performed after all layers have been deposited.

Coating composition

The coating composition is a two-pack coating composition wherein the first package comprises an epoxy-containing component and the second package comprises a component reactive with an epoxy group, such as an amine-containing compound. The use of a two-pack composition will cure at temperatures between 0 and 50 °C.

The coating composition comprises an epoxy functional group-containing resin, an amine curing agent for the epoxy functional group-containing resin, and an organic germanium-containing compound selected from the group consisting of organic germanes and organic germanium oxides, wherein the organic The molar ratio between the ruthenium atom of the ruthenium compound and the epoxy group in the coating composition is in the range of from 0.20 to 0.75:1.00, for example, in the range of from 0.25 to 0.75:1.00. As described above, the organic cerium-containing compound generally includes an epoxy functional group-containing decane or an epoxy functional group-containing decane, an amine group-containing decane or an amine group-containing oxane and/or none. An organic decane or an organic siloxane having an epoxy or amine functionality.

It has been found that if the molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition is not within the range of 0.20 to 0.75:1.00, the chemical resistance of the coating composition will be insufficient. .

The preferred molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition is within a range of from 0.25 to 0.75:1.00. More specifically, if the molar ratio between the ruthenium atom of the organic ruthenium-containing compound and the epoxy group in the coating composition is too small, The chemical resistance and high temperature resistance of the coating composition are adversely affected. On the other hand, if the molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition is too high, the coating will fail due to cracking and can damage the chemical (such as methanol). Or chemical resistance of certain concentrated caustic solutions. Optionally, the molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition may be from 0.21 to 0.75:1.00, from 0.22 to 0.75:1.00, from 0.23 to 0.75:1.00, from 0.24 to 0.75. : 1.00, 0.30 to 0.70: 1.00 or 0.40 to 0.60: 1.00.

In one embodiment of the invention, the amount of curing agent present in the coating composition is such that the equivalent ratio of active hydrogen to epoxy functional group-containing resin in the curing agent is between about 0.15 and 1.80: Between 1.00. This ratio of active hydrogen to epoxy groups is effective to cure the coating compositions of the present invention. In calculating this ratio, the term epoxy resin encompasses both cerium-containing epoxy resins (i.e., decane and decane containing epoxy functional groups) and fluorene-free epoxy resins. The active hydrogen in the term curing agent encompasses the active hydrogen from the amine-free curing agent and the guanamine-containing curing agent (i.e., the decane containing an amino functional group and the oxane containing an amino functional group).

In one embodiment of the invention, the equivalent ratio of active hydrogen to epoxy group epoxy resin in the curing agent is between about 0.70 and 1.30:1.00, more specifically between 0.85 and 1.10:1.00. In this embodiment, in order to achieve the highest chemical resistance, the environmental curing step and the post-curing step as described above are preferably carried out.

In another embodiment of the invention, the equivalent ratio of active hydrogen to epoxy group epoxy resin in the curing agent is between about 0.15 and 0.50:1.00, more specifically between 0.20 and 0.40:1.00. . In this embodiment, in order to achieve the highest chemical resistance state, the environmental curing step and the post-curing step as described above are preferably carried out. In this embodiment, the coating composition preferably further comprises a tertiary amine accelerator as described above, for example, in an amount of from 0.10 to 5 parts by weight relative to 100 parts by weight of the epoxy resin, more specifically in an amount of 2 to 5 parts by weight relative to 100 parts by weight of the epoxy resin (including both an antimony-free epoxy resin and a cerium-containing epoxy resin). This ensures that the epoxy-amine curing reaction is accompanied by anionic epoxy homopolymerization and alkoxythiol groups. The necessary amount of hydrolysis and self-condensation.

In another embodiment, the equivalent ratio of active hydrogen to epoxy group epoxy resin in the curing agent is between about 1.20 and 1.80:1.00, more specifically between 1.50 and 1.80:1.00. In this embodiment, only the environmental curing step is required.

Selecting the epoxy group within the specified range: the equivalent of active hydrogen / molar ratio ensures that the coating composition can be used for curing under ambient conditions (eg, 0 ° C to 50 ° C) due to epoxy and amine groups and as described above The hydrolysis and hardening of the alkoxyfluorene group of an organic germanium or an organic germanium alkoxide in the invention to cure and harden until water can be sprayed onto the coating or the coating can be physically treated without causing the coating The extent of surface rupture.

It should be noted that some endpoint values for the ranges quoted herein are counted to two decimal places (e.g., the molar ratio between the ruthenium atom containing the deuterated organic compound and the epoxy group in the coating composition). Such ranges are intended to include values falling within the recited range (including the endpoint values of the ranges) when rounded-up/down rules are rounded to two decimal places. For example, the range 0.25 to 0.75 includes the values 0.245 and 0.754 because if rounded to 2 decimal places according to mathematical rules, these values will be equal to 0.25 and 0.75. On the other hand, the value 0.244 will be rounded to 0.24 and will be below the lower limit of 0.25 and outside of this range. Similarly, a value of 0.755 would be rounded to 0.76 and would be above the upper limit of 0.75 and would be outside of this range.

The same mathematical rounding rules apply to the other values quoted herein.

The coating composition comprises an epoxy functional group-containing resin, an amine curing agent for the epoxy resin, and an organic cerium-containing compound selected from the group consisting of organodecane and organosiloxane. As described above, the organic cerium-containing compound includes an epoxy functional group-containing decane, an epoxy functional group-containing decane, an amine group-containing decane or an amine group-containing oxirane, epoxy-free or One or more of an amine functional organodecane and an epoxy- or amine-free organooxane.

In one embodiment, the coating composition comprises a non-ruthenium epoxy resin, an amine curing agent, and An organic decane or a decane containing an epoxy functional group. In this embodiment, the amine curing agent is preferably a non-amine amine curing agent. With regard to the nature of the various components, reference is made to the above. For the other components of the coating composition, reference is also made to the above.

In this embodiment, it has been found that if the epoxy-functional decane or decane provides 25 to 60% of the epoxy groups present in the coating composition, and the ruthenium-free epoxy resin is present in the The nature of the coating is particularly preferred for the 40 to 75% epoxy groups in the coating composition.

In one embodiment, the epoxy functional decane or decane provides 30 to 60%, specifically 40 to 60%, more specifically 45 to 55% epoxy groups present in the system. The non-ruthenium epoxy resin also preferably provides from 40 to 75%, specifically 40 to 60%, more specifically 45 to 55% epoxy groups present in the system. This embodiment has been found to provide an extremely wide range of chemical resistance, particularly when using an additional higher temperature cure stage, as will be discussed in more detail below.

In another embodiment, the epoxy-functional decane or decane provides 25 to 50%, specifically 25 to 35%, epoxy groups present in the system. The non-ruthenium epoxy resin may also preferably provide from 50 to 75%, in particular from 65 to 75%, of the epoxy groups present in the system. This example has been found to provide excellent dry heat resistance without the need for a specific additional high temperature cure stage prior to use.

In one embodiment of the present invention, the coating composition comprises a non-ruthenium epoxy resin, an amine curing agent, and an epoxy functional group-containing organodecane or a decane, wherein the epoxy functional organic decane or oxime The alkane provides from 30 to 60%, specifically 40 to 60%, more specifically 45 to 55% epoxy, present in the system, while the non-antimony epoxy provides 40 to 75% of the present in the system. Specifically, 40 to 60%, more specifically 45 to 55% epoxy groups, and the equivalent ratio of active hydrogen in the curing agent to the epoxy group of the epoxy resin is between about 0.70 and 1.30, More specifically between 0.85 and 1.10. In this embodiment, in order to achieve the highest chemical resistance, the environmental curing step and the post-curing step as described above are preferably carried out. The non-ruthenium epoxy resin is preferably a novolak resin. The curing agent is preferably a non-amine amine curing agent, specifically a cycloaliphatic amine curing agent. The composition preferably contains little or no RDGE as described above. A preferred decyl glycidoxypropyltrimethoxydecane (GOPTMS) containing an epoxy functional group. Preferred epoxy functional group-containing oxanes have the epoxy functional group-containing oxirane oligomers of the above formula 1, wherein R ¹ = -CH ₂ CH ₂ CH ₂ -, R ² = CH ₃ R ³ is absent, n=2 and m has a value in the range of 2 to 8, in particular 3 to 5, for example about 4. This material is manufactured by Momentive Performance Chemicals and sold under the trade name Momentive MP200.

In another embodiment, the coating composition comprises a non-ruthenium epoxy resin, an amine curing agent, and an epoxy functional group-containing organodecane or a decane, wherein the epoxy-functional organodecane or decane provides 25 to 50%, specifically 25 to 35% epoxy, present in the system, while non-antimony epoxy provides 50 to 75%, specifically 65 to 75% epoxy, present in the system And the equivalent ratio of the active hydrogen in the curing agent to the epoxy groups of the epoxy resins is between about 1.20 and 1.80, more specifically between 1.50 and 1.80. In this embodiment, the post-cure step can be eliminated. The non-ruthenium epoxy resin is preferably a bisphenol F epoxy resin or a phenol novolak epoxy resin. The curing agent is preferably a non-amine amine curing agent, specifically a cycloaliphatic amine curing agent. The composition preferably contains little or no RDGE as described above. A preferred decyl glycidoxypropyltrimethoxydecane (GOPTMS) containing an epoxy functional group.

In one embodiment of the invention, the coating composition comprises an epoxy resin, an amine functional organodecane or a decane, and optionally a guanamine-free curing agent. With regard to the nature of the various components, reference is made to the above. For the other components of the coating composition, reference is also made to the above.

As described above, the coating composition of the present invention comprises an organic cerium-containing compound selected from the group consisting of organodecane and organosiloxane. The organodecane and organodecane may comprise an epoxy functional decane or a decane, an amine functional decane or decane and/or epoxy free or An amine functional organic decane or an organic decane.

In one embodiment, at least a portion of the ruthenium atoms of the organic ruthenium containing compound present in the coating composition are preferably derived from an oxirane or oxime containing an epoxy functional group and/or a decane or oxime containing an amine functional group. The oxane is not derived from a non-functional decane or a decane (i.e., a decane or a decane having no epoxy or amine functionality). It is believed that in this manner, the ruthenium linkages in the organic network of the coating and the chemical resistance of the coating composition will be improved. In one embodiment, up to 80% of the germanium atoms of the organodecane and the organooxynitane are derived from a non-functional organodecane or a non-functional organodecane. Preferably, up to 60%, more specifically up to 40%, and more specifically up to 20% of the atomic atoms of the organodecane and the organodecane may be derived from a non-functional organodecane or a non-functional organoxonium. alkyl.

In one embodiment, at least a portion of the ruthenium atoms of the organic ruthenium containing compound present in the coating composition are preferably derived from an epoxy functional decane or an epoxy functional oxirane. It has been discovered that the use of an epoxy functional decane or an epoxy functional siloxane is an effective way to incorporate a relatively large amount of ruthenium in the coating composition. In one embodiment, at least 20% of the germanium atoms of the organodecane and the organooxynitane are derived from an epoxy functional decane or an epoxy functional siloxane. Preferably, at least 40%, or at least 60%, or at least 80% of the ruthenium atoms of the organodecane and the organosiloxane are derived from an oxirane containing an epoxy functional group or a oxirane containing an epoxy functional group.

In one embodiment, the coating composition comprises a combination of a non-functional organodecane or an organodecane with an epoxy or an amine-containing functional decane or a decane. This allowable rhodium content varies independently of the epoxy group and amine content, and the ratio of rhodium to epoxy groups can be more controlled, which is a key feature in controlling the chemical resistance of the coating composition. Thus, in one embodiment, a portion of the ruthenium atom of the organic ruthenium containing compound present in the coating composition (eg, 1 to 50%, specifically 1 to 20%, more specifically 5 to 20% by weight) An organoxanthene or a decane derived from an epoxy-free or amine-free functional group, and a part of the ruthenium atom of the organic ruthenium-containing compound present in the coating composition (for example, 50 to 99%, specifically 80 to 99) %, more specific 80 to 95% by weight) are decanes or decanes derived from oxiranes or oxiranes containing an epoxy functional group and/or amine functional groups.

In this embodiment, preferably, at least 40%, or at least 60%, or at least 80% of the ruthenium atoms of the epoxy or amine functional group-containing organodecane and organosiloxane are derived from epoxy-containing functional groups. A decane or an oxirane containing an epoxy functional group.

In one embodiment, the coating composition comprises an amine functional group-containing organodecane or an organomethoxyalkane in combination with an epoxy functional decane or a decane. This allowable rhodium content varies independently of the epoxy group content, and the ratio of rhodium to epoxy groups can be more controlled, which is a key feature in controlling the chemical resistance of the coating composition. Thus, in one embodiment, a portion (e.g., 1 to 99%, specifically 10 to 90%) of the ruthenium atoms of the organic ruthenium containing compound present in the coating composition is derived from an amine functional decane or oxime The alkane, and a portion (e.g., 1 to 99%, specifically 10 to 90%) of the ruthenium atoms of the organic ruthenium-containing compound present in the coating composition is derived from a decane or a decane containing an epoxy functional group.

In one embodiment, the coating composition comprises a non-ruthenium epoxy resin, an amine functional organodecane or a decane, and optionally a guanamine-free curing agent. With regard to the nature of the various components and their ratios, reference is made to the above. For the other components of the coating composition, reference is also made to the above.

In one embodiment, the coating composition comprises a non-ruthenium epoxy resin, an organofunctional decane or a decane containing an epoxy functional group, an organodecane or a decane having an amine functional group, and optionally a guanamine-free curing Agent. With regard to the nature of the various components and their ratios, reference is made to the above. For the other components of the coating composition, reference is also made to the above.

In one embodiment, the coating composition comprises a non-ruthenium epoxy resin, an organofunctional decane or decane containing an epoxy functional group, a non-functional organodecane or a decane, and a decylamine-free curing agent. With regard to the nature of the various components and their ratios, reference is made to the above. For the other components of the coating composition, reference is also made to the above.

The coating composition can be made by methods known in the art, without the need for It is further elaborated. It is within the ability of those skilled in the art to make coating compositions based on the above guidelines.

It is noted that the embodiments of the coating compositions described herein can be combined with one another in a manner that will be apparent to those skilled in the art. This applies to all properties and compositions, including the preferences of the various components and ratios between the various components. All of the examples and properties described for the coating are also applicable to a method of providing a sump liner for a sump and a sump having a lining of the cured coating composition.

Unless otherwise indicated, the specifications of the various components also apply to coating compositions containing such components.

The headings of this specification are for illustrative purposes only and are not to be considered as limiting in any way.

The invention will now be illustrated with reference to the following examples. The examples are intended to illustrate the invention and are not to be construed as limiting the scope thereof.

Example 1: Inventive Example 1 An epoxy functional decane and a non-fluorene epoxy resin and an amine curing agent

This example of the invention shows the mass absorption of vinyl acetate and dichloroethane when the epoxy functional decane is mixed with the fluorene-free epoxy resin without adding any resorcinol diglycidyl ether. The impact.

Glycidoxypropyltrimethoxydecane (5.456 g, 0.0231 epoxy equivalent) was added to DEN 431 (from Dow Chemicals) (4.0513 g, 0.0231 epoxy equivalent) and at room temperature with 2.2202 g of double ( A mixture of 4-aminocyclohexyl)methane (PACM) (0.0423 eq. NH) and ginseng (2,4,6-dimethylaminomethyl)phenol (0.2448 g) was thoroughly mixed.

In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 0.50:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.92:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Example 2: Examples of the invention: epoxy functional group-containing oxiranes and non-ruthenium epoxy resins and amine curing agents

This example shows the mass absorption of vinyl acetate and dichloroethane when the epoxy functional epoxy-containing alkane is mixed with an antimony-free epoxy resin without adding any resorcinol diglycidyl ether. influences.

Momentive MP200 (6.6 g, 0.0327 epoxy equivalent) was added to DEN 431 (from Dow Chemicals) (5.8 g, 0.03295 epoxy equivalent) and at room temperature with 3.12 g of bis(4-aminocyclohexyl)methane A mixture of (PACM) (0.05943 eq. NH), 1-methylimidazole (0.510 g) and 2-ethyl-4-methylimidazole (0.3136 g) was thoroughly mixed.

In the composition, the molar ratio of the ruthenium atom of the organoaluminoxane to the epoxy group in the composition is 0.50:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.91:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Example 3: Examples of the invention: epoxy functional group-containing oxiranes and non-ruthenium epoxy resins and amine curing agents

This example shows the mass absorption of vinyl acetate and dichloroethane when the epoxy functional epoxy-containing alkane is mixed with an antimony-free epoxy resin without adding any resorcinol diglycidyl ether. influences.

Momentive MP200 (1.622 g, 0.00803 epoxy equivalent) was added to DEN 431 (from Dow Chemicals) (1.419 g, 0.00809 epoxy equivalent) and at room temperature with 0.3557 g of tri-ethyltetramine (0.0145 eq. A mixture of NH) and 2,4,6-glycol (dimethylaminomethyl)phenol (0.077 g) was thoroughly mixed.

In the composition, the molar ratio of the ruthenium atom of the organoaluminoxane to the epoxy group in the composition is 0.50:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.90:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Example 4: Examples of the Invention: Epoxy-functional decane and non-ruthenium epoxy resin and amine curing agent

This example shows the effect on the mass absorption of vinyl acetate and dichloroethane when mixing an epoxy functional decane with a non-ruthenium epoxy resin in a tinted formulation.

Manufacturing a paint base of the invention, and comprising

5 g of the primer (0.01218 epoxy equivalent) was thoroughly mixed with 0.5924 g of Ancamine 2264 (0.011 eq. NH) and 0.0808 g of 2,4,6-glycol (dimethylaminomethyl)phenol at room temperature. .

In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 0.50:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.90:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Example 5: Examples of the invention: oxiranes containing epoxy functional groups, non-fluorene epoxy resins, decanes containing amino functional groups, and decylamine-free curing agents

This example shows the combination of an epoxy-functional decane with an amine-functional decane and an oxime-free epoxy resin in an untoned formulation without the addition of any resorcinol diglycidyl ether. The effect of the mass absorption of vinyl ester and dichloroethane.

Glycidoxypropyltrimethoxydecane (2.0163 g, 0.00854 epoxy equivalent) was added to DEN 431 (from Dow Chemicals) (5.9807 g, 0.0342 epoxy equivalent) and at room temperature with 3.4466 g of amine group A mixture of propyltrimethoxydecane (0.0384 eq. NH) and 0.2265 g of 2,4,6-gin(dimethylaminomethyl)phenol was thoroughly mixed.

In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 0.65:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.90:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after immersion for 30 days at room temperature.

Example 6: Examples of the invention: epoxy functional group-containing decane, amine functional group-containing decane, non-fluorene epoxy resin and decylamine-free curing agent

This example shows the combination of an epoxy-functional decane with an amine-functional decane and an oxime-free epoxy resin in an untoned formulation without the addition of any resorcinol diglycidyl ether. The effect of the mass absorption of vinyl ester and dichloroethane.

Glycidoxypropyltrimethoxydecane (2.019 g, 0.00854 epoxy equivalent) was added to DEN 431 (from Dow Chemicals) (5.9807 g, 0.0342 epoxy equivalent) and at room temperature with 0.7659 g of amine group Propyltrimethoxydecane (0.00854 eq. NH), 1.5849 g of bis(4-aminocyclohexyl)methane (0.0299 eq. NH) and 0.2265 g of 2,4,6-cis (dimethylaminomethyl) The mixture of phenols is thoroughly mixed.

In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 0.30:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.90:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after immersion for 23 days at room temperature.

Example 7: Examples of the invention: epoxy functional group-containing decane, amine functional group-containing decane, non-fluorene epoxy resin and decylamine-free curing agent

This example shows the combination of an epoxy-functional decane with an amine-functional decane and an oxime-free epoxy resin in an untoned formulation without the addition of any resorcinol diglycidyl ether. The effect of the mass absorption of vinyl ester and dichloroethane.

Glycidoxypropyltrimethoxydecane (2.02 g, 0.00855 epoxy equivalent) was added to DEN 431 (from Dow Chemicals) (6.017 g, 0.0344 epoxy equivalent) and at room temperature with 4.054 g of bis ( Trimethoxydecylpropyl)amine (Dynasylan 1124, 0.01187 eq. NH), 1.4204 g of bis(4-aminocyclohexyl)methane (0.0268 eq. NH) and 0.2423 g of 2,4,6-paraxyl The mixture of arylaminomethyl)phenol is thoroughly mixed.

In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 0.752:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.90:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating is fully dried within 24 hours. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after immersion for 23 days at room temperature.

Example 8: Examples of the invention: decanes containing an amino functional group, non-functional decane, an antimony-free epoxy resin and a decylamine-free curing agent

This example shows the incorporation of both an amino-functional functional decane and a non-functional decane and a non-ruthenium epoxy resin in an untoned formulation without the addition of any resorcinol diglycidyl ether. The effect of the mass absorption of dichloroethane.

Phenyltrimethoxydecane (0.5219 g) was added to DEN 431 (from Dow Chemicals) (4.037 g, 0.0228 epoxy equivalent) and at room temperature with 1.512 g of aminoethylaminopropyltrimethoxy A mixture of decane (0.0205 eq. NH) and 0.1321 g of 2,4,6-gin(dimethylaminomethyl)phenol was thoroughly mixed.

In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 0.40:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.90:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Example 9: Examples of the invention: an oxirane containing an epoxy functional group, a decane containing an amino functional group, a non-fluorene epoxy resin, and a decylamine-free curing agent

This example shows the combination of both an epoxy-functional oxirane with an amine-functional decane and an oxime-free epoxy resin in an untoned formulation without the addition of any resorcinol diglycidyl ether. The effect on the mass absorption of vinyl acetate and dichloroethane.

Momentive MP200 (0.874 g, 0.00433 epoxy equivalent) was added to DEN 431 (from Dow Chemicals) (3.059 g, 0.0174 epoxy equivalent) and at room temperature with 0.3917 g of aminopropyltrimethoxydecane (0.00437) eq.NH), 0.6515g isophorone A mixture of diamine (0.0153 eq. N-H) and 2,4,6-glucos(dimethylaminomethyl)phenol (0.1448 g) was thoroughly mixed.

In the composition, the molar ratio of the organodecane and the ruthenium atom of the organodecane to the epoxy group in the composition is 0.30:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.90:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Example 10: Examples of the invention: epoxy functional group-containing decane, amine functional group-containing decane, non-fluorene epoxy resin and decylamine-free curing agent

This example shows the incorporation of both epoxy-functional decane and amine-functional decane and ruthenium-free epoxy resin in uncolored without the addition of any resorcinol diglycidyl ether. The effect on the mass absorption of vinyl acetate and dichloroethane in the formulation.

Glycidoxypropyltrimethoxydecane (1.006 g, 0.00426 epoxy equivalent) was added to DEN 431 (from Dow Chemicals) (2.9787 g, 0.0170 epoxy equivalent) and at room temperature with 0.0906 g of different buddha Mixture of ketodiamine (0.00213 eq. NH), 0.1907 g of aminopropyltrimethoxydecane (0.00213 eq. NH) and 0.1692 g of 2,4,6-glycol (dimethylaminomethyl)phenol .

In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 0.25:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.20:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Example 11: Examples of the invention: epoxy functional group-containing decane, amine functional group-containing decane, non-fluorene epoxy resin and decylamine-free curing agent

This example shows the effect of mixing an epoxy functional decane with an amine functional group-containing decane and a non-ruthenium epoxy resin on the mass absorption of vinyl acetate and dichloroethane when combined in a tinted formulation.

0.5348 g of DEN 431 was added to the primer of Example 4 to obtain a modified primer having the following composition:

5 g of the primer (0.0138 epoxy equivalent) with 0.0956 g of aminopropyltrimethoxydecane (0.00107 eq NH), 0.107 g of Ancamine 2264 (0.00198 eq. NH) and 0.1212 g of 2,4,6 at room temperature The mixture of ginseng (dimethylaminomethyl)phenol is thoroughly mixed.

In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 0.43:1.00. The equivalent ratio of active hydrogen to epoxy group was 0.20:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Example 12: Examples of the Invention: Epoxy-functional decane, non-fluorene epoxy resin and decylamine-free curing agent

This example shows the performance of a high stoichiometric composition.

Two primers were made using Epikote 862, bisphenol F based epoxy resin. In one of these primers, sufficient glycidoxypropyltrimethoxydecane is added such that 30% of the epoxy groups are provided by the decane containing the epoxy functional group. A coating based on Ancamine 2264 was formulated without any glycidoxypropyltrimethoxydecane, and the ratio of amine N-H to epoxy was 0.80. A coating containing glycidoxypropyltrimethoxydecane was also formulated using an ancamine 2264-based curing agent having a ratio of amine N-H to epoxy group of 1.70. The coating was applied to a sandblasted steel substrate and allowed to cure at 25 ° C for 10 days. The dry heat resistance of the coatings was tested using ASTM D5499 Method A. The coating without any glycidoxypropyltrimethoxydecane gives acceptable performance up to 177 ° C, while the glycidoxypropyltrimethoxydecane-containing coating is up to 212 ° C and even Good performance at 250 ° C without any signs of cracking. Using the NACE TM0185 test for autoclave performance (3% sodium chloride solution at 185 ° C and 11 bar pressure), the glycidoxypropyltrimethoxydecane-containing coating was not immersed in the autoclave for 4 months. Any blistering trace For example, the coating without any glycidoxypropyltrimethoxydecane foams at temperatures as low as 80 °C.

Comparative Example 1: Comparative Example of Coating Using Phenolic Novolak Epoxy Resin as the Only Epoxy Resin

In this comparative example, various organic liquids showed relatively high absorption in a coating prepared using phenol novolac epoxy resin (DEN 431) as the sole epoxy resin.

DEN 431 (from Dow Chemicals) (5.0 g, 0.0285 epoxy equivalent) was thoroughly mixed with 1.496 g of bis(4-aminocyclohexyl)methane (PACM) (0.0285 eq. N-H) at room temperature. The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The equivalent ratio of active hydrogen to epoxy group is 1.00:1.00.

The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

Comparative Example 2: Comparative example using a coating based on an epoxy functional group-containing decane as the sole epoxy resin

Comparative examples show that cracking occurs in a coating made using an epoxy functional group-containing decane as the sole epoxy resin.

Momentive MP200 (from Momentive Performance Chemicals) (11.7959 g, 0.058 epoxy equivalent) and 2.7635 g of bis(4-aminocyclohexyl)methane (PACM) (0.0526 eq. NH), 0.4548 g 1-A at room temperature The mixture of imidazole and 0.2798 g of 2-ethyl-4-methyl-imidazole was thoroughly mixed. The equivalent ratio of active hydrogen to epoxy group was 0.91:1.00. In the composition, the molar ratio of the ruthenium atom of the organodecane to the epoxy group in the composition is 1:1.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature, and during the process, all of the films were severely cracked and delaminated. The free membrane was weighed (accurate to the 4th position after the decimal point) and placed in individual glass bottles containing vinyl acetate or 1,2-dichloroethane. The mass absorption of vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the film from its bottle, gently drying the surface of the film, and rapidly weighing the film to the nearest 4 decimal places. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The mass absorption % results could not be recorded because the immersion process caused the free films to further break into small pieces that could not be dried and weighed separately.

Comparative Example 3: Comparative example using RDGE-based coatings

In this comparative example, the lower active hydrogen to epoxy equivalent ratio and the latter The crystallization step causes an anionic polymerization of excess epoxy groups, and various organic liquids exhibit low absorption in a coating prepared using resorcinol diglycidyl ether (RDGE) as the sole epoxy resin. This example is representative of the teachings of WO 2012/119968.

Resorcinol diglycidyl ether (from CVC) (8.0 g, 0.06349 epoxy equivalent) and 1.1581 g of bis(4-aminocyclohexyl)methane (PACM) (0.02186 eq. NH), 0.1906 at room temperature A mixture of g 1-methylimidazole and 0.1173 g of 2-ethyl-4-methyl-imidazole was thoroughly mixed. The equivalent ratio of active hydrogen to epoxy group was 0.34:1.00.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate the average absorption of the three slides of each immersion liquid after 28 days of immersion at room temperature.

A comparison of this example with an example of the invention shows that the invention enables performance and RDGE basis Coatings that are as good as coatings are possible, while eliminating the use of highly sensitizing RDGE.

Comparative Example 4: Comparative example using a coating based on RDGE and phenol novolac epoxy resin

In this example, various organic liquids showed low absorption in coatings prepared using a blend of resorcinol diglycidyl ether (RDGE) and phenol novolac epoxy resin (DEN 431).

Resorcinol diglycidyl ether (from CVC) (5.0 g, 0.0397 epoxy equivalent) was added to 1.529 g (0.00871 epoxy equivalent) DEN 431 (from Dow chemicals) and at room temperature with 0.956 g Ancamine a mixture of 2264 (from Air Products) (0.0177 eq. NH), 0.1941 g of 1-methylimidazole, 0.078 g of 2-ethyl-4-methyl-imidazole and 0.122 g of tris(dimethylaminomethyl)phenol Completely mixed. The equivalent ratio of active hydrogen to epoxy group was 0.37.

The mixture was applied to 6 microscope slides pre-weighed to 4 positions after the decimal point using a 400 μm cube applicator. The coated slides were then placed in an environmental control chamber maintained at 23 ° C and 50% relative humidity and allowed to cure for 24 hours. The coating was thoroughly dried over a 24 hour period. The coated slides were then placed in a fan assisted oven maintained at 80 ° C for 16 hours. Upon removal of the oven, the slides were allowed to cool to room temperature and the coated slides were weighed to the nearest 4 decimal places. Each slide was placed in a separate glass vial containing vinyl acetate or 1,2-dichloroethane. Three coated slides were used for each solvent. The vinyl acetate or 1,2-dichloroethane was monitored by periodically removing the slides from their bottles, drying the surface of the coated slides, and quickly weighing the slides to the nearest 4 decimal places. The mass absorption of the alkane. The amount of absorption is expressed as % of the original film quality and is calculated as follows:

The results given in the table below indicate that the three slides of each immersion liquid are immersed at room temperature. The average absorption after 28 days.

A comparison of this example with the examples of the present invention shows that the present invention makes it possible to obtain a coating that performs as well as an RDGE-based coating while eliminating the use of highly sensitizing RDGE.

Claims (15)

A method for providing a coating to a metal or concrete surface of a chemical device, comprising the steps of: providing a coating composition comprising an epoxy functional group-containing resin and an amine curing of the epoxy functional group-containing resin And the coating composition comprising an organic cerium-containing compound selected from the group consisting of organic decane and an organic decane, wherein a molar ratio between the cerium atom of the organic cerium-containing compound and the epoxy group in the coating composition The coating composition is applied to the metal or concrete surface of the chemical equipment to form a coating in the range of 0.20 to 0.75: 1.00, and the coating is cured at a temperature in the range of 0 to 50 °C. The method of claim 1, wherein the coating further undergoes a post-cure step at a temperature above 50 °C. The method of claim 1 or 2, wherein the chemical device is a chimney, a pipe or a sump, such as a cargo tank or storage tank. The method of claim 1 or 2, wherein the molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition is in the range of 0.25 to 0.75:1.00. The method of claim 1 or 2, wherein the organic ruthenium containing compound comprises an epoxy functional decane or decane, an amine functional decane or decane, and/or no epoxy or amine functionality. Organic decane or organic decane. The method of claim 5, wherein the coating composition comprises an epoxy functional decane or a decane and a non-ruthenium epoxy resin. The method of claim 6 wherein the epoxy-functional decane or decane provides 25 to 75% of the epoxy groups present in the coating composition, specifically providing 25 to 25 of the system. 60%, more specifically 40 to 60%, and more specifically 45 to 55% of an epoxy group, and the non-antimony epoxy resin provides 25 to 75% of the epoxy groups present in the coating composition, in particular 40 to 75% of the coating composition, more Specifically, 40 to 60%, and more specifically 45 to 55% of the epoxy groups. The method of claim 1 or 2, wherein the coating composition comprises an amine functional group-containing decane or a decane and optionally a guanamine-free curing agent. The method of claim 5, wherein the organic cerium-containing compound comprises an organic decane or an organic decane having no epoxy or amine functionality. The method of claim 1 or 2, wherein the coating composition comprises less than 10% by weight RDGE (resorcinol diglycidyl ether), specifically less than 5% by weight RDGE, such as less than 2% by weight RDGE. The method of claim 1 or 2, wherein the amount of the curing agent present in the coating composition is such that the equivalent ratio of active hydrogen in the amine curing agent to the epoxy group-containing resin is about 0.15 Between 1.80. A chemical apparatus comprising a metal or concrete surface having a lining of a cured coating composition, wherein the cured coating composition is derived from a resin comprising an epoxy functional group-containing resin and an amine curing agent for the epoxy functional group-containing resin a coating composition, wherein the coating composition comprises an organic cerium compound selected from the group consisting of organo decane and an organic decane, wherein the cerium atom of the organic cerium-containing compound and the epoxy group in the coating composition The molar ratio is in the range of 0.20 to 0.75:1.00. The chemical device of claim 12, which is a chimney, pipe or sump, such as a cargo tank or storage tank. A coating composition suitable for providing a coating to a metal or concrete surface of a chemical device, wherein the coating composition comprises an epoxy functional group-containing resin and an amine curing agent for the epoxy functional group-containing resin, wherein The coating composition comprises an organic cerium-containing compound selected from the group consisting of organo decane and organic decane, wherein The molar ratio between the ruthenium atom of the organic ruthenium containing compound and the epoxy group in the coating composition is in the range of from 0.20 to 0.75:1.00, preferably from 0.25 to 0.75:1.00. A coating composition according to claim 14 which is a two-pack coating composition.