阅读说明：本技术 来自c12-c23二酸的粉末涂料树脂 (Powder coating resins from C12-C23 diacids ) 是由 J·T·卡夫梅耶 D·B·加尔巴克 于 2019-01-25 设计创作，主要内容包括：描述了粉末涂料树脂和使用该粉末涂料树脂制备的涂料。该粉末涂料树脂基于C<Sub>12</Sub>至C<Sub>23</Sub>二酸的使用。使C<Sub>12</Sub>至C<Sub>23</Sub>二酸与具有醇官能团和胺官能团的反应物反应,以形成具有酯官能团和酰胺官能团的羧酸封端的聚合物。或者,使C<Sub>12</Sub>至C<Sub>23</Sub>二酸与具有醇官能团和胺官能团的反应物反应,以形成中间体多元醇,然后使该中间体多元醇与乙酰乙酸或其酯反应,以形成乙酰乙酸酯封端的聚合物。(Powder coating resins and coatings prepared using the powder coating resins are described. The powder coating resin is based on C 12 To C 23 The use of diacids. Make C 12 To C 23 The diacid is reacted with a reactant having alcohol functionality and amine functionality to form a carboxylic acid-terminated polymer having ester functionality and amide functionality. Or, make C 12 To C 23 Reacting a diacid with a reactant having alcohol and amine functionality to form an intermediate polyol, and then reacting the intermediate polyol with acetoacetic acid or ester thereof to form acetoacetyl esterAn acid ester terminated polymer.)

1. A powder coating resin comprising:

a first carboxylic acid-terminated polymer having an ester functional group and an amide functional group, comprising a first C₁₂To C₂₃A reaction product of a diacid and a first reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof; or

A first acetoacetate-capped polyol comprising the reaction product of a first intermediate polyol and acetoacetate or an ester thereof, and whereinThe first intermediate polyol comprises a second C₁₂To C₂₃A reaction product of a diacid and a second reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof.

2. The resin of claim 1, further comprising one or more of:

a second carboxylic acid-terminated polymer having ester and amide functional groups, comprising a third C₁₂To C₂₃A reaction product of a diacid and a third reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or combinations thereof, and wherein the third C for the second carboxylic acid terminated polymer₁₂To C₂₃Diacid with said first C for said first carboxylic acid terminated polymer₁₂To C₂₃The diacids are different; or

A second diacetoacetate terminated polyol comprising the reaction product of a second intermediate polymer and acetoacetic acid or ester thereof, and wherein the second intermediate polyol comprises a fourth C₁₂To C₂₃A reaction product of a diacid and a fourth reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or combinations thereof, and wherein the fourth C for the second diacetoacetate terminated polyol₁₂To C₂₃The second C for the diacid and the polyol capped with the first acetoacetate ester₁₂To C₂₃The diacids are different; or

A third carboxylic acid-terminated polymer having an ester functional group and an amide functional group, wherein the third carboxylic acid-terminated polymer is a reaction product of a third intermediate polyol and a first diacid, and wherein the third intermediate polyol is C₁₂To C₂₃The reaction product of a diester and a fifth reactant comprising an aminoalcohol, or a mixture of a polyamine and a polyolOr a mixture of amine alcohol and polyamine, or a mixture of amine alcohol and polyol, or a combination thereof, and wherein the C for the third carboxylic acid terminated polymer₁₂To C₂₃The diester has the first C with the polymer for the first carboxylic acid end-capping₁₂To C₂₃The different number of carbon atoms of the diacid; and is

Wherein the third carboxylic acid polymer is present in an amount less than 50 wt% of the resin.

3. The resin of any of claims 1-2, wherein one or more of the first, second, third, fourth, or fifth reactants comprises the amine alcohol comprising ethanolamine, N-methylethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-butanol, 4-amino-2-butanol, 3-amino-2-methyl-1-propanol, 3-amino-2-methyl-1-butanol, 4-amino-3-methyl-2-butanol, 2- (aminomethyl) -1-butanol, 1-propanol, 2-amino-2-methyl-1-butanol, or a mixture thereof, 3-amino-2, 2-dimethyl-1-propanol, 4-amino-2-pentanol, 1-amino-3-pentanol, 3-amino-1-pentanol, 4-amino-2-methyl-2-butanol, 3-amino-3-methyl-1-butanol, 3-amino-2- (aminomethyl) -1-propanol, diethanolamine, 3-amino-1, 2-propanediol, 2- (aminomethyl) -1, 3-propanediol, 3-amino-1, 5-pentanediol, 2-amino-1, 4-butanediol, or combinations thereof.

4. The resin of any of claims 1-3, wherein one or more of the first, second, third, fourth, or fifth reactants comprises: the polyamine comprising ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, piperazine, or a combination thereof; or the polyol comprising ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, glycerol, trimethylolpropane, or a combination thereof.

5. The resin of any of claims 1-4, wherein the first C₁₂To C₂₃Diacid, second C₁₂To C₂₃Diacid, third C₁₂To C₂₃Diacid or fourth C₁₂To C₂₃The diacid comprising C₁₆To C₂₃Diacid, or wherein said C₁₂To C₂₃The diester comprising C₁₆To C₂₃A diester.

6. The resin of any one of claims 1-5, wherein the first diacid comprises oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid, and undecanedioic acid, tridecanedioic acid, or a combination thereof.

7. The resin of any one of claims 1-6:

wherein the first C for the first carboxylic acid terminated polymer₁₂To C₂₃The diacid is C₁₂To C₂₃Diacid, or said second C for said first acetoacetate-capped polyol₁₂To C₂₃The diacid is C₁₂To C₂₃A diacid; and is

Wherein said third C for said second carboxylic acid terminated polymer₁₂To C₂₃The diacid is C₂To C₁₁Diacid, or said fourth C for said second acetoacetate-capped polyol₁₂To C₂₃The diacid is C₂To C₁₁Diacid, or the C for the third carboxylic acid terminated polymer₁₂To C₂₃The diester being C₂To C₁₁A diester.

8. A method of preparing a powder coating comprising:

blending the resin of any of claims 1-7 with a crosslinker compound, processing into powder form, and subsequently exposing to curing conditions to form a crosslinked coating, wherein the crosslinker comprises an epoxy crosslinker compound or resin, a hydroxyalkylamide crosslinker, or a combination thereof.

9. A method of preparing a powder coating resin comprising one or more of the following steps:

make the first C₁₂To C₂₃Reacting a diacid with a first reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a combination thereof, to form a first carboxylic acid-terminated polymer having an ester functional group and an amide functional group; or

Let a second C₁₂To C₂₃Reacting a diacid with a second reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof, to form a first intermediate polyol; and reacting the first intermediate polyol with acetoacetate or an ester thereof to form a first acetoacetate ester-capped polyol.

10. The method of claim 9, further comprising one or more of the following steps:

let a third C₁₂To C₂₃Reacting a diacid with a third reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof, to form a second carboxylic acid terminated polymer having an ester functional group and an amide functional group; or

Make the fourth C₁₂To C₂₃Reacting the diacid with a fourth reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof, to form a second intermediate polyol; and reacting the second intermediate polyol with acetoacetic acid or ester thereof to form a second diacetoacetate terminated polyol; or

Make C₁₂To C₂₃Reacting the diester with a fifth reactant comprising an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof, to form a third intermediate polyol; and reacting said third intermediate polyolReacting with a first diacid to form a third carboxylic acid-terminated polymer having ester functional groups and amide functional groups; and

blending the first carboxylic acid terminated polymer, or the first acetoacetate-terminated polyol, or both, with one or more of: the second carboxylic acid terminated polymer, or the second diacetoacetate terminated polyol, or the third carboxylic acid terminated polymer; and is

Wherein the third carboxylic acid polymer is present in an amount less than 50 wt% of the resin.

11. The method of any one of claims 9-10, wherein one or more of the first, second, third, fourth, or fifth reactant comprises the amine alcohol comprising ethanolamine, N-methylethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-butanol, 4-amino-2-butanol, 3-amino-2-methyl-1-propanol, 3-amino-2-methyl-1-butanol, 4-amino-3-methyl-2-butanol, 2- (aminomethyl) -1-butanol, or a mixture thereof, 3-amino-2, 2-dimethyl-1-propanol, 4-amino-2-pentanol, 1-amino-3-pentanol, 3-amino-1-pentanol, 4-amino-2-methyl-2-butanol, 3-amino-3-methyl-1-butanol, 3-amino-2- (aminomethyl) -1-propanol, diethanolamine, 3-amino-1, 2-propanediol, 2- (aminomethyl) -1, 3-propanediol, 3-amino-1, 5-pentanediol, 2-amino-1, 4-butanediol, or combinations thereof.

12. The method of any one of claims 9-11, wherein one or more of the first, second, third, fourth, or fifth reactants comprises: the polyamine comprising ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, piperazine, or a combination thereof; or wherein the polyol comprises ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, glycerol, trimethylolpropane, or a combination thereof.

13. As claimed in claims 9 to 12The method of any one of, wherein the first C₁₂To C₂₃Diacid, second C₁₂To C₂₃Diacid, third C₁₂To C₂₃Diacid or fourth C₁₂To C₂₃The diacid comprising C₁₆To C₂₃Diacid, or wherein said C₁₂To C₂₃The diester comprising C₁₆To C₂₃A diester.

14. The method of any one of claims 9-13, wherein the first diacid comprises oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid and undecanedioic acid, tridecanedioic acid, or a combination thereof.

15. The method of any one of claims 9-14:

wherein the first C for the first carboxylic acid terminated polymer₁₂To C₂₃The diacid is C₁₂To C₂₃Diacid, or said second C for said first acetoacetate-capped polyol₁₂To C₂₃The diacid is C₁₂To C₂₃A diacid; and is

Wherein said third C for said second carboxylic acid terminated polymer₁₂To C₂₃The diacid is C₂To C₁₁Diacid, or said fourth C for said second acetoacetate-capped polyol₁₂To C₂₃The diacid is C₂To C₁₁Diacid, or the C for the third carboxylic acid terminated polymer₁₂To C₂₃The diester being C₂To C₁₁A diester.

Description of the invention

The present application relates to compounds derived from aliphatic C₁₂To C₂₃Compositions of polymer resins of diacids, powder coatings prepared from the polymer resins, and methods of preparing the polymer resins. These resins contain amide (functional) and ester functionality, as well as reactive carboxylic acid or acetoacetoxy terminal functionality, which allows the resin to be cured with a crosslinker to form thermoset polymers particularly useful for coating and powder coating applications. Having suitable physical properties to be comminuted into a free-flowing powder, the resins also exhibit relatively low melting points, low melt viscosities, low solubility in common solvents, and reactivity with conventional curing agents, which makes them particularly suitable for low temperature curing powder coatings, and in particular for the coating of heat-sensitive substrates. In addition, in some cases, desirable C for use in these resins₁₂To C₂₃The diacids can be derived from bio-based feedstocks, such as fatty acids from soybeans.

Biobased polyester building blocks (e.g., triglyceride oils and related fatty acids) have been engineered and transformed for use in coating applications due to a range of physical properties (e.g., flexibility and hydrophobicity).

The study of biobased materials for resin development provides a way to introduce new structural units with properties and characteristics that can be influenced to meet the changes in requirements for heat sensitive substrates. In addition, the incorporation of bio-based resins from renewable feedstocks, such as soybean oil, introduces aspects of sustainability that are particularly attractive in the coating of wood products, such as hardwood products or Medium Density Fiberboard (MDF). MDF is one of the largest opportunities for expanding powder coatings today because it is used in a wide variety of consumer products, including modular furniture, cabinets, countertops and other building materials, store displays and point of purchase (POP) devices, and a wide range of other products for homes and offices.

The oleochemical industry continues to introduce new products derived from animal fats and vegetable oils that are not readily available from petroleum feedstocks. One such emerging product family is aliphaticLong-chain diacids, which are commercially produced from fatty acids via fermentation or olefin metathesis routes. Chemical conversion of readily available fatty acids to produce C₁₈Octadecanedioic acid structural unit, its preparation and use in petroleum-based C₆Adipic acid or even biobased C₉Azelaic acid is similar but still significantly different.

Prior experience with these long chain diacids includes the observation of interesting melting characteristics of long chain diester and amide derivatives with well-defined, relatively high melting points. It is hypothesized that long chain diacid resin analogs will have greater solvent resistance, hydrolytic stability, toughness, and flexibility relative to the properties of short chain aliphatic systems, and that these resin analogs can be designed to have suitable melt characteristics for use in low temperature powder coating resins. To be an effective improvement over current resins, a target cure temperature of 125 ℃ or less is particularly desirable for low temperature powder coatings for heat sensitive substrates.

C-based PCT application having Ser. No. ____________, attorney docket No. 17876PCT/130637PCT, entitled Powder Coating Resins from C12-C23 polyesters filed on the same day as the present application, which application is incorporated herein by reference in its entirety, was developed₁₂To C₂₃Powder coating technology for the use of diesters.

Via C₁₂To C₂₃Classical condensation polymerization of diacids with different amino alcohols to prepare a first type of resin results in fully aliphatic, carboxy-functional resins as set forth belowA polyester-amide resin binder. The molecular weight, acid number and functionality are controlled by selective stoichiometry of acid groups with amines and alcohols, resulting in resins with reactive carboxylic acid functional groups. The molecular weight of the resin is typically greater than 475 g/mol and less than 10,000 g/mol, or greater than 475 g/mol and less than 7,500 g/mol, or greater than 475 g/mol and less than 5,000 g/mol. As the molecular weight increases, the acid number of the resin decreases, which is determined as the amount of potassium hydroxide (in mg KOH/g) needed to neutralize the acid functionality in 1 gram of resin.

Below shows C₁₈General resin synthesis scheme for carboxylic acid functional diacid polyester-amide resins. For clarity, the incorporated branching functionality attributed to diethanolamine has been omitted.

The resin technology of the invention is based on C₁₂To C₂₃The use of diacids in powder coating resins and powder coatings prepared using the powder coating resins.

The diacids used include C₁₂To C₂₃Diacid, or C₁₆To C₂₃Diacid, or C₁₈To C₂₃A diacid. Mixtures of diacids may be used. Mixtures of diacids comprising two or more C₁₂To C₂₃A mixture of diacids. Some mixtures include one or more C₁₈To C₂₃Diacid and one or more C₁₂To C₁₆A diacid. In addition, one or more C may be used₁₂To C₂₃Diacids with one or more C₂To C₁₁Mixing the diacids.

C can be produced from petroleum or bio-based sources₁₂To C₂₃A diacid. Biobased C₁₂To C₂₃Diacids can be derived from microbial fermentation of fatty acids, microbial fermentation of sugars, chemical oxidation of fatty acids, metathesis of fatty acids or fatty esters, and methoxycarbonylation of fatty acids or fatty esters. The fatty acid and fatty acid ester are derived from animal fat, algae oil, and vegetable oil (p)And a fat organic oil) including, but not limited to, soybean oil, canola oil, rapeseed oil, sunflower oil, palm oil, cottonseed oil, corn oil, safflower oil, and tall oil, and including high oleic acid variants.

Make C₁₂To C₂₃The diacid is reacted with a reactant having alcohol functionality and amine functionality. The reactants may have primary or secondary amine functionality, and/or primary or secondary alcohol functionality. They may be monofunctional or polyfunctional amines and/or monofunctional or polyfunctional alcohols.

The reactant may be an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof.

Suitable amine alcohols include, but are not limited to, amine monoalcohols and amine polyols. Examples include, but are not limited to, ethanolamine, N-methylethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-butanol, 4-amino-2-butanol, 3-amino-2-methyl-1-propanol, 3-amino-2-methyl-1-butanol, 4-amino-3-methyl-2-butanol, 2- (aminomethyl) -1-butanol, 3-amino-2, 2-dimethyl-1-propanol, 4-amino-2-pentanol, 1-amino-3-pentanol, 3-amino-1-pentanol, ethanol, 4-amino-2-methyl-2-butanol, 3-amino-3-methyl-1-butanol, 3-amino-2- (aminomethyl) -1-propanol, diethanolamine, 3-amino-1, 2-propanediol, 2- (aminomethyl) -1, 3-propanediol, 3-amino-1, 5-pentanediol, 2-amino-1, 4-butanediol, or a combination thereof. The amine alcohols also include N-alkyl substituted amine alcohols wherein the alkyl group has 1 to 10 carbon atoms.

Suitable polyamines include, but are not limited to, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexamethylenediamine, or combinations thereof.

Suitable polyols include, but are not limited to, ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, or combinations thereof.

The ratio of amine functional groups to alcohol functional groups can be adjusted to increase or decrease the physical properties (e.g., melting point temperature) of the resin. For example, increasing the number of amide groups generally increases the melting temperature and decreases solubility in common solvents. Increasing the ester groups can lower the melting temperature.

The resin mixture may also include a carboxylic acid-terminated polymer having an ester functional group and an amide functional group that is the reaction product of a polyol and a first diacid. The polyol is C₁₂To C₂₃The reaction product of a diester and reactants comprising: an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof. C for the carboxylic acid-terminated Polymer₁₂To C₂₃The diester having an acid group with C₁₂To C₂₃Carboxylic acid terminated polymers made from diacids have different numbers of carbon atoms. The third carboxylic acid polymer is present in an amount less than 50 wt% of the resin. The first diacid can include short chain diacids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanoic acid, and undecanedioic acid, brassylic acid, or combinations thereof. Suitable amine alcohols, polyamines and polyols for use in this reaction are described above.

The resin produced may have an acid number within the following range: 20-90 mg KOH/g, or 30-70 mg KOH/g, or 40-50 mg KOH/g, or 43-47 mg KOH/g. The acid number is achieved by an excess of diacid over the amount of amine alcohol, polyamine and polyol used. The diacid is used in excess to ensure that there are available carboxylic acid groups in the formulated powder coating that react with the crosslinker.

The resin may have a peak melting point of 90-130 ℃ or 118-123 ℃.

The resin may have the following viscosity at 125 ℃: less than 4000 centipoise, or less than 3000 centipoise, or less than 2000 centipoise, or less than 1000 centipoise, or 700 to 900 centipoise.

If desired, the resin can be produced without the addition of a catalyst. This is advantageous because typical polyester resins require catalysts, and some catalysts have health concerns.

The resins may be formulated into powder coatings. The formulation includes a cross-linking agent that is reactive with the carboxylic acid end groups. Suitable crosslinkers include, but are not limited to, epoxy crosslinker compounds and resins, Hydroxyalkylamide (HAA) crosslinkers, or combinations thereof, and the like. Epoxy-type crosslinking agents include, but are not limited to, triglycidyl isocyanurate (TGIC), glycidyl esters, glycidyl methacrylate resins, aliphatic ethylene oxides, combinations thereof, or the like.

The powder coating formulation may include other components as are known in the art that are typically included in powder coating compositions. These additional components may include, but are not limited to, one or more of the following: catalysts, flow agents, accelerators, degassing agents, pigments, pigment dispersion aids, fillers, UV absorbers, light stabilizers, antioxidants, antistatic/charge control additives, tribocharging additives (tribo-charging additives), antiblocking additives, scratch-resistant additives, slip agents, texturing additives (texturing additives), matting agents, and the like.

The powder coating may be electrostatically applied to a substrate and thermally cured. The cure time is typically less than 30 minutes, or less than 20 minutes, or less than 10 minutes, or less than 5 minutes, or less than 3 minutes.

The powder coating can be cured at temperatures in the range of 120-220 ℃. Typical coatings cure at temperatures in the range of 180-220 deg.C, while other coatings cure at temperatures in the range of 150-170 deg.C, and additional coatings cure at temperatures in the range of 125-140 deg.C.

Powder coatings have good aesthetic appearance and useful properties including gloss (e.g., greater than 60gu at 60 °), adhesion (e.g., 5B), flexibility (e.g., 160 in-lb forward and reverse impacts), and solvent resistance (e.g., 100 double rubs using MEK). The powder coatings show excellent durability by QUV-B accelerated aging testing.

May be specific for C used to produce powder coating resins₁₂To C₂₃The diacid, amine alcohol, polyamine and/or polyol, and the amounts are selected to achieve the properties desired for a particular application. Some applications have higher requirements for physical properties than others. Thus, while a powder coating resin may be unacceptable for one application having high physical property requirements, it may be acceptable for other applications that do not require the same level of physical properties.

Compared with shorter C₁₂To C₁₆Diacid, longer C₁₈To C₂₃Diacids generally give better properties in terms of chemical resistance.

The second type of resin contains ester and amide functional groups. It has an acetoacetate (AcAc) terminal functional group. In this chemistry, by reacting C₁₂To C₂₃The diacid is reacted with an amine alcohol, or a mixture of a polyamine and a polyol, or a mixture of an amine alcohol and a polyamine, or a mixture of an amine alcohol and a polyol, or a combination thereof to produce a polyol. The polyol is then esterified or transesterified with acetoacetate or its ester. C to form the tetra-AcAc functionality is shown below₁₈The reaction sequence of diacid and diethanolamine.

Suitable acetoacetylated compounds include, but are not limited to, acetoacetic acid or esters thereof. Suitable esters include, but are not limited to, t-butyl acetoacetate and ethyl acetoacetate.

The diacids, amine alcohols, polyamines, and polyols used herein are as described above.

Suitable crosslinkers for acetoacetate-capped polyols include, but are not limited to, polyisocyanates, polyaldehydes, melamine resins, and unsaturated compounds suitable for Michael addition reactions, or combinations thereof.

Examples