阅读说明：本技术 用于制造水可分散聚合物和水分散的聚合物的方法 (Process for making water-dispersible polymers and water-dispersed polymers ) 是由 约瑟夫·D·德索萨 亚瑟·里兹 本杰明·J·韦伯斯特 罗伯特·M·奥`布赖恩 卡拉斯·B·萨 于 2018-12-11 设计创作，主要内容包括：通过以下方式来制造水可分散的或水分散的聚合物：使(i)含有一个或多个环状碳酸酯基团的不饱和单体或(ii)含有多个环状碳酸酯基团的不饱和或饱和低聚物或聚合物与叔胺在酸存在下反应以提供水可分散的或水分散的单体、低聚物或聚合物。当步骤a)提供单体或低聚物时,所述单体或低聚物与一种或多种单体在引发剂存在下反应以提供水可分散的或水分散的聚合物。当步骤a)提供聚合物时,任选地使用所述聚合物来支持一种或多种不饱和单体在引发剂存在下的乳液聚合,以提供水可分散的或水分散的进一步聚合物。(A water-dispersible or water-dispersible polymer is made by: reacting (i) an unsaturated monomer containing one or more cyclic carbonate groups or (ii) an unsaturated or saturated oligomer or polymer containing a plurality of cyclic carbonate groups with a tertiary amine in the presence of an acid to provide a water-dispersible or water-dispersible monomer, oligomer or polymer. When step a) provides a monomer or oligomer, the monomer or oligomer is reacted with one or more monomers in the presence of an initiator to provide a water-dispersible or water-dispersible polymer. When step a) provides a polymer, the polymer is optionally used to support emulsion polymerization of one or more unsaturated monomers in the presence of an initiator to provide a further polymer that is water dispersible or water dispersible.)

1. A process for making a water-dispersible or water-dispersible polymer, the process comprising the steps of:

a) reacting (i) an unsaturated monomer containing one or more cyclic carbonate groups or (ii) an unsaturated or saturated oligomer or polymer containing a plurality of cyclic carbonate groups with a tertiary amine in the presence of an acid, or with an acid in the presence of a tertiary amine or in the presence of an acid and a tertiary amine to provide a water-dispersible or water-dispersible monomer, oligomer or polymer; and

b1) when step a) provides a water-dispersible or water-dispersible monomer or oligomer, reacting such monomer or oligomer with one or more monomers in the presence of an initiator to provide a water-dispersible or water-dispersible polymer; and

b2) when step a) provides a water-dispersible or water-dispersible polymer, such polymers are optionally used to support emulsion polymerization of one or more unsaturated monomers in the presence of an initiator to provide a further polymer that is water-dispersible or water-dispersible.

2. The method of claim 1, wherein step a) comprises reacting an unsaturated monomer containing one or more cyclic carbonate groups with a tertiary amine.

3. The method of claim 1, wherein step a) comprises reacting an oligomer or polymer containing a plurality of cyclic carbonate groups with a tertiary amine.

4. The method of claim 1, wherein step a) comprises reacting an unsaturated monomer containing one or more cyclic carbonate groups and a polymer containing a plurality of cyclic carbonate groups with a tertiary amine.

5. The method of claim 1, wherein step a) comprises reacting unsaturated monomers and prepolymers containing one or more cyclic carbonate groups with one or more unsaturated monomers in the presence of an initiator to provide an addition polymer containing a plurality of cyclic carbonate groups; and reacting such addition polymers with tertiary amines to provide water dispersible or water dispersible polymers.

6. The method of claim 5, wherein the prepolymer contains a plurality of cyclic carbonate groups.

7. The method of claim 5, wherein the prepolymer is free of cyclic carbonate groups.

8. The process of any preceding claim, wherein step a) comprises reacting an unsaturated monomer, oligomer or polymer containing a cyclic carbonate group with an acid in the presence of a tertiary amine, or reacting an unsaturated monomer, oligomer or polymer containing a cyclic carbonate group in the presence of an acid and a tertiary amine.

9. A method according to any preceding claim, wherein the cyclic carbonate group is a five-membered ring.

10. The process according to any preceding claim, wherein the cyclic carbonate group is a six-membered ring.

11. The method of claim 1, wherein step a) comprises reacting an unsaturated monomer with a tertiary amine, and such monomer is of formula Ia:

wherein:

each R¹Independently selected from hydrogen or an organic group;

R²selected from hydrogen or alkyl;

n is 0 or 1;

w, if present, is a linking group;

represents one or more methylene groups, which independently may be substituted or unsubstituted; and is

q is 1 or greater.

12. The method of claim 11, wherein q is 1.

13. The method of claim 11, wherein such monomer is glycerol carbonate methacrylate.

14. The method of claim 1, wherein step a) comprises reacting a polymer containing a plurality of cyclic carbonate groups with a tertiary amine in the presence of an acid, or with an acid in the presence of a tertiary amine or in the presence of an acid and a tertiary amine, and such polymer has formula Ib:

wherein:

p is a polymer backbone;

m is 2 or greater;

n is 0 or 1;

w, if present, is a linking group;

represents one or more methylene groups, which independently may be substituted or unsubstituted; and is

q is 1 or greater.

15. The method of claim 14, wherein such polymer is of formula Ic:

wherein:

p is the polymer backbone:

m is 2 or greater; and is

Represents one or more methylene groups, which independently may be substituted or unsubstituted; and is

q is 1 or greater.

16. The method of claim 14 or claim 15, wherein q is 1.

17. A process according to any preceding claim, wherein step a) provides a water-dispersible or water-dispersible monomer, oligomer or polymer containing quaternary ammonium salt groups.

18. The method of claim 1, wherein step a) provides a quaternary ammonium salt group-containing unsaturated monomer having formula IIa:

(R¹)₂C＝C(R²)W_nCH(OH)(CH₂)_qN⁺(R³)₃A^-IIa

wherein:

each R¹Independently selected from hydrogen or an organic group;

R²selected from hydrogen or alkyl;

n is 0 or 1;

w, if present, is a linking group;

q is 1 or greater;

each R³Independently selected from the group consisting of carbon-containing groups-CR⁴R⁵R⁶Wherein R is⁴、R⁵And R⁶Each of which is hydrogen or an organic group; and is

A^-Is the anion of the deprotonated acid HA.

19. The method of claim 1, wherein step a) provides a quaternary ammonium salt group-containing polymer having formula lib:

P-[W_nCH(OH)(CH₂)_qN⁺(R³)₃]_mmA^-IIb

wherein:

p is a polymer backbone;

m is 2 or greater;

n is 0 or 1;

w, if present, is a linking group;

q is 1 or greater;

each R³Independently selected from the group consisting of carbon-containing groups-CR⁴R⁵R⁶Wherein R is⁴、R⁵And R⁶Each of which is hydrogen or an organic group; and is

A^-Is the anion of the deprotonated acid HA.

20. The method of any one of claims 11, 14, 18, or 19, wherein W is present and is a heteroatom-containing linkage comprising an amide linkage, a carbonate linkage, an ester linkage, an ether linkage, a urea linkage, or a urethane linkage.

21. The method of any preceding claim, wherein step a) provides a quaternary ammonium salt group-containing polymer having formula IIc:

P-[C(O)OCH₂CH(OH)(CH₂)_qN⁺(R₃)₃]m mA^-IIc

wherein:

p is a polymer backbone;

m is 2 or greater:

q is 1 or greater;

each R³Independently selected from the group consisting of carbon-containing groups-CR⁴R⁵R⁶Wherein R is⁴、R⁵And R⁶Each of which is hydrogen or an organic group; and is

A^-Is the anion of the deprotonated acid HA.

22. The method of any preceding claim, wherein the tertiary amine comprises trimethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, ethylmethylethanolamine, dimethylethylamine, dimethylpropylamine, N-dimethyl 3-hydroxy-1-propylamine, dimethylbenzylamine, N-dimethyl 2-hydroxy-1-propylamine, diethylmethylamine, N-dimethyl 1-hydroxy-2-propylamine, triethylamine, tributylamine, N-methylmorpholine, or a mixture thereof.

23. The method of any preceding claim, wherein the tertiary amine comprises triethylamine or dimethylethanolamine.

24. The method of any preceding claim, wherein the acid contains one or more carboxylic acid groups.

25. The method of any preceding claim, wherein the acid comprises an acid functional polymer.

26. The method of claim 24, wherein the acid functional polymer contains a plurality of cyclic carbonate groups.

27. The method of claim 24, wherein the acid functional polymer does not contain cyclic carbonate groups.

28. The method of any preceding claim, wherein the cyclic carbonate group is reacted with a tertiary amine or acid at a temperature greater than 60 ℃.

29. The method of any preceding claim, wherein the cyclic carbonate group is reacted with a tertiary amine or acid at a temperature greater than 80 ℃.

30. The method of any preceding claim, wherein the cyclic carbonate group is reacted with a tertiary amine or acid at greater than ambient pressure.

31. The process of any preceding claim, wherein the water-dispersible or water-dispersible polymer in step b1) or b2) has formula IIIa:

P-[W_nCH(OH)(CH₂)_qN⁺(R³)₃]_mmA^-IIIa

wherein:

p is a polymer backbone;

m is 2 or greater;

n is 0 or 1;

w, if present, is a linking group;

q is 1 or greater;

each R³Independently selected from the group consisting of carbon-containing groups-CR⁴R⁵R⁶Wherein R is⁴、R⁵And R⁶Each of which is hydrogen or an organic group; and is

A^-Is the anion of the deprotonated acid HA.

32. The method of claim 31, wherein W is present and is a heteroatom-containing linkage comprising an amide linkage, a carbonate linkage, an ester linkage, an ether linkage, a urea linkage, or a urethane linkage.

33. The method of claim 31, wherein W is present, is an ester bond, and the carbonyl atom of the ester is attached to an unsaturated carbon atom of the monomer or oligomer or to the polymer backbone.

34. The process of claim 31, wherein the water-dispersible or water-dispersible polymer in step b1) or b2) has formula IIIb:

P-[C(O)OCH₂CH(OH)(CH₂)_qN⁺(R₃)₃]_mmA^-IIIb.

wherein:

p is a polymer backbone;

m is 2 or greater;

q is 1 or greater;

each R³Independently selected from the group consisting of carbon-containing groups-CR⁴R⁵R⁶Wherein R is⁴、R⁵And R⁶Each of which is hydrogen or an organic group; and is

A^-Is the anion of the deprotonated acid HA.

35. The method of any preceding claim, wherein step a), step b1) or step b2) provides a polymer containing from 1 to 20 wt% quaternary ammonium salt groups.

36. The method of any preceding claim, wherein step a), step b1) or step b2) provides a polymer containing from 1 to 10 wt% quaternary ammonium salt groups.

37. The process of any preceding claim, wherein step a), step b1), or step b2) provides a water dispersible polymer.

38. The method of any preceding claim, wherein step a), step b1), or step b2) provides a polymer dispersed in water.

39. The method of any preceding claim, wherein step a), step b1), or step b2) provides a polyether polymer.

40. The method of any preceding claim, wherein step a), step b1), or step b2) provides a polyether- (meth) acrylic copolymer.

41. The method of any preceding claim, wherein step a), step b1), or step b2) provides an emulsion polymerized latex polymer.

42. The method of claim 41, wherein the latex polymer is formed using a polymeric surfactant and the unsaturated monomer containing one or more cyclic carbonate groups and one or more other unsaturated monomers are emulsion polymerized in the presence of the polymeric surfactant.

43. The method of claim 42, wherein the acid in step a) comprises a polymeric surfactant comprising an acid-functional or anhydride-functional organic solution polymerized acrylic polymer.

44. The method of claim 41, wherein the latex polymer is formed using a non-polymeric surfactant and the unsaturated monomer containing one or more cyclic carbonate groups and one or more other unsaturated monomers are emulsion polymerized in the presence of the non-polymeric surfactant.

45. The method of claim 44, wherein the acid in step a) comprises one or more acid functional ethylenically unsaturated monomers.

46. The method of any preceding claim, wherein the water-dispersible or water-dispersible polymer is made from 1 to 10 weight percent cyclic carbonate monomers, based on the weight of other monomers used to form the polymer.

47. A water-dispersible or water-dispersible polymer made according to the process of any preceding claim.

48. A method of formulating an aqueous coating composition for a food or beverage can, the method comprising the step of including in the coating composition a water-dispersible or water-dispersible polymer made according to the method of any preceding claim.

49. A food or beverage container coating composition comprising a water-dispersible or water-dispersible polymer made according to the method of any preceding claim.

50. A food or beverage can aqueous coating composition comprising the water-dispersible or water-dispersible polymer produced from the method of any preceding claim.

51. A coating composition according to claim 49 or claim 50, wherein the non-volatile film-forming component of the coating composition comprises from 5% to 70% by weight of the water-dispersible or water-dispersible polymer.

52. A coating composition according to claim 49 or claim 50, wherein the non-volatile film-forming component of the coating composition comprises from 50 to 95% by weight of the water-dispersible or water-dispersible polymer.

53. The coating composition of any one of claims 49 to 52, wherein the composition is a food or beverage can in-spray coating composition.

54. A method of applying a coating composition, the method comprising applying the coating composition of any one of claims 49-53 to a metal substrate before or after forming the metal substrate into a food or beverage can or portion thereof.

55. The method of claim 54, wherein the composition is applied by spraying.

56. A food or beverage container or part thereof having an interior surface coated with a coating composition comprising a water-dispersible or water-dispersible polymer made according to the method of any one of claims 1 to 46.

57. The food or beverage container or portion thereof of claim 56, wherein the coating composition has cured or hardened.

58. The food or beverage container of claim 57, further comprising a food or beverage sealed within the container.

59. The food or beverage container of claim 56 or claim 57, wherein the container is a metallic food or beverage can.

60. The food or beverage container of any one of claims 56-59, wherein the coating composition contains less than 1,000 parts per million (ppm) of bisphenol A.

Technical Field

The present invention relates to water-dispersible or water-dispersible polymers, food and beverage container coatings, and coated food and beverage containers.

Background

Metallic food and beverage containers typically employ an internal coating that prevents the contents from contacting the metal substrate of the container. Such contact can lead to metal corrosion and contamination of the packaged product. This is particularly true when the contents of the container are chemically aggressive in nature. Protective coatings are also applied to the interior of food and beverage containers to protect the headspace between the food fill line and the container lid from corrosion, and also to the exterior of such containers to prevent damage or other damage to the substrate, label, or graphics.

The packaging coating should preferably be capable of high speed application to the substrate and should provide the necessary characteristics when hardened to perform in this demanding end use. For example, the coating should be safe for food contact, not adversely affect the taste of the packaged food or beverage product, have excellent substrate adhesion, resist staining and other coating defects (e.g., "popping", "whitening" and "blistering"), and resist degradation for extended periods of time, even when exposed to harsh environments. In addition, the coating should generally be capable of maintaining suitable film integrity during container manufacture and be capable of withstanding processing conditions to which the container may be subjected during product packaging and shipping. It has proven difficult to find coatings that provide satisfactory performance for all desired characteristics.

Disclosure of Invention

Many container coatings comprise water-dispersible or water-dispersible polymers. For example, surfactants present in the coating composition or functional groups on the polymeric binder can promote dispersibility. Quaternary ammonium groups are one such functional group and may be formed, for example, by reacting oxirane functional groups on the polymer binder with tertiary amines. The oxirane functional groups can be provided in the polyether polymer, for example, by reacting hydroxyl groups (e.g., phenolic groups) in the polyether polymer with epichlorohydrin, and can be provided in the acrylic polymer or polyether-acrylic copolymer, for example, by including Glycidyl Methacrylate (GMA) in the monomers forming the acrylic polymer segment. Although coating compositions containing oxirane functional groups (or derived from polymers containing oxirane functional groups) have been widely used and generally accepted, it is desirable to provide alternative reaction methods and reactants to address potential supply issues or other issues that may arise in connection with the use of oxirane functional groups. Accordingly, in one aspect, the present invention provides a process for making a water-dispersible or water-dispersible polymer, said process comprising the steps of:

a) reacting (i) an unsaturated monomer containing one or more cyclic carbonate groups or (ii) an unsaturated or saturated oligomer or polymer containing a plurality of cyclic carbonate groups with a tertiary amine in the presence of an acid (or with an acid in the presence of a tertiary amine or in the presence of an acid and a tertiary amine) to provide a water-dispersible or water-dispersible monomer, oligomer or polymer; and

b1) when step a) provides a water-dispersible or water-dispersible monomer or oligomer, reacting such monomer or oligomer with one or more unsaturated or saturated monomers (preferably saturated monomers) in the presence of an initiator to provide a water-dispersible or water-dispersible polymer; and

b2) when step a) provides a water-dispersible or water-dispersible polymer, such polymers are optionally used to support emulsion polymerization of one or more unsaturated monomers in the presence of an initiator to provide a further polymer that is water-dispersible or water-dispersible.

In one embodiment, the reaction in step a) is carried out in a solvent and the reaction in step b1) or step b2) (if performed) is carried out in water. In another embodiment, the reactions in step a) and step b1) or step b2) are performed in a solvent. In another embodiment, the reaction in step a) is carried out in water, and the reaction in step b1) or step b2) (if performed) is also carried out in water.

In one embodiment, the unsaturated monomer in step a) has the formula Ia:

wherein:

each R¹Independently selected from hydrogen or an organic group;

R²selected from hydrogen or alkyl;

n is 0 or 1;

w (if present) is a linking group (e.g., a divalent linking group);

represents one or more methylene groups, which independently may be substituted or unsubstituted; and is

q is 1 or more, preferably not more than 3, and more preferably 1 or 2.

In another embodiment, the polymer containing a plurality of cyclic carbonate groups in step a) has the formula Ib:

wherein:

p is a polymer backbone;

m is 2 or greater, and preferably such that the indicated groups in parentheses represent from about 1 wt% to about 15 wt%, more preferably from about 1 wt% to about 10 wt% of the polymer; and is

n、W、And q is as defined above.

In another embodiment, the water-dispersible or water-dispersible monomer provided in step a) is an ammonium salt group-containing unsaturated monomer having the formula IIa:

(R¹)₂C＝C(R²)W_nCH(OH)(CH₂)_qN⁺(R³)₃A^-IIa

wherein:

each R¹Independently selected from hydrogen or an organic group;

R²selected from hydrogen or alkyl;

n、W、and q is as defined above.

Each R³Independently selected from the group consisting of carbon-containing groups-CR⁴R⁵R⁶Wherein R is⁴、R⁵And R⁶Each of which is hydrogen or an organic group; and is

A^-Is the anion of the deprotonated acid HA.

In another embodiment, the water-dispersible or water-dispersible polymer provided in step a) has formula lib:

P-[W_nCH(OH)(CH₂)_qN⁺(R³)₃]_mmA^-IIb

wherein:

P、m、n、W、each R³And A^-As defined above.

In another embodiment, the water-dispersible or water-dispersible polymer used in step b1) or step b2) has formula IIIa:

P-[W_nCH(OH)(CH₂)_qN⁺(R³)₃]_mmA^-IIIa

wherein:

P、m、n、W、q, each R³And A^-As defined above.

In certain embodiments, the monomer, oligomer or polymer containing a plurality of cyclic carbonate groups in step a) is or is derived from glycerol carbonate methacrylate ("GCMA", C)₈H₁₀O₅CAS No. 13818-44-5), also known as "glycerol methacrylate carbonate" or "(2-oxo-1, 3-dioxolan-4-yl) methyl-2-methylprop-2-enoate", and having the formula IV:

in certain embodiments, the water dispersible or water dispersible monomer in step a) is, or the water dispersible or water dispersible oligomer or polymer in step b1) or the further polymer in step b2) may be derived from a compound having the formula V:

in an additional embodiment, the instant invention provides a food or beverage container coating composition comprising a water-dispersible or water-dispersible polymer made according to any of the above-described methods. In another embodiment, the present invention provides a food or beverage container or portion thereof having an interior surface coated with a coating composition comprising a water-dispersible or water-dispersible polymer made according to any of the above-described methods. In other embodiments, the present invention provides such food or beverage containers, and further comprises a food or beverage sealed within the container.

Detailed Description

As used herein, "a," "an," "the," "at least one," and "one or more" or lack thereof are used interchangeably. Thus, for example, a coating composition comprising "a" stabilizer can be interpreted to mean that the coating composition comprises "one or more" stabilizers.

The term "backbone" when used with respect to a polymer refers to a series of consecutive covalently bonded atoms that together form a chain (typically the longest chain) in the polymer.

The term "comprising" and its variants do not have a limiting meaning when these terms appear in the description and claims.

The term "crosslinker" refers to a molecule capable of forming covalent bonds between copolymers (e.g., between polymers) or between two different regions of the same copolymer.

The term "easy open end" refers to a can end (typically the end of a food or beverage container) that includes (i) a frangible opening portion (which, for some beverage can ends, functions as a drinking spout) and (ii) a riveted portion for attaching a tab thereto for the purpose of opening the frangible opening portion to access a product contained in the can or container.

The term "estrogenic activity" or "estrogenic agonist activity" refers to the ability of a compound to mimic hormone-like activity by interacting with an endogenous estrogen receptor (typically the endogenous human estrogen receptor).

The term "ethylenically unsaturated" refers to a carbon-carbon double or triple bond capable of participating in a free radical initiated polymerization reaction and is not intended to encompass the carbon-carbon double bonds present in aryl groups (e.g., the phenyl group of styrene). Thus, for example, dodecylbenzenesulfonic acid is not considered to contain ethylenically unsaturated groups.

The term "food-contact" when used in reference to a surface or coating refers to an exposed surface (e.g., an uncoated substrate or a coating on a substrate) of an article (e.g., a food or beverage container) that is in contact with or is suitable for prolonged contact with a food or beverage product.

The term "functional group" when used with respect to a polymer refers to a group that can react (e.g., with a molecule, crosslinker, or salt of another polymer) and thereby alter a characteristic of the polymer, including characteristics such as molecular weight, solubility, surface energy, further reactivity, and the like.

The term "glass transition temperature" or "Tg" when used with respect to a polymer in a coating composition or a coated article coated with such a composition refers to the measured Tg obtained prior to any curing of such a coating composition, and can be measured using differential scanning calorimetry ("DSC").

The term "latex" polymer refers to a dispersion or emulsion of polymer particles formed in the presence of water and one or more secondary dispersants or emulsifiers (e.g., surfactants, alkali soluble polymers, or mixtures thereof) necessary to form the dispersion or emulsion. The secondary dispersant or emulsifier is typically separated from the polymer after it is formed. In some embodiments, the reactive dispersant or emulsifier may become part of the polymer particles as they are formed.

The term "extractable" when used in reference to a compound in a coating composition means when the coating composition is applied (typically about 1 mg/cm)²) Examples of such test conditions include exposure of the cured coating to HP L grade C acetonitrile for 24 hours at 25 deg.C other examples include exposure of the cured coating to 3 wt% acetic acid (a mimetic of aqueous and acidic food), 10 vol% ethanol (a mimetic of alcoholic food containing up to 10% alcohol), 50 vol% ethanol (a mimetic of dairy food), rectified olive oil, or a substitute for olive oilSuch as 95 vol% ethanol, isooctane or modified polyphenylene ether (MMPO). Exemplary procedures and restrictions are set forth in EU Commission directives 82/711/EEC, 93/8/EEC, and 97/48/EC, and in section 175.300 of 21CFR, paragraphs (d) and (e). For such extraction procedures to be unable to accurately distinguish a particular compound from one or more derivatives of such compound (e.g., to distinguish a bisphenol from a diglycidyl ether or diglycidyl ester of such bisphenol), then the amount of such compound should be taken as the total amount of extraction detected for the particular compound and its derivatives.

The term "oligomer" refers to a molecule consisting of two, three or four monomeric units. Generally, if one of the monomer units is removed from an oligomer, the chemical nature of the oligomer will change significantly.

The term "on" when used in the context of a coating applied to a surface or substrate includes both coatings applied directly or indirectly to the surface or substrate. Thus, for example, application of a coating to a primer layer overlying a substrate constitutes application of the coating to the substrate.

The term "organic group" refers to a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that can be further classified as an aliphatic group, a cyclic group (e.g., aromatic and cycloaliphatic), or a combination of aliphatic and cyclic groups (e.g., alkaryl and aralkyl groups). The term "aliphatic group" refers to a saturated or unsaturated, linear or branched hydrocarbon group. For example, the term is used to encompass alkyl, alkenyl, and alkynyl groups. The term "alkyl" refers to a saturated straight or branched chain hydrocarbon group (e.g., n-propylisopropyl). The term "alkenyl" refers to an unsaturated straight or branched chain hydrocarbon group having one or more carbon-carbon double bonds (e.g., a vinyl group). The term "cyclic group" refers to a closed-ring hydrocarbon group that is classified as an alicyclic group or an aromatic group, both of which can contain heteroatoms. The term "alicyclic group" refers to a cyclic hydrocarbon group having characteristics similar to those of an aliphatic group. Groups that are the same or different from other groups may be referred to as "independent" items. Substitutions on the organic groups of the compounds of the present invention are contemplated. The terms "group" and "fragment" can be used to distinguish between a chemical species that allows for substitution or that may be substituted, and a chemical species that does not allow for substitution or that may not be so substituted. The term "group" is intended to be a recitation of a particular fragment, as well as a recitation of the broader class of substituted and unsubstituted structures that comprise that fragment. Thus, when the term "group" is used to describe a chemical substituent, the chemical material being described comprises the unsubstituted group and, for example, the group having O, N, Si or S atoms in the chain (as in an alkoxy group) as well as a carbonyl group or other conventionally substituted group. When the term "fragment" is used to describe a chemical compound or substituent, it is intended to include only unsubstituted chemical materials. For example, the phrase "alkyl group" is intended to include not only pure open-chain saturated hydrocarbon alkyl substituents (e.g., methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, pentyl, 2-ethylhexyl, and the like), but also alkyl substituents bearing other substituents known in the art (e.g., hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, and the like). Thus, "alkyl group" includes ether groups, haloalkyl groups, nitroalkyl groups, carboxyalkyl groups, hydroxyalkyl groups, sulfoalkyl groups, and the like. On the other hand, the phrase "alkyl moiety" is limited to include only pure open-chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, pentyl, 2-ethylhexyl, and the like.

The term "pendant group," when used with respect to a polymer, refers to a group (i.e., a pendant group) that is attached to the polymer at one or more atoms located between the terminal atoms of the polymer backbone. In general, the pendent group can be a functional group or a non-functional group.

The term "polyphenol" refers to a polyhydroxy-based material having at least two phenylene groups each comprising a six carbon ring and at least one hydroxyl group attached to a carbon atom of the ring, wherein the rings of phenylene do not share any common atoms.

Unless otherwise specified, the term "polymer" includes both homopolymers and copolymers (e.g., polymers of two or more different monomers). Similarly, unless otherwise indicated, use of a term (e.g., "polyether") that refers to a polymer class is intended to include both homopolymers and copolymers (e.g., polyether-acrylate copolymers).

The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

The term "substantially free," when used with respect to a coating composition that may contain a particular compound, means that the coating composition contains less than 1,000 parts per million (ppm) by weight of the compound. The term "substantially free," when used with respect to a coating composition that may contain a particular compound, means that the coating composition contains less than 100 parts per million (ppm) by weight of the compound. The term "substantially completely free," when used with respect to a coating composition that may contain a particular compound, means that the coating composition contains less than 5 parts per million (ppm) of the compound. The term "completely free," when used with respect to a coating composition that may contain a particular compound, means that the coating composition contains less than 20 parts per billion (ppb) by weight of the compound. When the phrases "free of" (outside the context of the above phrases), "excluding any", and the like are used herein, such phrases are not intended to exclude the presence of trace amounts of related structures or compounds that may be present as or due to environmental contaminants.

The term "end group" when used with respect to a polymer refers to a group attached to the polymer at one or more terminal atoms of the polymer backbone. Typically, the terminal groups will be functional groups.

The term "unsaturated", when used in the context of a compound, refers to a compound that contains at least one non-aromatic (e.g., aliphatic) carbon-carbon double or triple bond.

The term "water-dispersible" when used in reference to a polymer means that the polymer is capable of combining with water itself without the use of secondary dispersants or emulsifiers to obtain an aqueous dispersion or emulsion of polymer particles that has a storage stability of at least one month at normal storage temperatures.

The term "water-dispersed" when used with respect to a polymer means that the polymer is present as an aqueous dispersion or emulsion of polymer particles that has a storage stability of at least one month at normal storage temperatures.

Also herein, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4,5, etc.).