POLY(LACTONE)S, METHOD OF MANUFACTURE, AND USES THEREOF

1 . A poly(lactone) comprising units of formula I

wherein

each b=0 or 1;

the molar ratio of w:r:s:t=(0-30):(99.9-2):(0-98):(0-30), wherein

w is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, t is the number of crosslinked repeat units, and

w+s+t is at least 1;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group optionally containing a heteroatom wherein Q′ is covalently bonded to at least a second polymer backbones, wherein the second polymer backbone comprises units of formula I;

X is a nucleophile residue;

G′ is a single bond to an additional polymer backbone or G is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I;

when w>0, the total number of units (w+r+s+t) is 100 or greater,

when w=0 and t>0, the total number of units (r+s+t) is 5,000 or greater;

when w=0 and t=0, the total number of units is (r+s) is effective to provide a weight average molecular weight of 5,000 or greater.

2 . The poly(lactone) of claim 1 having the formula I-a

wherein

each b=0 or 1;

the molar ratio of the total of each of w:r:s:t=(0-30):(99.9-2):(0-98):(0.01-30), wherein w is the number of post-reacted α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, t is the number of crosslinked α-methylene lactone repeat units, provided that t is at least 1;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-a, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-a;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-a;

when w>0, the total number of units (w+r+s+t) is 100 or greater,

when w=0 and t>0, the total number of units (r+s+t) is 5,000 or greater;

when w=0 and t=0, the total number of units is (r+s) is effective to provide a weight average molecular weight of 500,000 g/mole or greater.

3 . The poly(lactone) of claim 1 having the formula I-b

wherein

each b=0 or 1;

the molar ratio of the total of each of w:r:s:t=(0-30):(99.9-2):(0-98):(0.01-30), wherein

w is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, and t is the number of crosslinked α-methylene lactone repeat units, and

each value of w, r, s, and t are independent of any other value of w, r, s, and t;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone) I-b and at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;

G is a single bond or a C 1-30 hydrocarbyl group;

c=1-5 and d=0-5 provided that c+d=1-5, and

when w>0, the total number of units (w+r+s+t) is 100 or greater,

when w=0, the total number of units (r+s+t) is 5,000 or greater;

4 . The poly(lactone) of claim 1 having the formula I-c

wherein

each b=0 or 1;

the molar ratio of r:s:t=(99.9-2):(0-98):(0-30), wherein r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, t is the number of crosslinked repeat units, s+t is at least 1;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-c, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones; and

the total number of units (r+s+t) is 5,000 or greater.

5 . The poly(lactone) of claim 1 having the formula I-d

wherein

each b=0 or 1;

the molar ratio of the total of each of r:s:t=(99.9-2):(0-98):(0-30), wherein

r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, t is the number of crosslinked repeat units, and s+t=at least 1, and

each value of r, s, and t are independent of any other value of r, s, and t;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone) I-d and at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,

G is a single bond or a C 1-30 hydrocarbyl group;

when t>0, c=0-5 and d=0-5 provided that c+d=1-5; and

the total number of units (r+s+t) is 5,000 or greater.

6 . The poly(lactone) of claim 1 having the formula I-e

wherein

each b=0 or 1;

the molar ratio of the total of each r:t=(99.99-70):(0.01-30), wherein each value of r and t are independent of any other value of r and t and;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,

G is a single bond or a C 1-30 hydrocarbyl group;

c=1-5 and d=0-4, provided that c+d=1-5.

7 . The poly(lactone) of claim 1 having the formula I-f

wherein

each b=0 or 1;

the molar ratio of the total of each of w:r:s:t=(0.01-30):(99.99-2):(0-98):(0-30), wherein

w is the mole fraction of post-reacted and post-crosslinked α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, and t is the number of crosslinked α-methylene lacto repeat units, and

each value of w, r, s, and t is independent of every other value of w, r s, and t;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-f, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;

Q′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-f; and

the total number of units (w+r+s+t) is 5,000 or greater.

8 . The poly(lactone) of claim 1 having the formula I-g

wherein

each b=0 or 1;

the molar ratio of the total of each of (w1+w2+w3+w4):r:s:t=(0.01-30):(99.99-2):(0-98):(0-30) wherein

(w1+w2+w3+w4) is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, wherein w1 is the number of post-crosslinked α-methylene lactone repeat units in a first polymer backbone and is at least 1, w2 is the number of post-reacted, uncrosslinked α-methylene lactone repeat units in the first polymer backbone, w3=1, and w4 is the number of α-methylene lactone repeat units in an additional polymer backbone post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones,

r is the number of α-methylene lactone repeat units,

s is the number of comonomer repeat units,

t is the number of crosslinked repeat units, and

each value of w1, w2, w4, r, s, and t are independent of any other value of w1, w2, w4, r, s, and t, and; and

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-g;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-g, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;

Q is a C 1-30 hydrocarbyl group, X is a nucleophile residue;

L is a leaving group;

f=1-5 and e=1-5 provided that e+1-5; and

the total number of units (w1+w2+w3+w4+r+s+t) is 100 or greater.

9 . The poly(lactone) of claim 1 having the formula I-h

wherein

each b=0 or 1;

the molar ratio of w:r:s=(0.01-30):(99.99-2):(0-97.99), wherein w is the mole fraction of post-reacted and post-crosslinked α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, and s is the number of comonomer repeat units;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-h, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-h;

the total number of units (w+r+s) is 100 or greater.

10 . The poly(lactone) of claim 1 having the formula I-i

wherein

each b=0 or 1;

the molar ratio of the total of each of (w1+w2+w3+w4):r:s:t=(0.01-30):(99.9-2):(0-98):(0-30) wherein

(w1+w2+w3+w4) is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, wherein w1 is the number of post-crosslinked α-methylene lactone repeat units in a first polymer backbone and is at least 1, w2 is the number of post-reacted, uncrosslinked α-methylene lactone repeat units in the first polymer backbone, w3=1, and w4 is the number of α-methylene lactone repeat units in an additional polymer backbone post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones,

r is the number of α-methylene lactone repeat units,

s is the number of comonomer repeat units, and

each value of w1, w2, w4, r, s, and t are independent of any other value of w1, w2, w4, r, s, and t;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-i, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones;

Q is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,

X is a nucleophile residue;

L is a leaving group;

f=1-5 and e=1-5 provided that e+1-5; and

the total number of units (w1+w2+w3+w4+r+s) is 100 or greater;

11 . The poly(lactone) of claim 1 having the formula I-j

wherein

each b=0 or 1;

the molar ratio of w:r=(0.01-30):(99.99-70), wherein w is the mole fraction of post-reacted and post-crosslinked α-methylene lactone repeat units and r is the number of α-methylene lactone repeat units;

X is a nucleophile residue;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group wherein at least one Q′ is crosslinked with one to five additional polymer backbones; and

the total number of units (w+r) is 100 or greater.

12 . The poly(lactone) of claim 1 having the formula I-k

wherein

each b=0 or 1;

the molar ratio of the total of each of (w1+w2+w3+w4):r=(0.01-30):(99.9-70) wherein

(w1+w2+w3+w4) is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, wherein w1 is the number of post-crosslinked α-methylene lactone repeat units in a first polymer backbone and is at least 1, w2 is the number of post-reacted, uncrosslinked α-methylene lactone repeat units in the first polymer backbone, w3=1, and w4 is the number of α-methylene lactone repeat units in an additional polymer backbone post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, and

r is the number of α-methylene lactone repeat units;

each value of w1, w2, w4, and r are independent of any other value of w1, w2, w4, r, s, and t;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones;

Q is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,

X is a nucleophile residue;

L is a leaving group;

f=1-5 and e=1-5 provided that e+1-5; and

the total number of units (w1+w2+w3+w4+r) is 100 or greater.

13 . The poly(lactone) of claim 1 having the formula I-m

wherein

each b=0 or 1;

the molar ratio of r:s=(99.99-2):(0.01-98);

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F and F is the same or different in each instance; and

r and s are integers effective to provide a polymer having a weight average molecular weight of at least 500,000 g/mol.

14 . The poly(lactone) of claim 1 having the formula I-n

wherein each b=0 or 1 and n is a number effective to provide a molecular weight of at least 500,000 g/mol.

15 . (canceled)

16 . The poly(lactone) of claim 1 , wherein the methyl group is located gamma to the carbonyl group.

17 . The poly(lactone) of claim 1 , wherein R 4 and R 5 are hydrogen, R 6 is methyl or hydrogen, and R 7 is carboxylic acid.

18 . The poly(lactone) of claim 1 , wherein c=1-4.

19 . (canceled)

20 . (canceled)

21 . The poly(lactone) of claim 1 , wherein G is a single bond or a C 1-12 alkyl substituted with 0-6 (C 1-6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-12 alkenyl substituted with 0-6 (C 1-6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-12 alkynyl substituted with 0-6 (C 1-6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 3-8 cycloalkyl substituted with 0-4 (C 1-6 )alkoxycarbonyl groups, 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 3-8 heterocycloalkyl substituted with 0-4 (C 1-6 )alkoxycarbonyl groups, 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 6-12 aryl substituted with 0-6 (C 1-6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 4-12 heteroaryl substituted with 0-4 (C 1-6 )alkoxycarbonyl groups, 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-24 (C 1-4 alkyloxy) e (C 1-4 alkyl)) groups wherein e=1-16 substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing.

22 . The poly(lactone) of claim 1 further comprising a crosslink between two F groups, wherein the crosslink is the crosslink residue of a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a diacid or higher acid, the C 1-3 alkyl esters thereof, or the acid halide thereof, a diepoxide or higher epoxide, an alcohol-amine, a compound having two or more ethylenic unsaturations, a polyvalent ion, or a combination comprising at least one of the forgoing crosslinkers.

23 . (canceled)

24 . A method of preparing a poly(lactone) of claim 1 , the method comprising

polymerizing an ethylenically unsaturated monomer of formula II,

wherein each b=0 or 1, optionally with

a crosslinking monomer of formula III, a comonomer of formula IV, or a combination comprising one or both of crosslinking monomer III and comonomer IV,

wherein

R 1 , R 2 , and R 3 are each independently hydrogen or C 1-4 alkyl;

G is a single bond or a C 1-30 hydrocarbyl group; and

y=1-5; and

R 4 , R 5 , R 6 and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone), and at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F, and F is the same or different in each instance, to form an optionally crosslinked polymer; and

optionally, crosslinking the optionally crosslinked polymer with a crosslinking agent, a post-crosslinking monomer of formula V, or a combination thereof

[LX]-Q-[XL] z   V

wherein

Q is a C 1-30 hydrocarbyl group;

X is a nucleophile reactive with a lactone group;

L is a leaving group; and

z=1-5.

25 . The method of claim 24 , wherein the crosslinking monomer III is an N,N′—(C 1-12 alkyl)bis(meth)acrylamide, a di-, tri-, tetra-, penta-, or hexa(meth)acrylic ester of a C 1-12 polyol, a di-, tri-, tetra-, penta- or hexa(meth)acrylic ester of a C 1-24 alkyleneoxide polyol, a mono-, di-, tri-, tetra-, or higher polyester of a mono- di-, tri-, tetra-, or higher carboxylic acid having 2-6 terminal unsaturations, a di-, tri-, tetra-, penta-, or hexa(meth)allyl(C 1-12 alkane), and di-, tri-, and tetravinyl substituted C 6-12 aryl compounds.

26 . The method claim 24 , wherein the crosslinking monomer III is an N,N′-methylenebis(meth)acrylamide, 1,2-, 1,3-, and 1,4-butanediol di(meth)acrylate, ethyleneglycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, polyethyleneoxide glycol di(meth)acrylate, dipropyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, 1,2- and 1,3-propanediol di(meth)acrylate, 1,2-, 1,3-, 1,4, 1,5- and 1,6-hexanediol di(meth)acrylate, 1,2- and 1,3-cyclohexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, triallyl isocyanurate, allyl(meth)acrylate, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diallyl ether, tetrallyloxyethane, tetrallyloxypropane, tetrallyloxybutane, divinylbenzene, divinyltoluene, divinyl xylene, trivinyl benzene, and divinyl ether.

27 . The method of claim 24 , wherein the comonomer IV is acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, maleic anhydride, maleimide, itaconic anhydride, styrene, n-butyl acrylate, N,N-dimethyl acrylamide, octadecyl acrylate, p-styrene sulfonate, butadiene, 2-vinylpyridine, 4-vinyl benzoic acid, N-vinyl pyrrolidone, methacrylic acid, divinyl benzene, butadiene, or a combination comprising at least one of the foregoing.

28 . The method of claim 24 , wherein the crosslinking agent is a compound having two or more ethylenic unsaturations, a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a dicarboxylic acid or higher carboxylic acid, the C 1-3 alkyl esters thereof, or the acid halide thereof, a polyvalent ion, an alcohol-amine, or a combination comprising at least one of the forgoing crosslinking agents.

29 . The method of claim 24 , wherein the post-crosslinking monomer of formula V is a diol, triol, tetrol, pentol, or hexol; a diamine, triamine, tetramine, pentamines, or hexamine, or a combination comprising at least one of the forgoing the post-crosslinking monomers.

30 . A coating composition comprising

a polymer binder;

an aqueous phase; and

the poly(lactone) of claim 1 .

31 . A method of preparing the coating composition of claim 30 , comprising:

combining the polymer binder, the poly(lactone) of claim 1 , and an aqueous phase.

32 . A coated substrate, comprising:

a substrate having a surface; and

a coating disposed on the surface, wherein the coating comprises

a polymer binder;

optionally a pigment or a dye; and

the poly(lactone) of claim 1 .

33 . (canceled)

34 . A method of coating a substrate, comprising:

contacting a coating composition comprising

a polymer binder,

an aqueous phase,

optionally a pigment or a dye; and

the poly(lactone) of claim 1 with a surface of the substrate to form a coating; and

drying the coating.

35 . A poly(lactone) comprising units of formula I

wherein

each b=0 or 1;

the molar ratio of w:r:s:t=(0-30):(99.9-2):(0-98):(0-30), wherein

w is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, t is the number of crosslinked repeat units, and

w+s+t is at least 1;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group wherein Q′ is covalently bonded to at least a second polymer backbones, wherein the second polymer backbone comprises units of formula I;

X is N, 0, P or S

G′ is a single bond to an additional polymer backbone or G is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I;

when w>0, the ratio of (w+r):t is greater than 100:1;

when w=0 and t>0, the ratio of r:t is greater than 5000:1;

when w=0 and t=0, the total of (r+s) is effective to provide a weight average molecular weight of 500,000 g/mol or greater.

36 . The poly(lactone) of claim 35 having the formula I-a

wherein

each b=0 or 1;

the molar ratio of the total of each of w:r:s:t=(0-30):(99.9-2):(0-98):(0.01-30), wherein w is the number of post-reacted α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, t is the number of crosslinked α-methylene lactone repeat units, provided that t is at least 1;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-a, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-a;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-a;

when w>0, the ratio of (w+r):t is greater than 100:1 when w=0 and t>0, the ratio of r:t is greater than 5000:1.

37 . The poly(lactone) of claim 35 having the formula I-b

wherein

each b=0 or 1;

the molar ratio of the total of each of w:r:s:t=(0-30):(99.9-2):(0-98):(0.01-30), wherein

w is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, and t is the number of crosslinked α-methylene lactone repeat units, and

each value of w, r, s, and t are independent of any other value of w, r, s, and t;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone) I-b and at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones;

G′ is a single bond to an additional polymer backbone or G is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;

G is a single bond or a C 1-30 hydrocarbyl group;

c=1-5 and d=0-5 provided that c+d=1-5, and

when w>0, the ratio of (w+r):t is greater than 100:1

when w=0 and t>0, the ratio of r:t is greater than 5000:1.

38 . The poly(lactone) of claim 35 having the formula I-c

wherein

each b=0 or 1;

the molar ratio of r:s:t=(99.9-2):(0-98):(0-30), wherein r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, t is the number of crosslinked repeat units, s+t is at least 1;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-c, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,

when t>0, the ratio of r:t is greater than 5000:1; and

when t=0, the total of (r+s) is effective to provide a weight average molecular weight of 500,000 g/mol or greater.

39 . The poly(lactone) of claim 35 having the formula I-d

wherein

each b=0 or 1;

the molar ratio of the total of each of r:s:t=(99.9-2):(0-98):(0-30), wherein

r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, t is the number of crosslinked repeat units, and s+t=at least 1, and

each value of r, s, and t are independent of any other value of r, s, and t;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone) I-d and at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

G is a single bond or a C 1-30 hydrocarbyl group;

when t>0,

c=0-5 and d=0-5 provided that c+d=1-5, and

the ratio of r:t is greater than 5000:1; and

when t=0, the total of (r+s) is effective to provide a weight average molecular weight of 500,000 g/mol or greater.

40 . The poly(lactone) of claim 35 having the formula I-e

wherein

each b=0 or 1;

the molar ratio of the total of each r:t=(99.99-70):(0.01-30), wherein each value of r and t are independent of any other value of r and t and;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

G is a single bond or a C 1-30 hydrocarbyl group;

c=1-5 and d=0-4, provided that c+d=1-5

when t>0,

c=0-5 and d=0-5 provided that c+d=1-5, and

the ratio of r:t is greater than 5000:1; and

when t=0, the total of (r+s) is effective to provide a weight average molecular weight of 500,000 g/mol or greater.

41 . The poly(lactone) of claim 35 having the formula I-f

wherein

each b=0 or 1;

the molar ratio of the total of each of w:r:s:t=(0.01-30):(99.99-2):(0-98):(0-30), wherein

w is the mole fraction of post-reacted and post-crosslinked α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, s is the number of comonomer repeat units, and t is the number of crosslinked α-methylene lacto repeat units, and

each value of w, r, s, and t is independent of every other value of w, r s, and t;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-f, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

G′ is a single bond to an additional polymer backbone or G is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;

Q′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-f;

when t>0, the ratio of (w+r):t is greater than 100:1; and

when t=0, the total of (w1+w2+w3+w4+r+s) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking.

42 . The poly(lactone) of claim 1 having the formula I-g

wherein

each b=0 or 1;

the molar ratio of the total of each of (w1+w2+w3+w4):r:s:t=(0.01-30):(99.99-2):(0-98):(0-30) wherein

(w1+w2+w3+w4) is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, wherein w1 is the number of post-crosslinked α-methylene lactone repeat units in a first polymer backbone and is at least 1, w2 is the number of post-reacted, uncrosslinked α-methylene lactone repeat units in the first polymer backbone, w3=1, and w4 is the number of α-methylene lactone repeat units in an additional polymer backbone post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones,

r is the number of α-methylene lactone repeat units,

s is the number of comonomer repeat units,

t is the number of crosslinked repeat units, and

each value of w1, w2, w4, r, s, and t are independent of any other value of w1, w2, w4, r, s, and t, and; and

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-g;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-g, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

G′ is a single bond to an additional polymer backbone or G′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones;

Q is a C 1-30 hydrocarbyl group, X is a nucleophile residue;

L is a leaving group;

f=1-5 and e=1-5 provided that e+1-5;

when t>0, the ratio of (w1+w2+w3+w4+r):t is greater than 100:1; and

when t=0, the total of (w1+w2+w3+w4+r+s) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking.

43 . The poly(lactone) of claim 35 having the formula I-h

wherein

each b=0 or 1;

the molar ratio of w:r:s=(0.01-30):(99.99-2):(0-97.99), wherein w is the mole fraction of post-reacted and post-crosslinked α-methylene lactone repeat units, r is the number of α-methylene lactone repeat units, and s is the number of comonomer repeat units;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-h, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones, wherein the additional polymer backbone comprises units of formula I-h;

when w>0, the total of (w+r+s) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking.

44 . The poly(lactone) of claim 35 having the formula I-i

wherein

each b=0 or 1;

the molar ratio of the total of each of (w1+w2+w3+w4):r:s:t=(0.01-30):(99.9-2):(0-98):(0-30) wherein

(w1+w2+w3+w4) is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, wherein w1 is the number of post-crosslinked α-methylene lactone repeat units in a first polymer backbone and is at least 1, w2 is the number of post-reacted, uncrosslinked α-methylene lactone repeat units in the first polymer backbone, w3=1, and w4 is the number of α-methylene lactone repeat units in an additional polymer backbone post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones,

r is the number of α-methylene lactone repeat units,

s is the number of comonomer repeat units, and

each value of w1, w2, w4, r, s, and t are independent of any other value of w1, w2, w4, r, s, and t;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl, or F, wherein F is a functional group that imparts a property to the poly(lactone) I-i, at least one and no more than two of R 4 , R 5 , R 6 , and R 7 are F, and F is the same or different in each instance;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones;

Q is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,

X is a nucleophile residue;

L is a leaving group;

f=1-5 and e=1-5 provided that e+1-5; and

the total of (w1+w2+w3+w4+r+s) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking;

45 . The poly(lactone) of claim 35 having the formula I-j

wherein

each b=0 or 1;

the molar ratio of w:r=(0.01-30):(99.99-70), wherein w is the mole fraction of post-reacted and post-crosslinked α-methylene lactone repeat units and r is the number of α-methylene lactone repeat units;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group wherein at least one Q′ is crosslinked with one to five additional polymer backbones; and

the total of (w+r) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking.

46 . The poly(lactone) of claim 35 having the formula I-k

wherein

each b=0 or 1;

the molar ratio of the total of each of (w1+w2+w3+w4):r=(0.01-30):(99.9-70) wherein

(w1+w2+w3+w4) is the number of post-reacted and post-crosslinked α-methylene lactone repeat units, wherein w1 is the number of post-crosslinked α-methylene lactone repeat units in a first polymer backbone and is at least 1, w2 is the number of post-reacted, uncrosslinked α-methylene lactone repeat units in the first polymer backbone, w3=1, and w4 is the number of α-methylene lactone repeat units in an additional polymer backbone post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones, and

r is the number of α-methylene lactone repeat units;

each value of w1, w2, w4, and r are independent of any other value of w1, w2, w4, r, s, and t;

Q′ is a C 1-30 hydrocarbyl group post-reacted with a crosslinking group and optionally crosslinked with one to five additional polymer backbones;

Q is a C 1-30 hydrocarbyl group crosslinked with one to five additional polymer backbones,

X is a nucleophile residue;

L is a leaving group;

f=1-5 and e=1-5 provided that e+1-5; and

the total of (w1+w2+w3+w4+r) is effective to provide a weight average molecular weight of 10,000 g/mol or greater prior to cross-linking.

47 . The poly(lactone) of claim 35 , wherein the methyl group is located gamma to the carbonyl group.

48 . The poly(lactone) of claim 35 , wherein R 4 and R 5 are hydrogen, R 6 is methyl or hydrogen, and R 7 is carboxylic acid.

49 . The poly(lactone) of claim 35 , wherein c=1-4.

50 . (canceled)

51 . (canceled)

52 . The poly(lactone) of claim 35 , wherein G is a single bond or a C 1-12 alkyl substituted with 0-6 (C 1-6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-12 alkenyl substituted with 0-6 (C 1-6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-12 alkynyl substituted with 0-6 (C 1-6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 3-8 cycloalkyl substituted with 0-4 (C 1-6 )alkoxycarbonyl groups, 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 3-8 heterocycloalkyl substituted with 0-4 (C 1-6 )alkoxycarbonyl groups, 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 6-12 aryl substituted with 0-6 (C 1-6 )alkoxycarbonyl groups, 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 4-12 heteroaryl substituted with 0-4 (C 1-6 )alkoxycarbonyl groups, 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-24 (C 1-4 alkyloxy) e (C 1-4 alkyl)) groups wherein e=1-16 substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing.

53 . The poly(lactone) of claim 35 further comprising a crosslink between two F groups, wherein the wherein the crosslink is the crosslink residue of a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a diacid or higher acid, the C 1-3 alkyl esters thereof, or the acid halide thereof, a diepoxide or higher epoxide, an alcohol-amine, a compound having two or more ethylenic unsaturations, a polyvalent ion, or a combination comprising at least one of the forgoing crosslinkers.

54 . (canceled)

55 . A method of preparing a poly(lactone) of claim 35 , the method comprising

polymerizing an ethylenically unsaturated monomer of formula II,

wherein each b=0 or 1, optionally with

a crosslinking monomer of formula III, a comonomer of formula IV, or a combination comprising one or both of crosslinking monomer III and comonomer IV,

wherein

R 1 , R 2 , and R 3 are each independently hydrogen or C 1-4 alkyl;

G is a single bond or a C 1-30 hydrocarbyl group; and

y=1-5; and

R 4 , R 5 , R 6 and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the poly(lactone), and at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F, and F is the same or different in each instance, to form an optionally crosslinked polymer; and

optionally, crosslinking the optionally crosslinked polymer with a crosslinking agent, a post-crosslinking monomer of formula V, or a combination thereof

[LX]-Q-[XL] z   V

wherein

Q is a C 1-30 hydrocarbyl group;

X is a nucleophile reactive with a lactone group;

L is a leaving group; and

z=1-5.

56 . The method of claim 55 , wherein the crosslinking monomer III is an N,N′—(C 1-12 alkyl)bis(meth)acrylamide, a di-, tri-, tetra-, penta-, or hexa(meth)acrylic ester of a C 1-12 polyol, a di-, tri-, tetra-, penta- or hexa(meth)acrylic ester of a C 1-24 alkyleneoxide polyol, a mono-, di-, tri-, tetra-, or higher polyester of a mono- di-, tri-, tetra-, or higher carboxylic acid having 2-6 terminal unsaturations, a di-, tri-, tetra-, penta-, or hexa(meth)allyl(C 1-12 alkane), and di-, tri-, and tetravinyl substituted C 6-12 aryl compounds.

57 . The method claim 55 , wherein the crosslinking monomer III is an N,N′-methylenebis(meth)acrylamide, 1,2-, 1,3-, and 1,4-butanediol di(meth)acrylate, ethyleneglycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, polyethyleneoxide glycol di(meth)acrylate, dipropyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, 1,2- and 1,3-propanediol di(meth)acrylate, 1,2-, 1,3-, 1,4, 1,5- and 1,6-hexanediol di(meth)acrylate, 1,2- and 1,3-cyclohexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, triallyl isocyanurate, allyl(meth)acrylate, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, diallyl ether, tetrallyloxyethane, tetrallyloxypropane, tetrallyloxybutane, divinylbenzene, divinyltoluene, divinyl xylene, trivinyl benzene, and divinyl ether.

58 . The method of claim 55 , wherein the comonomer IV is acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, maleic anhydride, maleimide, itaconic anhydride, styrene, n-butyl acrylate, N,N-dimethyl acrylamide, octadecyl acrylate, p-styrene sulfonate, butadiene, 2-vinylpyridine, 4-vinyl benzoic acid, N-vinyl pyrrolidone, methacrylic acid, divinyl benzene, butadiene, or a combination comprising at least one of the foregoing.

59 . The method of claim 55 , wherein the crosslinking agent is a compound having two or more ethylenic unsaturations, a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a dicarboxylic acid or higher carboxylic acid, the C 1-3 alkyl esters thereof, or the acid halide thereof, a polyvalent ion, an alcohol-amine, or a combination comprising at least one of the forgoing crosslinking agents.

60 . The method of claim 55 , wherein the post-crosslinking monomer of formula V is a diol, triol, tetrol, pentol, or hexol; a diamine, triamine, tetramine, pentamines, or hexamine, or a combination comprising at least one of the forgoing the post-crosslinking monomers.

61 . A coating composition comprising

a polymer binder;

an aqueous phase; and

the poly(lactone) of claim 35 .

62 . A method of preparing the coating composition of claim 61 , comprising:

combining the polymer binder, the poly(lactone) of claim 35 , and an aqueous phase.

63 . A coated substrate, comprising:

a substrate having a surface; and

a coating disposed on the surface, wherein the coating comprises

a polymer binder;

optionally a pigment or a dye; and

the poly(lactone) of claim 35 .

64 . (canceled)

65 . A method of coating a substrate, comprising:

contacting a coating composition comprising

a polymer binder,

an aqueous phase,

optionally a pigment or a dye; and

the poly(lactone) of claim 35 with a surface of the substrate to form a coating; and

drying the coating.