MODIFIED FIBER-BASED MATERIALS AND METHODS OF MAKING THE SAME

1 . A fiber-based composite comprising:

a network comprising a multiplicity of fibers; and

a coating on the multiplicity of fibers, wherein the coating comprises:

one or more compounds of Formula IA; and

one or more compounds of Formula IIA,

wherein a ratio of a total weight of the one or more compounds of Formula IA to a total weight of the one or more compounds of Formula IIA is in a range of 1:1 to 99:1,

Formula IA is:

or a salt thereof when R is C 1 -C 6 alkyl optionally substituted with one or more of OH and C 1 -C 6 alkoxy,

wherein:

R is selected from the group consisting of H and C 1 -C 6 alkyl optionally substituted with one or more of OH and C 1 -C 6 alkoxy;

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of: H, OH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 1 -C 6 alkoxy;

each occurrence of R 10A , R 10B , R 11A , and R 11B is independently selected from the group consisting of: H, OH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 1 -C 6 alkoxy;

any two R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10A , R 10B , R 11A , and R 11B on adjacent carbon atoms can be taken together with the carbon atoms to which they are attached to form a double bond, a 3- to 6-membered ring heterocycle, or a C 3 -C 6 cycloalkyl;

o is an integer from 0 to 17;

p is an integer from 0 to 17; and

the sum of o and p is from 0 to 17, and

Formula IIA is:

wherein:

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of: H, OH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 1 -C 6 alkoxy; and

each occurrence of R 10A , R 10B , R 11A , and R 11B is independently selected from the group consisting of: H, OH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 1 -C 6 alkoxy;

any two R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10A , R 10B , R 11A , and R 11B on adjacent carbon atoms can be taken together with the carbon atoms to which they are attached to form a double bond, a 3- to 6-membered ring heterocycle, or a C 3 -C 6 cycloalkyl;

o is an integer from 0 to 17;

p is an integer from 0 to 17;

the sum of o and p is from 0 to 17;

X n+ is a cationic moiety having formal charge n; and

wherein a surface of the fiber-based composite is hydrophobic and lipophobic.

2 . The composite of claim 1 , wherein the ratio is in a range of 2:1 to 20:1 or 5:1 to 10:1.

3 . The composite of claim 1 , wherein:

a carbon chain length of at least one of the compounds of Formula IA is in a range of C12 to C30,

a carbon chain length of at least one of the compounds of Formula IIA is in a range of C12 to C30, or

a carbon chain length of at least one of the compounds of Formula IA is in a range of C12 to C30 and a carbon chain length of at least one of the compounds of Formula IIA is in a range of C12 to C30.

4 . The composite of claim 1 , wherein:

a carbon chain length of at least one of the compounds of Formula IA is in a range of C16 to C24,

a carbon chain length of at least one of the compounds of Formula IIA is in a range of C16 to C24, or

a carbon chain length of at least one of the compounds of Formula IA is in a range of C16 to C24 and a carbon chain length of at least one of the compounds of Formula IIA is in a range of C16 to C24.

5 . The composite of claim 1 , wherein the network defines pores, and some of the pores are at least partially filled with the coating.

6 . The composite of claim 1 , wherein the coating comprises a polymerization product of one or more compounds of Formula IA-B, wherein Formula IA-B is Formula IA when R is hydrogen.

7 . The composite of claim 6 , wherein:

at least one of the one or more compounds of Formula IA-B has a chain length of C16 or C18,

at least one of the one or more compounds of Formula IA-B has 0, 1, 2, or 3 hydroxyl groups, or

at least one of the one or more compounds of Formula IA-B has a chain length of C16 or C18 and at least one of the one or more compounds of Formula IA-B has 0, 1, 2, or 3 hydroxyl groups.

8 . The composite of claim 6 , wherein:

the one or more compounds of Formula IA-B comprise two or more compounds of Formula IA-B, and the two or more compounds of Formula IA-B comprise at least:

a first compound of Formula IA-B and a second compound of Formula IA-B;

a first compound of Formula IA-B and a third compound of Formula IA-B; or

a second compound of Formula IA-B and a third compound of Formula IA-B,

wherein:

the first compound of Formula IA-B is an omega hydroxy compound, wherein at least one of R 1 , R 2 , R 3 , R 4 , and R 5 or at least one occurrence of R 10A , R 10B , R 11A , and R 11B is a hydroxyl group,

the second compound of Formula IA-B is a mid-chain hydroxy compound, wherein at least one of R 4 , R 5 , R 6 , and R 7 or at least one occurrence of R 10A , R 10B , R 11A , and R 11B is a hydroxyl group, and

the third compound of Formula IA-B is a dihydroxy compound, wherein two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 or at least one occurrence of R 10A , R 10B , R 11A , and R 11B are hydroxyl groups.

9 . The composite of claim 1 , wherein the coating is hydrophobic and lipophobic.

10 . The composite of claim 9 , wherein:

a contact angle of water on the surface in air at 25° C. is at least 50°, and

a contact angle of an oil on the surface in air at 25° C. is at least 50°.

11 . The composite of claim 1 , wherein the surface is a first exterior surface, and a second exterior surface opposite the first exterior surface is hydrophilic, lipophilic, or both.

12 . The composite of claim 1 , wherein the multiplicity of fibers comprises one or more cellulose-containing materials.

13 . An article comprising the fiber-based composite of claim 1 .

14 . The article of claim 13 , wherein a surface of the article is hydrophobic and lipophobic.

15 . The article of claim 13 , wherein the fiber-based article is a package, a dish, or a container.

16 . A method of making the fiber-based composite of claim 1 , the method comprising:

contacting the network comprising the multiplicity of fibers with a liquid composition, wherein the liquid composition comprises:

the one or more compounds of Formula IA; and

the one or more compounds of Formula IIA; and

drying the liquid composition to yield the fiber-based composite.

17 . A method of making a fiber-based composite, the method comprising:

combining a multiplicity of fibers and a liquid to yield a slurry;

combining one or more compounds of Formula IA with the slurry;

removing some of the liquid from the slurry to yield a fibrous mass; and

drying the fibrous mass, wherein drying the fibrous mass comprises polymerizing the one or more compounds of Formula IA, thereby forming a polymer in contact with the multiplicity of fibers to yield the fiber-based composite,

wherein a surface of the fiber-based composite is hydrophobic and lipophobic, and

Formula IA is:

or a salt thereof when R is C 1 -C 6 alkyl optionally substituted with one or more of OH and C 1 -C 6 alkoxy,

wherein:

R is selected from the group consisting of H and C 1 -C 6 alkyl optionally substituted with one or more of OH and C 1 -C 6 alkoxy;

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of: H, OH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 1 -C 6 alkoxy;

each occurrence of R 10A , R 10B , R 11A , and R 11B is independently selected from the group consisting of: H, OH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 1 -C 6 alkoxy;

any two R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10A , R 10B , R 11A , and R 11B on adjacent carbon atoms can be taken together with the carbon atoms to which they are attached to form a double bond, a 3- to 6-membered ring heterocycle, or a C 3 -C 6 cycloalkyl;

o is an integer from 0 to 17;

p is an integer from 0 to 17; and

the sum of o and p is from 0 to 17.

18 . The method of claim 17 , further comprising disposing a liquid comprising one or more compounds of Formula IA and one or more compounds of Formula IIA on the surface of the fiber-based composite to form a coating on the fiber-based composite, wherein Formula IIA is:

wherein:

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are independently selected from the group consisting of: H, OH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 1 -C 6 alkoxy; and

each occurrence of R 10A , R 10B , R 11A , and R 11B is independently selected from the group consisting of: H, OH, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 1 -C 6 alkoxy;

any two R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10A , R 10B , R 11A , and R 11B on adjacent carbon atoms can be taken together with the carbon atoms to which they are attached to form a double bond, a 3- to 6-membered ring heterocycle, or a C 3 -C 6 cycloalkyl;

o is an integer from 0 to 17;

p is an integer from 0 to 17;

the sum of o and p is from 0 to 17; and

X n+ is a cationic moiety having formal charge n.

19 . The method of claim 18 , wherein the fiber-based composite defines pores, and some of the pores are at least partially filled with the coating.

20 . The method of claim 17 , wherein drying the fibrous mass comprises forming a fiber-based article comprising the fiber-based composite.

21 . The method of claim 17 , wherein drying the fibrous mass comprises heating the fibrous mass to a temperature greater than 140° C.

22 . The method of claim 18 , wherein forming the coating comprises removing at least a portion of the solvent by heating to a temperature at least 10° C. less or at least 20° C. less than a melting point or glass transition temperature of at least one of the one or more compounds of Formula IA.

23 . The method of claim 18 , wherein forming the coating comprises removing at least a portion of the solvent by heating the fibrous mass to a temperature in a range of 50° C. to 100° C.

24 . The method of claim 17 , wherein drying the fibrous mass comprises thermoforming the fibrous mass.

25 . The method of claim 17 , wherein the fiber-based composite defines pores, and some of the pores are at least partially filled with a polymerization product of one or more compounds of Formula IA-B, wherein Formula IA-B is Formula IA when R is hydrogen.

26 . The method of claim 17 , wherein the multiplicity of fibers comprises one or more cellulose-containing materials.

27 . A fiber-based composite formed by the method of claim 17 .

28 . An article comprising the fiber-based composite of claim 27 .

29 . The article of claim 28 , wherein a surface of the article is hydrophobic and lipophobic.

30 . The article of claim 28 , wherein the fiber-based article is a package, a dish, or a container.