Salt sensitive aqueous emulsions

• US 6,683,129 B1
• Filed: 03/31/2000
• Issued: 01/27/2004
• Est. Priority Date: 03/31/2000
• Status: Expired due to Fees

• Current Assignee: Celanese International Corporation (Celanese Corporation)
• Original Assignee: National Starch and Chemical Investment Holding Corporation (Ingredion Incorporated)
• Inventors: Eknoian, Michael W.
• Primary Examiner(s): REDDICK, MARIE L
• Application Number:
  US09/540,033
• Time in Patent Office: 1,397 Days
• Field of Search: 524/547, 524/548, 524/555, 524/556, 524/558, 524/559, 524/808, 524/812, 524/814, 524/815, 524/816, 524/817, 524/819, 524/820, 524/823, 524/824, 524/832, 524/833, 524/549
• US Class Current: 524/547
• CPC Class Codes: C08F 2/24 with the aid of emulsifying agents
• CPC Class Codes: C08F 218/08 Vinyl acetate
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08F 220/1809 C9-(meth)acrylate
• CPC Class Codes: C08F 222/06 Maleic anhydride

Abstract

This invention relates to aqueous emulsions comprising a water-dispersible copolymer which is non-dispersible in aqueous solutions containing 0.5% or more of an inorganic salt, comprising acidic ethylenically unsaturated monomers and ethylenically unsaturated monomers. The acidic ethylenically unsaturated monomers and the ethylenically unsaturated monomers are defined herein. The present invention also pertains to emulsion polymerization methods for making the aqueous emulsions with or without a surfactant.

Claims

1. An aqueous emulsion comprising a water-dispersible copolymer characterized in that films formed from said water-dispersible copolymer are dispersible in water, yet non-dispersible in aqueous solutions containing 0.5% by weight or more of an inorganic salt, and wherein the water-dispersible copolymer comprises in percentages by weight:

(A) from about 25% to about 80% of acidic ethylenically unsaturated monomer units, with the proviso that the acidic ethylenically unsaturated monomer units are not acrylic acid;

(B) from about 10% to about 80% of ethylenically unsaturated monomer units selected from the group of monomer formulas consisting of;

(i) CH₂═

C(R₁)COR₂;

(i) R₃OOC—

CH═

CH—

COOR₄;

(iii) CH₂═

C(R₅)OCOR₆;

(iv) CH₂═

C(COOR₇)CH₂COOR₈;

(v) CH₃CH═

CHCOOR₉;

(vi) R₁₀C₆H₄CR₁₁═

CHR₁₁; and

(vii) R₁₂CH═

CHR₁₃;

 

wherein R₁ is hydrogen or methyl and R₂ is —

OZ′

or —

N(Z″

)(Z″

), wherein Z′

is an alkyl group having from 1 to 7 carbon atoms, and Z″

is independently selected from the group consisting of hydrogen and alkyl groups having from 1 to 6 carbon atoms;

R₃ and R₄ are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R₃ and R₄ are not both hydrogen;

R₅ is hydrogen or methyl and R₆ is an alkyl group having from 1 to 7 carbon atoms;

R₇ and R₈ are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R₇ and R₈ are not both hydrogen;

R₉ is an alkyl group having from 1 to 7 carbon atoms;

R₁₀ and R₁₁ are hydrogen; and

R₁₂ and R₁₃ are independently selected from the group consisting of hydrogen, —

CN, —

NHCHO, and an all group having from 1 to 7 carbon atoms; and

(C) from about 10% to about 80% of ethylenically unsaturated monomer units selected from the group of monomer formulas consisting of;

(i) CH₂═

C(R′

₁)COR′

₂;

(ii) R′

₃OOC—

CH═

CH—

COOR′

₄;

(iii) CH₂═

C(R′

₅)OCOR′

₆;

(iv) CH₂═

C(COOR′

₇)CH₂COOR′

₈;

(v) CH₃CH═

CHCOOR′

₉;

(vi) R′

₁₀C₆H₄CR′

₁₁═

CHR′

₁₁; and

(vii) R′

₁₂CH═

CHR′

₁₃;

 

wherein R′

₁ is hydrogen or methyl, and R′

₂ is selected from the group consisting of —

OZ′

, —

N(Z″

)(Z″

), and —

OZ′

″

OH, wherein Z′

is an alkyl group having from 8 to 18 carbon atoms;

Z″

is independently selected from the group consisting of alkyl groups having from 7 to 10 carbon atoms, dimethylamino alkyl groups having from 1 to 5 carbon atoms, and hydroxyalkyl groups having from 1 to 5 carbon atoms; and

Z′

″

is an alkyl group having from 1 to 4 carbon atoms;

R′

₃ and R′

₄ are independently an alkyl group having from 8 to 18 carbon atoms;

R′

₅ is hydrogen or methyl and R′

₆ is an alkyl group having from 8 to 18 carbon atoms;

R′

₇ and R′

₈ are independently an alkyl group having from 8 to 18 carbon atoms;

R′

₉ is an alkyl group having from 8 to 18 carbon atoms;

R′

₁₀ and R′

₁₁ are independently an alkyl group having from 1 to 2 carbon atoms;

R′

₁₂ and R′

₁₃ are independently selected from the group consisting of 2-pyrrolidinone, N-caprolactam, and an alkyl group having from 7 to 18 carbon atoms, with the proviso that R₁₂ and R₁₃ are not both 2-pyrrolidinone, are not both N-caprolactam, or are not a mixture thereof; and

the copolymer has a weight average molecular weight greater than about 25,000 and is present in an amount from about 20% to about 70% by weight, based on the aqueous emulsion.

2. The aqueous emulsion according to claim 1, wherein the acidic ethylenically unsaturated monomer from (A) contains a carboxylic acid group and is selected from the group consisting of methacrylic acid, maleic acid, maleic acid half esters, maleic anhydride, itaconic acid, and crotonic acid.

3. The aqueous emulsion according to claim 1, wherein the acidic ethylenically unsaturated monomer from (A) contains a sulfonic acid group and is selected from the group consisting of styrene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid.

4. The aqueous emulsion according to claim 1, wherein the acidic ethylenically unsaturated monomer from (A) contains a phosphoric acid group and is selected from the group consisting of styrene phosphoric acid, and CH₂═

C(CH₃)COO(CH₂)_nOPO₃H, wherein n is from 2 to 4.

5. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (B) is (i) CH₂═

C(R₁)COR₂, wherein R₁ is methyl and R₂ is —

OZ′

₁ wherein Z′

is an alkyl group having from 1 to 4 carbon atoms.

6. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (B) is (ii) R₃OOC—

CH═

CH—

COOR₄, wherein R₃ and R₄ are independently an alkyl group having from 2 to 4 carbon atoms.

7. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (B) is (iii) CH₂═

C(R₅)OCOR₆, wherein R₅ is methyl and R₆ is an alkyl group having from 1 to 4 carbon atoms.

8. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (B) is (iv) CH₂═

C(COOR₇)CH₂COOR₆, wherein R₇ and R₈ are independently an alkyl group having from 2 to 4 carbon atoms.

10. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (B) is (vi) R₁₀C₈H₄CR₁₁═

CHR₁₁, wherein R₁₀ and R₁₁ are hydrogen.

11. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (B) is (vii) R₁₂CH═

CHR₁₃, wherein R₁₂ and R₁₃ are independently hydrogen or methyl.

12. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (C) is (i) CH₂═

C(R′

₁)COR′

₂, wherein R′

₁ is methyl, R′

₂ is selected from the group consisting of —

OZ′

, —

N(Z″

)(Z″

), and —

OZ′

″

OH, wherein Z′

is an alkyl group having from 8 to 12 carbon atoms;

Z″

is independently selected from the group consisting of alkyl groups having from 8 to 10 carbon atoms, dimethylamino alkyl groups having from 1 to 3 carbon atoms, and hydroxyalkyl groups having from 1 to 3 carbon atoms; and

Z′

″

is an alkyl group having from 1 to 2 carbon atoms.

13. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (C) is (ii) R′

₃OOC—

CH═

CHCOOR′

₄, wherein R′

₃ and R′

₄ are independently an alkyl group having from 8 to 12 carbon atoms.

14. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (C) is (iii) CH₂═

C(R′

₅)OCOR′

₆, wherein R′

₅ is methyl, and R′

₆ is an alkyl group having from 8 to 12 carbon atoms.

15. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (C) is (iv) CH₂═

C(COOR′

₇)CH₂COOR′

₆, wherein R′

₇ and R′

₅ are independently an alkyl group having from 8 to 12 carbon atoms.

16. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (C) is (v) CH₃CH═

CHCOOR′

₉, and R′

₉ is an alkyl group having from 8 to 12 carbon atoms.

17. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (C) is (vi) R′

₁₀C₆H₄CR′

₁₁═

CHR′

₁₁, and R′

₁₀ and R′

₁₁, are independently an alkyl group having 1 carbon atom.

18. The aqueous emulsion according to claim 1, wherein the ethylenically unsaturated monomer from (C) is (vii) R′

₁₂CH═

CHR′

₁₃, wherein R′

₁₂ and R′

₁₃ are independently selected from the group consisting of 2-pyrrolidinone, N-caprolactam, and an alkyl group having from 7 to 12 carbon atoms.

9. The aqueous emulsion according to claim wherein the ethylenically unsaturated monomer from (B) is (v) CH₃CH═

CHCOOR₉, wherein R₉ is an alkyl group having from 2 to 4 carbon atoms.

19. A method for preparing an aqueous emulsion comprising a water-dispersible copolymer characterized in that films formed from said water-dispersible copolymer are dispersible in water, yet non-dispersible in aqueous solutions containing 0.5% by weight or more of an inorganic salt, comprising the steps of:

(a) providing the following monomers in percentages by weight;

(A) from about 40% 25% to about 80% of acidic ethylenically unsaturated monomers;

(B) from about 10% to about 80% of ethylenically unsaturated monomer u selected from the group of monomer formulas consisting of;

(i) CH₂═

C(R₁)COR₂;

(ii) R₃OOC—

CH═

CH—

COOR₄,

(iii) CH₂═

C(R₅)OCOR₆;

(iv) CH₂═

C(COOR₇)CH₂COOR₈;

(v) CH₃CH═

CHCOOR₉;

(vi) R₁₀C₆H₄CR₁₁═

CHR₁₁; and

(vii) R₁₂CH═

CHR₁₃;

 

wherein R₁ is hydrogen or methyl and R₂ is —

OZ′

or —

N(Z″

)(Z″

), wherein Z′

is an alkyl group having from 1 to 7 carbon atoms, and Z″

is independently selected from the group consisting of hydrogen and alkyl groups having from 1 to 6 carbon atoms;

R₃ and R₄ are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R₃ and R₄ are not both hydrogen;

R₅ is hydrogen or methyl and R₆ is an alkyl group having from 1 to 7 carbon atoms;

R₇ and R₈ are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R₇ and R₈ are not both hydrogen;

R₉ is an alkyl group having from 1 to 7 carbon atoms;

R₁₀ and R₁₁ are hydrogen; and

R₁₂ and R₁₃ are independently selected from the group consisting of hydrogen, —

CN, —

NHCHO, and an alkyl group having from 1 to 7 carbon atoms; and

(C) from about 10% to about 80% of ethylenically unsaturated monomer selected from the group of monomer formulas consisting of;

(i) CH₂═

C(R′

₁)COR′

₂;

(ii) R′

₃OOC—

CH═

CH—

COOR′

₄;

(iii) CH₂═

C(R′

₅)OCOR′

₆;

(iv) CH₂═

C(COOR′

₇)CH₂COOR′

₈;

(v) CH₃CH═

CHCOOR′

₉;

(vi) R′

₁₀C₆H₄CR′

₁₁═

CHR′

₁₁; and

(vii) R′

₁₂CH═

CHR′

₁₃;

 

wherein R′

₁ is hydrogen or methyl, and R′

₂ is selected from the group consisting of —

OZ′

, —

N(Z″

)(Z″

), and —

OZ′

″

OH, wherein Z′

is an alkyl group having from 8 to 18 carbon atoms;

Z″

is independently selected from the group consisting of alkyl groups having from 7 to 10 carbon atoms, dimethylamino alkyl groups having from 1 to 5 carbon atoms, and hydroxyalkyl groups having from 1 to 5 carbon atoms; and

Z′

″

is an alkyl group having from 1 to 4 carbon atoms;

R′

₃ and R′

₄ are independently an alkyl group having from 8 to 18 carbon atoms;

R′

₅ is hydrogen or methyl and R′

₆ is an alkyl group having from a to 18 carbon atoms;

R′

₇ and R′

₈ are independently an alkyl group having from 8 to 18 carbon atoms;

R′

₉ is an alkyl group having from 8 to 18 carbon atoms, R′

₁₀ and R′

₁₁ are independently an alkyl group having from 1 to 2 carbon atoms;

R′

₁₂ and R′

₁₃ are independently selected from the group consisting of 2-pyrrolidinone, N-caprolactam, and an alkyl group having from 7 to 18 carbon atoms, with the proviso that R₁₂ and R₁₃ are not both 2-pyrrolidinone, are not both N-caprolactam, or are not a mixture thereof, and

(b) emulsion polymerizing the monomers from (A), (B), and (C) in water at a solids level from about 20% to about 70% by weight, based on the aqueous emulsion, in the presence of a surfactant to form a copolymer having a weight average molecular weight greater than about 25,000.

20. The method according to claim 19, wherein the acidic ethylenically unsaturated monomer from (A) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic acid half esters, maleic anhydride, itaconic acid, crotonic acid, styrene sulfonic acid, 2-acylamido-2-methylpropane sulfonic acid, styrene phosphoric acid, and CH₂═

C(CH₃)COO(CH₂)_nOPO₃H, wherein n is from 2 to 4.

21. The method according to claim 19, wherein the ethylenically unsaturated monomer from (B) is selected from the group consisting of

(i) CH₂═ C(R₁)COR₂, wherein R₁ is methyl and R₂ is —

OZ′

₁, wherein Z′

is an alkyl group having from 1 to 4 carbon atoms;

(ii) R₃OOC—

CH═

CH—

COOR₄, wherein R₃ and R₄ are independently an alkyl group having from 1 to 4 carbon atoms;

(iii) CH₂═

C(R₅)OCOR₆, wherein R₅ is methyl and R₆ is an alkyl group having from 1 to 4 carbon atoms;

(iv) CH₂═

C(COOR₇)CH₂COOR₈, wherein R₇ and R₈ are independently an alkyl group having from 1 to 4 carbon atoms;

(v) CH₃CH═

CHCOOR₉, wherein R₉ is an alkyl group having from 1 to 4 carbon atoms;

(vi) styrene; and

(vii) R₁₂CH═

CHR₁₃, wherein R₁₂ and R₁₃ are independently hydrogen or methyl.

22. The method according to claim 19, wherein the ethylenically unsaturated monomer from (C) is selected from the group consisting of

(i) CH₂═

C(R′

₁)COR′

₂, wherein R′

₁ is methyl, R′

₂ is selected from the group consisting of —

OZ′

, —

N(Z″

)(Z″

), and —

OZ′

″

OH, wherein Z′

is an alkyl group having from 8 to 12 carbon atoms;

Z″

is independently selected from the group consisting of alkyl groups having from 8 to 10 carbon atoms, dimethylamino alkyl groups having from 1 to 3 carbon atoms, and hydroxyalkyl groups having from 1 to 3 carbon atoms; and

Z′

″

is an alkyl group having from 1 to 2 carbon atoms;

(ii) R′

₃OOC—

CH═

CH—

COOR′

₄, wherein R′

₃ and R₄ are independently an alkyl group having from 8 to 12 carbon atoms;

(iii) CH₂═

C(R′

₅)OCOR′

₆, wherein R′

₅ is methyl, and R′

₆ is an alkyl group having from 8 to 12 carbon atoms;

(iv) CH₂═

C(COOR′

₇)CH₂COOR′

₈, wherein R′

₇ and R′

₈ are independently an alkyl group having from 8 to 12 carbon atoms;

(v) CH₃CH═

CHCOOR′

₉, and R′

₉ is an alkyl group having from 8 to 12 carbon atoms;

(vi) R′

₁₀C₈H₄CR′

₁₁═

CHR′

₁₁, and R′

₁₀ and R′

₁₁ are independently methyl; and

(vii) R′

₁₂CH═

CHR′

₁₃, wherein R′

₁₂ and R′

₁₃ are independently selected from the group consisting of 2-pyrrolidinone, N-caprolactam, and an alkyl group having from 7 to 12 carbon atoms.

23. A method for preparing an aqueous emulsion comprising a water-dispersible copolymer characterized in that films formed from said water-dispersible copolymer are dispersible in water, yet non-dispersible in aqueous solutions containing 0.5% or more of an inorganic salt, comprising the steps of:

(a) providing the following monomers in percentages by weight;

(A) from about 40% 25% to about 60% of acidic ethylenically unsaturated monomer;

(B) from about 10% to about 80% of ethylenically unsaturated monomer selected from the group of monomer formulas consisting of;

(i) CH₂═

C(R₁)COR₂;

(ii) R₃OOC—

CH═

CH—

COOR₄;

(iii) CH₂═

C(R₅)OCOR₈;

(iv) CH₂═

C(COOR₇)CH₂COOR₈;

(v) CH₃CH═

CHCOOR₉;

(vi) R₁₀C₆H₄CR₁₁═

CHR₁₁; and

(vii) R₁₂CH═

CHR₁₃;

 

wherein R₁ is hydrogen or methyl and R₂ is —

OZ′

or —

N(Z″

)(Z″

), wherein Z′

is an alkyl group having from 1 to 7 carbon atoms, and Z′

is independently selected from the group consisting of hydrogen and alkyl groups having from 1 to 6 carbon atoms;

R₃ and R₄ are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R₃ and R₄ are not both hydrogen;

R₅ is hydrogen or methyl and R₆ is an alkyl group having from 1 to 7 carbon atoms;

R₇ and R₈ are independently hydrogen or an alkyl group having from 1 to 7 carbon atoms, with the proviso that R₇ and R₈ are not both hydrogen;

R₉ is an alkyl group having from 1 to 7 carbon atoms;

R₁₀ and R₁₁ are hydrogen; and

R₁₂ and R₁₃ are independently selected from the group consisting of hydrogen, —

CN, —

NHCHO, and an alkyl group having from 1 to 7 carbon atoms; and

(C) from about 10% to about 80% of ethylenically unsaturated monomer 4 selected from the group of monomer formulas consisting of;

(i) CH₂═

C(R′

₁)COR′

₂;

(ii) R′

₃OOC—

CH═

CH—

COOR′

₄;

(iii) CH₂═

C(R′

₅)OCOR′

₆;

(iv) CH₂═

C(COOR′

₇)CH₂COOR′

₈;

(v) CH₃CH═

CHCOOR′

₉;

(vi) R′

₁₀C₆H₄CR′

₁₁═

CHR′

₁₁; and

(vii) R′

₁₂CH═

CHR′

₁₃;

 

wherein R′

₁ is hydrogen or methyl, and R′

₂ is select from the group consisting of —

OZ′

, —

N(Z″

)(Z′

), and —

OZ′

″

OH, wherein Z′

is an alkyl group having from 8 to 18 carbon atoms;

Z″

is independently selected from the group consisting of alkyl groups having from 7 to 10 carbon atoms, dimethylamino alkyl groups having from 1 to 5 carbon atoms, and hydroxyalkyl groups having from 1 to 5 carbon atoms; and

Z′

″

is an alkyl group having from 1 to 4 carbon atoms;

R′

₃ and R′

₄ are independently an alkyl group having from 8 to 18 carbon atoms;

R′

₅ is hydrogen or methyl and R′

₆ is an alkyl group having from 8 to 18 carbon atoms;

R′

₇ and R′

₈ are independently an alkyl group having from 8 to 18 carbon atoms;

R′

₉ is an alkyl group having from 8 to 18 carbon atoms;

R′

₁₀ and R′

₁₁ are independently an alkyl group having from 1 to 2 carbon atoms;

R′

₁₂ and R′

₁₃ are independently selected from the group consisting of 2-pyrrolidinone, N-caprolactam, and an alkyl group having from 7 to 18 carbon atoms with the proviso that R₁₂ and R₁₃ are not both 2-pyrrolidinone, are not both N-caprolactam, or are not a mixture thereof; and

(b) neutralizing the monomers from (A), (B), and (C) in water to a level from about 2% to about 15% molar of the acidic ethylenically unsaturated monomer from (A); and

(c) emulsion polymerizing the monomers from (A), (B), and (C) at a solids level from about 20% to about 70% by weight, based on the aqueous emulsion, without a surfactant, to form a copolymer having a weight average molecular weight greater than about 25,000.

24. The method according to claim 23, wherein the acidic ethylenically unsaturated monomer from (A) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic acid half esters, maleic anhydride, itaconic acid, crotonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene phosphoric acid, and CH₂═

C(CH₃)COO(CH₂)_nOPO₃H, wherein n is from 2 to 4.

25. The method according to claim 23, wherein the ethylenically unsaturated monomer from (B) is selected from the group consisting of:

(i) CH₂═

C(R₁)COR₂, wherein R₁ is methyl and R₂ is —

OZ′

, wherein Z′

is an alkyl group having from 1 to 4 carbon atoms;

(ii) R₃OOC—

CH═

CH—

COOR₄, wherein R₃ and R₄ are independently an alkyl group having from 1 to 4 carbon atoms;

(iii) CH₂═

C(R₅)OCOR₆, wherein R₅ is methyl and R₆ is an alkyl group having from 1 to 4 carbon atoms;

(iv) CH₂═

C(COOR₇)CH₂COOR₈, wherein R₇ and R₈ are independently an alkyl group having from 1 to 4 carbon atoms;

(v) CH₃CH═

CHCOOR₈, wherein R₉ is an alkyl group having from 1 to 4 carbon atoms;

(vi) styrene; and

(vii) R₁₂CH═

CHR₁₃, wherein R₁₂ and R₁₃ are independently hydrogen or methyl.

26. The method according to claim 23, wherein the ethylenically unsaturated monomer from (C) is selected from the group consisting of:

(i) CH₂═

C(R′

₁)COR′

₂, wherein R′

₁ is methyl, R′

₂ is selected from the group consisting of —

OZ′

, N(Z″

)(Z″

), and OZ′

″

OH, wherein Z′

is an alkyl group having from 8 to 12 carbon atoms;

Z″

is independently. selected from the group consisting of alkyl groups having from 8 to 10 carbon atoms, dimethylamino alkyl groups having from 1 to 3 carbon atoms, and hydroxyalkyl groups having from 1 to 3 carbon atoms; and

Z′

″

is an alkyl group having from 1 to 2 carbon atoms;

(ii) R′

₃OOC—

CH═

CH—

COOR′

₄, wherein R′

₃ and R′

₄ are independently an alkyl group having from 8 to 12 carbon atoms;

(iii) CH₂═

C(R′

₅)OCOR′

₆, wherein R′

₅ is methyl, and R′

₆ is an alkyl group having from 8 to 12 carbon atoms;

(iv) CH₂═

C(COOR′

₇)CH₂COOR′

₈, wherein R′

₇ and R′

₈ are independently an alkyl group having from 8 to 12 carbon atoms;

(v) CH₃CH═

CHCOOR′

₉, and R′

₉ is an alkyl group having from 8 to 12 carbon atoms;

(vi) R′

₁₀C₆H₄CR′

₁₁═

CHR′

₁₁, and R′

₁₀ and R′

₁₁ are independently methyl; and

(vii) R′

₁₂CH═

CHR′

₁₃, wherein R′

₁₂ and R′

₁₃ are independently selected from the group consisting of 2-pyrrolidinone, N-caprolactam, and an alkyl group having from 7 to 12 carbon atoms.