(METH)ACRYLIC OLIGOMERS

• US 20190308924A1
• Filed: 07/06/2017
• Published: 10/10/2019
• Est. Priority Date: 07/06/2016
• Status: Active Grant

• Current Assignee: Synthomer Adhesive Technologies LLC (Eastman Chemical Company)
• Original Assignee: Eastman Chemical Company
• Inventors: Lester, Christopher Lee, Goetz, Sarah Exley, Blayney, Timothy Harold, Ashley, Gabrielle Rose, Pavlin, Mark Stanley, Atkins, Douglas Grant, Liu, Zhufang
• Granted Patent: US 11,485,699 B2
• Time in Patent Office: Days
• CPC Class Codes: C07C 67/00 Preparation of carboxylic acid esters
• CPC Class Codes: C07C 67/465 by oligomerisation
• CPC Class Codes: C07C 69/54 Acrylic acid esters; Methacrylic acid esters
• CPC Class Codes: C08F 120/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 120/18 with acrylic or methacrylic acids
• CPC Class Codes: C08F 120/20 of polyhydric alcohols or polyhydric phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 20/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 20/18 with acrylic or methacrylic acids
• 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 220/1808 C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
• CPC Class Codes: C08F 8/04 Reduction, e.g. hydrogenation
• CPC Class Codes: C09J 133/06 of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C09J 133/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C09J 133/10 Homopolymers or copolymers of methacrylic acid esters

Abstract

The invention provides (meth)acrylic oligomers prepared from C1-C20 alkyl and C5-C20 cycloalkyl (meth)acrylates, wherein said oligomers have a Mn of about 300 g/mole to about 3,000 g/mole; a Mw of about 700 g/mole to about 6,000 g/mole; a Mz of about 900 g/mole to about 10,000 g/mole. The oligomers may have a Yellowness Index, according to ASTM E313 of less than 2. The oligomers of the invention are useful as tackifiers in adhesive compositions, but also are believed to be useful also in general polymer modification as plasticizers, leveling agents, viscosity reducers (i.e., rheology modifiers), and for increasing solids content in solvent-borne applications of all types with little detrimental impact on viscosity. The invention also provides adhesive compositions and laminate articles coated on at least one side with the adhesive compositions of the invention.

Claims

1. (Meth)acrylic oligomers prepared from C₁-C₂₀ alkyl and C₅-C₂₀ cycloalkyl (meth)acrylates, wherein said oligomers have a M_n of from about 300 to about 3000 g/mole;

a M_z of from about 900 to 10,000 g/mole; and

wherein the Yellowness Index, according to ASTM E313 is less than 2.

2. The oligomers of claim 1, wherein the M_n is from about 700 to about 2500 g/mole.

3. The oligomers of claim 1, wherein the M_z is from about 1400 to about 6000 g/mole.

4. The oligomers of claim 1, wherein the C₁-C₂₀ alkyl and C₅-C₂₀ cycloalkyl is selected from the group consisting of cyclohexyl, methyl, t-butyl, isobutyl, norbornyl, dicyclopentadienyl, and isobornyl.

6. The oligomers of claim 1, wherein said oligomers have been hydrogenated to reduce any residual unsaturated bonds.

8. The oligomers of claim 1, wherein the glass transition temperature of the oligomer is −

100 to 120°

C.

9. The oligomers of claim 1, wherein the polydispersity (M_w/M_n) is less than 3.5.

10. The oligomers of claim 1, wherein the polydispersity (M_w/M_n) is less than 2.5.

11. The oligomers of claim 1, wherein the polydispersity (M_w/M_n) is less than 2.0.

16. The oligomers of claim 1, wherein the Ring &

Ball softening point of the oligomers is in the range of from 65°

C. to 125°

C.

17. The oligomers of claim 1, wherein the M_w is in the range of about 700 to about 6000 g/mole and the glass transition temperature of the oligomers is in the range of from 5 to 55°

C.

55. A composition comprising the oligomers of claim 1.

56. An article comprising said composition of claim 55.

57. An adhesive comprising the oligomers of claim 1.

5. (canceled)

7. (canceled)

12-15. -15. (canceled)

18-37. -37. (canceled)

38. (Meth)acrylic oligomers prepared from at least one type of monomer, wherein said monomer is selected from the group consisting of isobutyl (meth)acrylate, t-butyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, norbornyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, wherein said oligomers have a M_n molecular weight of from about 300 to about 3000;

a M_z molecular weight of from about 900 to about 10,000; and

a M_w molecular weight of from about 700 to about 6000, and wherein said oligomers are hydrogenated to a residual olefin content, measured by ¹H NMR, of less than 3.5 weight percent.

40. The oligomers of claim 38, wherein said oligomers have a Ring &

Ball softening point in the range of from 60°

C. to 125°

C.

41. The oligomers of claim 38, wherein said oligomers have a glass transition temperature in the range of from about 5°

C. to about 60°

C.

43. The oligomers of claim 38, wherein the polydispersity (M_w/M_n) of the oligomer is less than 2.5.

44. The oligomers of claim 38, wherein said oligomers are hydrogenated to a residual olefin content, measured by ¹H NMR, of less than 1.5 weight percent.

45. The oligomers of claim 38, wherein said oligomers have an Mz molecular weight of 2000 to 6000, a Ring and Ball softening point of 70°

C. to 120°

C., a glass transition temperature of from 10 to 55°

C., and a Yellowness Index according to ASTM E313 of less than 2, and wherein according to TGA ASTM E2550-11 to record onset of degradation, the temperature at which 10% weight loss of the oligomer backbone is achieved is in the range of from about 300°

C. to about 330°

C.

39. (canceled)

42. (canceled)

46-54. -54. (canceled)