Polymer modified bitumen compositions

• US 20030149140A1
• Filed: 02/06/2003
• Published: 08/07/2003
• Est. Priority Date: 02/07/2002
• Status: Active Grant

• Current Assignee: Kraton Polymers US LLC (DL Holdings Co., Ltd.)
• Original Assignee: Kraton Polymers US LLC (DL Holdings Co., Ltd.)
• Inventors: Handlin, Dale L. Jr., Willis, Carl L., Stephens, Keith E., Kluttz, Robert Q.
• Granted Patent: US 6,759,454 B2
• Time in Patent Office: Days
• US Class Current: 524/59
• CPC Class Codes: C08F 287/00 Macromolecular compounds obtained by polymerising monomers on to block polymers
• CPC Class Codes: C08F 297/04 polymerising vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: C08L 101/00 Compositions of unspecified macromolecular compounds
• CPC Class Codes: C08L 23/10 Homopolymers or copolymers of propene
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/02 of vinyl-aromatic monomers and conjugated dienes
• CPC Class Codes: C08L 53/025 modified
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 95/00 Compositions of bituminous materials, e.g. asphalt, tar, pitch
• CPC Class Codes: C09D 153/02 Vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: C09D 153/025 modified
• CPC Class Codes: C09J 153/02 Vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: C09J 153/025 modified

Abstract

The present invention is a polymer modified bituminous composition having improved phase stability, heat aging and viscosity characteristics. The bituminous compositions are blends comprising bitumen and from about 0.5 to about 25% of a novel anionic block copolymer where one of the blocks is a controlled distribution copolymer of a conjugated diene and a mono-alkenyl arene having a specific arrangement of the monomers in the copolymer block. The composition of the invention is useful for paving, roofing felts, water-proof membrane, adhesive, mopping asphalt, carpet backing and pipe coating applications.

Claims

1. A bituminous composition comprising:

I) from about 75 percent to about 99.5 percent bitumen; and

II) from about 0.5 percent to about 25 percent weight of a block copolymer having at least one A block and at least one B block wherein;

a) each A block is a mono-alkenyl arene homopolymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono-alkenyl arene;

b) each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 30,000 and about 300,000;

c) each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono-alkenyl arene units;

d) the total amount of mono-alkenyl arene in the block copolymer is about 20 percent weight to about 80 percent weight; and

e) the weight percent of mono-alkenyl arene in each B block is between about 10 percent and about 75 percent.

2. The bituminous composition of claim 1 wherein said mono-alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.

3. The bituminous composition of claim 1 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in the block B have 1,2-configuration.

4. The bituminous composition of claim 1 wherein said conjugated diene is butadiene, and wherein about 20 to about 40 mol percent of the condensed butadiene units in the B block have 1,2-configuration.

5. The bituminous composition of claim 1 wherein the styrene blockiness index of the block B is less than about 42 percent

6. The bituminous composition of claim 1 wherein the styrene blockiness index of the block B is less than about 22 percent.

7. The bituminous composition of claim 3 wherein the weight percentage of styrene in the B block is between about 10 weight percent and about 50 weight percent, and the styrene blockiness index of the block B is less than about 25 percent, said styrene blockiness index being the proportion of styrene units in the B block having two styrene neighbors on the polymer chain.

8. The bituminous composition of claim 1 wherein the block copolymer has the general configuration (A—

B)_n, (A—

B—

A)_n, (A—

B)_nX or (A—

B—

A)_nX and mixtures thereof where X is the residue of a coupling agent and n is an integer from 1 to about 30.

9. The bituminous composition of claim 8 wherein the coupling agent residue derives from coupling agents selected from the group consisting of divinyl arenes, silicon halides, alkoxy silanes, aliphatic epoxies, glycidyl aromatic epoxies, and diesters.

10. The bituminous composition of claim 9 wherein the coupling agent is tetra-ethoxy silane.

11. The bituminous composition of claim 9 wherein the coupling agent is dialkyl adipate.

12. The bituminous composition of claim 9 wherein the coupling agent is a glycidyl aromatic epoxy formed by the reaction of bisphenol A and epichlorohydrin.

13. The bituminous composition of claim 9 wherein the coupling agent is m-divinyl-benzene.

14. The bituminous composition of claim 8 wherein the block copolymer comprises at least 70 percent A—

B—

A configuration.

15. The bituminous composition of claim 8 wherein the block copolymer comprises at least 70 percent (A—

B)_nX configuration where n is from 3 to 5 and X is the residue of a coupling agent.

16. The bituminous composition of claim 1 wherein the block copolymer is from about 0.5 percent to about 8 percent weight.

17. The bituminous composition of claim 1 wherein the block copolymer is from 8 percent to about 25 percent weight.

18. The bituminous composition of claim 1 wherein the bitumen has a penetration from about 40 to about 120 dmm at 25°

C.

19. The bituminous composition of claim 1 wherein the bitumen has a ring and ball softening point from about 110 to about 150°

C.

20. A paving formulation comprising the bituminous composition of claim 1.

21. A roofing felt comprising the bituminous composition of claim 1.

22. A water-proofing membrane comprising the bituminous composition of claim 1.

23. An adhesive comprising the bituminous composition of claim 1.

24. A pipe coating comprising the bituminous composition of claim 1.

25. A carpet backing comprising the bituminous composition of claim 1.

26. A bituminous composition comprising:

I) from about 75 percent to about 99.5 percent bitumen; and

II) from about 0.5 percent to about 25 percent weight of an unhydrogenated block copolymer having at least one A block and at least one B block wherein;

a) each A block is a mono-alkenyl arene homopolymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono-alkenyl arene;

b) each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 30,000 and about 300,000;

c) each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono-alkenyl arene units;

d) the total amount of mono-alkenyl arene in the block copolymer is about 20 percent weight to about 80 percent weight; and

e) the weight percent of mono-alkenyl arene in each B block is between about 10 percent and about 75 percent.

27. A bituminous composition comprising:

I) from about 75 percent to about 99.5 percent bitumen; and

II) from about 0.5 percent to about 25 percent weight of a hydrogenated block copolymer having at least one A block and at least one B block wherein;

a) each A block is a mono-alkenyl arene homopolymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono-alkenyl arene;

b) each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 30,000 and about 300,000;

c) each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono-alkenyl arene units;

d) the total amount of mono-alkenyl arene in the block copolymer is about 20 percent weight to about 80 percent weight; and

e) the weight percent of mono-alkenyl arene in each B block is between about 10 percent and about 75 percent.

28. The bituminous composition of claim 27 wherein the block copolymer has the general configuration (A—

B)_n, (A—

B—

A)_n, (A—

B)_nX or (A—

B—

A)_nX and mixtures thereof where X is the residue of a coupling agent and n is an integer from 1 to about 30.

29. The bituminous composition of claim 27 wherein the conjugated diene is selectively hydrogenated to saturate at least 80% of the double bonds.

30. The bituminous composition of claim 27 wherein the said mono-alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.

31. The bituminous composition of claim 27 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in the block B have 1,2-configuration.

32. The bituminous composition of claim 27 wherein the styrene blockiness index of the block B is less than about 42 percent.

33. A mopping asphalt comprising the bituminous composition of claim 27