Ultrahigh melt flow styrenic block copolymers

Patent metadata

Field	Value
Publication number	US-10920064-B2
Application number	US-201916360094-A
Country	US
Kind code	B2
Filing date	Mar 21, 2019
Priority date	Mar 23, 2018
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

Abstract

The disclosure relates to a hydrogenated styrenic block copolymer with high vinyl content, low viscosity, low order-disorder temperature and improved processability. The hydrogenated styrenic block copolymers can be extruded or molded with a minimum of additives. The hydrogenated styrenic block copolymers have high melt flows allowing for ease in processing such as injection molding, overmolding, dipping, extrusion, roto-molding, slush molding, fiber spinning, film making, 3D printing and foaming.

First claim

The invention claimed is:

1. A selectively hydrogenated block copolymer having an S block and an E or E 1 block and having a general formula: S-E-S, (S-E 1 ) n X, or mixtures thereof,
wherein:
n has a value of 2 to 6;
X is a coupling agent residue;
the S block has a peak molecular weight of 4,400 to 5,600 g/mol;
the block copolymer has a solution viscosity of less than 80 centipoise (cP) as measured at 25 wt. % toluene and 25° C.;
the block copolymer has a polystyrene content of 25 to 40 wt. %; and
up to 50 wt. % of diblock units in the block copolymer have a general formula S-E or S-E 1 ,

wherein prior to hydrogenation:
the S block is a polystyrene block;
the E block is a polydiene block selected from the group consisting of polybutadiene, polyisoprene and mixtures thereof, and having a peak molecular weight of from 18,000 to 26,000 g/mol;
the E 1 block is a polydiene block selected from the group consisting of polybutadiene, polyisoprene and mixtures thereof, and having a peak molecular weight of from 9,000 to 13,000 g/mol;
the polydiene block has a total vinyl content of 60 to 85%; and

wherein subsequent to hydrogenation:
0-10 percent of styrene double bonds in the block copolymer are reduced, and
at least 80 percent of conjugated diene double bonds in the block copolymer are reduced.

2. The block copolymer of claim 1 , wherein the block copolymer has an order-disorder temperature (ODT) of less than 230° C.

3. The block copolymer of claim 1 , wherein the block copolymer has a formula S-E-S, with less than 10 wt. % of a diblock copolymer of formula S-E.

4. The block copolymer of claim 1 , wherein the block copolymer has a formula (S-E 1 ) n X, with between 5 and 50 wt. % of a diblock copolymer of formula S-E 1 .

5. The block copolymer of claim 1 , wherein the coupling agent is selected from the group of methyl benzoate, silicon tetrachloride, alkoxy silanes, polyepoxides, polyisocyanates, polyimines, polyaldehydes, polyketones, polyanhydrides, polyesters, polyhalides, diesters, methoxy silanes, divinyl benzene, 1,3,5-benzenetricarboxylic acid trichloride, glycidoxytrimethoxy silanes, oxydipropylbis(trimethoxy silane), and mixtures thereof.

6. The block copolymer of claim 1 , wherein the block copolymer has a formula of S-E-S, and a solution viscosity ranging from 10 cP to 80 cP.

7. The block copolymer of claim 1 , wherein the block copolymer has a formula of (S-E 1 ) n X, and a solution viscosity ranging from 10 to 50 cP.

8. The block copolymer of claim 1 , wherein the block copolymer has a melt index from 80 to 600 g/10 min. at 190° C. and 2.16 kg weight.

9. The block copolymer of claim 1 wherein the block copolymer has an elongation at break of at least 300%.

10. The block copolymer of claim 1 wherein the block copolymer has a tensile strength of at least 4 MPa.

11. The block copolymer of claim 1 wherein the block copolymer is functionalized with a functional group selected from fumaric acid, itaconic acid, citraconic acid, acrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and their derivatives and derivatives thereof.

12. The block copolymer of claim 11 , wherein the block copolymer is functionalized by grafting maleic anhydride onto the block copolymer.

13. An adhesive composition comprising:
0 to about 80 wt. % of a poly-alpha-olefin
10 to about 60 wt. % of a tackifying resin, and
10 to about 50 wt. % of the hydrogenated block copolymer of claim 1 .

14. A composition comprising:
the selectively hydrogenated block copolymer of claim 1 ;
0.001 to 90 wt. % of an additive selected from olefin polymers, thermoplastic polyurethane, thermoplastic copolyester, styrene polymers, thermoplastic elastomers, tackifying resins, polymer extending oil, waxes, fillers, lubricants, stabilizers, engineering thermoplastic resins, and mixtures thereof.

15. The composition of claim 14 , wherein the additive is a high flow polyolefin having a melt flow rate of >40 g/10 min, according to ASTM D1238 at 190° C. and 2.16 kg weight.

16. The composition of claim 14 , wherein the selectively hydrogenated block copolymer has an order-disorder temperature (ODT) of 140-230° C.

17. An article comprising the composition of claim 14 , wherein the article is selected from the group of toys, medical devices, films, tubing, profiles, 3D printed article, sheet, coating, band, strip, molding, tube, foam, tape, fabric, thread, filament, ribbon, fibers, fibrous web, overmolded automotive parts, dipped goods, sheet molded articles, hot melt adhesives, tie-layers, roofing sheets, membranes, tire treads, and tire inner layers.

18. The article of claim 17 , wherein the article is formed by injection molding, overmolding, dipping, extrusion, roto-molding, slush molding, fiber spinning, film making, 3D printing or foaming.

19. A composition comprising:
a selectively hydrogenated block copolymer having an S block and an E or E 1 block and having the general formula S-E-S, (S-E 1 ) n X or mixtures thereof,
wherein:
n has a value of 2 to 6,
X is a coupling agent residue,
the block copolymer has a styrene content of 29 to 37 wt. %, and a solution viscosity of 10 to 80 centipoise (cP) as measured at 25 wt. % toluene and 25° C.; and

wherein prior to hydrogenation
the S block is a polystyrene block,
the E block is a polydiene block, selected from the group consisting of polybutadiene, polyisoprene and mixtures thereof, having a peak molecular weight of from 18,000 to 26,000 g/mol,
the E 1 block is a polydiene block, selected from the group consisting of polybutadiene, polyisoprene and mixtures thereof, having a peak molecular weight of from 9,000 to 13,000 g/mol, and
the polydiene blocks have a total vinyl content of 70 to 85%; and

wherein subsequent to hydrogenation
0-10 percent of the styrene double bonds have been hydrogenated; and

wherein the block copolymer contains from 0.1 to 10 wt. % of a functional group selected from fumaric acid, itaconic acid, citraconic acid, acrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and derivatives thereof as a grafted monomer.

20. The composition of claim 19 , wherein the selectively hydrogenated block copolymer has an order-disorder temperature (ODT) of less than 230° C.

21. A composition consisting essentially of the selectively hydrogenated block copolymer of claim 1 .

22. An article consisting essentially of the selectively hydrogenated block copolymer of claim 1 , wherein the article is selected from the group of toys, medical devices, films, tubing, profiles, 3D printed article, sheet, coating, band, strip, molding, tube, foam, tape, fabric, thread, filament, ribbon, fibers, fibrous web, overmolded automotive parts, dipped goods, sheet molded articles, hot melt adhesives, tie-layers, roofing sheets, membranes, tire treads, and tire inner layers.

23. The article of claim 22 , wherein the article is formed by injection molding, overmolding, dipping, extrusion, roto-molding, slush molding, fiber spinning, film making, 3D printing or foaming.

24. The composition of claim 14 , wherein the composition comprises 0.001 to 90 wt. % of an additive selected from olefin polymers, thermoplastic polyurethane, thermoplastic copolyester, styrene polymers, thermoplastic elastomers, tackifying resins and mixtures thereof.

Assignees

• Kraton Polymers Llc

Inventors

• Flood John E
• Muyldermans Xavier

Classifications

• C08F8/04

  Reduction, e.g. hydrogenation · CPC title

• C08L53/025 Primary

  modified · CPC title

• C08F297/044 Primary

  using a coupling agent · CPC title

• C09J123/00

  Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers · CPC title

• C08F2810/00

  Chemical modification of a polymer · CPC title