Granted Patent B2

US 8,008,398 · App. 10/589,705 · Granted Aug 30, 2011

Abstract

Claims (42)

1. Foamable compositions which are usable for the manufacture of foamed, flexible, heat resistant, thermoplastic elastomeric articles, and which comprise at least:

(a) 100 parts by weight of one or more selectively hydrogenated block copolymers, having at least two resinous blocks A of non-hydrogenated predominantly polymerized monovinyl arene, and a selectively hydrogenated elastomeric block B, wherein said block B prior to hydrogenation being predominantly a polymerized conjugated diene of polybutadiene, said block copolymer having a total apparent molecular weight from 250-600 kg/mole, and containing polymerized monovinyl arene blocks of true molecular weight of from 18 to 60 kg/mole, and said polymerized monovinyl arene content is in the range of from 20 to 35 wt %,

b) 5 to 50 parts by weight per 100 parts by weight of component (a) of one or more selectively hydrogenated block copolymers having at least two resinous blocks A′ of non-hydrogenated predominantly polymerized monovinyl arene, and an selectively hydrogenated elastomeric block B′, wherein said block B′ prior to hydrogenation has been derived from a polymerized conjugated diene or dienes as a major component which may be mixed with 25 or less wt. % of other copolymers, and said block copolymer having a total apparent molecular weight in the range of from 50 to 180 kg/mole, while the resinous blocks A′ shown an true molecular weight in the range of from 3 to 20 kg/mole,

c) from 42 to 80 parts by weight per 100 parts by weight of component (a) of a linear crystalline polymer comprising propylene as major component, with a Vicat softening temperature in the range of from 130° C. to 180° C. and a MFR in the range of from 0.5 to 30 dg/min and a polydisperity index of at least 4.5,

(d) from 100 to 250 parts by weight per 100 parts by weight of component (a) of a softener compatible with blocks B and B′,

(e) from 0.01 to 3 wt %, relative to the weight of the primary components (a) up to (e) of a solid chemical nucleating agent of the endothermic group in combination with a blowing agent, and optionally

(f) one or more secondary components selected from PPO and/or any resins compatible with block copolymer component (a), antioxidants, UV-stabilizers, flame retardants, surface modifying agents and inorganic fillers.

2. The foamable compositions of claim 1 , which comprise as components (a) and (b) at least one block copolymers of the general formulae

ABA or (AB) n X and A′B′A′ or (A′B′) n X

respectively, wherein A, A′ represent a poly(monovinyl arene) block and B, B′ represent a hydrogenated poly(conjugated diene(s)) block, wherein n is an integer ≧2 and wherein X is the remainder of a coupling agent, wherein the blocks A, A′ are different and the blocks A are larger than the blocks A′.

3. The foamable compositions of claim 2 , wherein the block copolymer component (b) has the formula A′B′A′ or (A′B′) n X, has a total apparent molecular weight in the range of from 80 to 160 kg/mole, wherein A′ represents a substantially pure poly(styrene) block, each having a molecular weight in the range of from 5 to 15 kg/mole.

4. The foamable compositions of claim 2 , wherein

i) the block copolymer component (a) has the formula ABA or (AB) n X, has a total apparent molecular weight in the range of from 250,000 to 600,000, wherein A represents a substantially pure poly(styrene) block and wherein the poly(styrene) block content in said block copolymer (a) is in the range of from 20 to 35 wt % and wherein B represents a hydrogenated poly(butadiene) block;

ii) the weight ratio between the block copolymer components (a) and (b) is in the range of from 10 to 40 parts by weight of component (b) per 100 parts by weight of component (a);

iii) component (e) is a single polymer or a mixture of polymers predominantly composed of propylene monomer or copolymer of predominantly propylene with a minor proportion of a different alkylene selected from ethylene or butylenes, having a melt flow rate in the range of between 2 and 15 dg/min at 230° C./2.16 kg, a Vicat softening temperature in the range of from 130 to 170° C., and occurs in a weight ratio of from 42 to 65 parts by weight of (c) per 100 parts by weight of (a);

iv) component (d) is a paraffinic oil; and

v) component (e) is selected from the group consisting of a mixture of NaHCO 3 with citric acid and a mixture of NaHCO 3 with sodium citrate, in amounts of from 0.5 to 1 wt %,

relative to the weight of components (a) up through (e).

5. The foamable compositions of claim 2 , wherein

i) the block copolymer component (b) has the formula A′B′A′ or (A′B′) n X, has a total apparent molecular weight in the range of from 80 to 160 kg/mole, wherein A′ represents a substantially pure poly(styrene) block, each having a molecular weight in the range of from 5 to 15 kg/mole;

ii) the weight ratio between the block copolymer components (a) and (b) is in the range of from 10 to 40 parts by weight of component (b) per 100 parts by weight of component (a);

iii) component (e) is a single polymer or a mixture of polymers predominantly composed of propylene monomer or copolymer of predominantly propylene with a minor proportion of a different alkylene selected from ethylene or butylenes, having a melt flow rate in the range of between 2 and 15 dg/min at 230° C./2.16 kg, a Vicat softening temperature in the range of from 130 to 170° C., and occurs in a weight ratio of from 42 to 65 parts by weight of (c) per 100 parts by weight of (a);

iv) component (d) is a paraffinic oil; and

v) component (e) is selected from the group consisting of a mixture of NaHCO 3 with citric acid and a mixture of NaHCO 3 with sodium citrate, in amounts of from 0.5 to 1 wt %,

relative to the weight of components (a) up through (e).

6. The foamable compositions of claim 1 , wherein the weight ratio between the block copolymer components (a) and (b) is in the range of from 10 to 40 parts by weight of component (b) per 100 parts by weight of component (a).

7. The foamable compositions of claim 1 , wherein component (c) is a single polymer or a mixture of polymers predominantly composed of propylene monomer or a copolymer of predominantly propylene with less than 25 wt % of a different alkylene selected from ethylene or butylenes.

8. The foamable compositions of claim 7 , wherein component (c) has a melt flow range between 2 and 15 dg/min at 230° C./2.16 kg, a Vicat softening temperature in the range of from 130 to 170° C., and occurs in a weight ratio of from 42 to 65 parts by weight of (c) per 100 parts by weight of (a).

9. The foamable compositions of claim 8 , wherein the component (c) shows a polydispersity index >5.

10. The foamable compositions of claim 1 , wherein component (d) is a paraffinic oil.

11. The foamable compositions of claim 1 , wherein component (e) is selected from the group consisting of a mixture of NaHCO 3 with citric acid and a mixture of NaHCO 3 with sodium citrate, in amounts of from 0.5 to 1 wt %,

relative to the weight of components (a) up through (e).

12. Pre-blends of the foamable compositions according to claim 1 , comprising either:

(A) a pre-blend comprising components (a), (c) and (d); or

(B) a pre-blend comprising components (b), (c) and/or (d).

13. Foamed articles comprising

(a) 100 parts by weight of one or more selectively hydrogenated block copolymers, having at least two resinous blocks A of non-hydrogenated predominantly polymerized monovinyl arene, and a selectively hydrogenated elastomeric block B, wherein said block B prior to hydrogenation being predominantly a polymerized conjugated diene of polybutadiene, said block copolymer having a total apparent molecular weight from 250-600 kg/mole, and containing polymerized monovinyl arene blocks of true molecular weight of from 18 to 60 kg/mole, and said polymerized monovinyl arene content is in the range of from 20 to 35 wt %,

b) 5 to 50 parts by weight per 100 parts by weight of component (a) of one or more selectively hydrogenated block copolymers having at least two resinous blocks A′ of non-hydrogenated predominantly polymerized monovinyl arene, and an selectively hydrogenated elastomeric block B′, wherein said block B′ prior to hydrogenation has been derived from a polymerized conjugated diem or dienes as a major component which may be mixed with 25 or less wt. % of other copolymers, and said block copolymer having a total apparent molecular weight in the range of from 50 to 1.80 kg/mole, while the resinous blocks A′ shown an true molecular weight in the range of from 3 to 20 kg/mole,

c) from 42 to 80 parts by weight per 100 parts by weight of component (a) of a linear crystalline polymer comprising propylene as major component, with a Vicat softening temperature in the range of from 130° C. to 180° C. and a MFR in the range of from 0.5 to 30 dg/min and a polydisperity index of at least 4.5,

(d) from 100 to 250 parts by weight per 100 parts by weight of component (a) of a softener compatible with blocks B and B′,

(e) from 0.01 to 3 wt %, relative to the weight of the primary components (a) up to (e) of a solid chemical nucleating agent of the endothermic group in combination with a blowing agent, and optionally

(f) one or more secondary components selected from PPO and/or any resins compatible with block copolymer component (a), antioxidants, UV-stabilizers, flame retardants, surface modifying agents and inorganic fillers.

Assignments (10)