COMPOSITE MATERIAL BASED ON VINYLAROMATIC POLYMERS HAVING ENHANCED THERMAL INSULATION PROPERTIES AND PROCESS FOR THE PREPARATION THEREOF

• US 20100148110A1
• Filed: 05/15/2008
• Published: 06/17/2010
• Est. Priority Date: 05/18/2007
• Status: Active Grant

• Current Assignee: Polimeri Europa SPA (Eni Petroleum Company Incorporated)
• Original Assignee: Polimeri Europa SPA (Eni Petroleum Company Incorporated)
• Inventors: Ghidoni, Dario, Felisari, Riccardo, Ponticiello, Antonio, Casalini, Alessandro, Simonelli, Alessandra
• Granted Patent: US 8,268,902 B2
• Time in Patent Office: Days
• US Class Current: 252/62
• CPC Class Codes: C08J 2201/03 Extrusion of the foamable blend
• CPC Class Codes: C08J 2325/06 Polystyrene
• CPC Class Codes: C08J 9/0066 Use of inorganic compounding ingredients
• CPC Class Codes: C08J 9/009 Use of pretreated compounding ingredients
• CPC Class Codes: C08J 9/16 Making expandable particles
• CPC Class Codes: C08K 3/04 Carbon

Abstract

Expandable particle composite material suitable for the preparation of expanded materials having a density lower than 40 g/l and a content of closed cells of at least 60%, including heterophase cavities and/or heterophase domains, whose matrix is a synthetic thermoplastic resin having at least 60% by weight of a vinyl aromatic polymer and in which an expanding system is contained, together with a heterogeneously distributed graphite material, having a graphitization degree, calculated by means of the Maire and Mering formula, of at least 0.2.

Claims

1. An expandable granular composite material having a polymeric matrix suitable for preparing expanded articles having a density lower than 40 g/l and a content of closed cells of at least 60% as determined according to ASTM D-2856 comprising heterophase domains including materials not completely miscible with said polymeric matrix, and/or cavities, embedded inside the polymeric matrix, wherein said polymeric matrix is a thermoplastic synthetic polymer having at least 60% by weight, with respect to the overall weight of the matrix, of a polymer deriving from a vinyl aromatic polymer, wherein said composite material contains an expanding system and graphite material not homogeneously distributed, having a graphitization degree, calculated by the Maire and Mering formula, of at least 0.2.

2. The expandable granular composite material according to claim 1, wherein said cavities are cavities of gas and/or liquid essentially consisting of the expanding system.

3. The granular composite material according to claim 1, wherein said cavities have diameters ranging from 2 to 90 micrometers and are included in the expandable composite material in a volumetric fraction ranging from 0.5 to 20.0%.

4. The expandable granular composite material according to claim 3, wherein said cavities of gas and/or liquid, are included in a volumetric fraction ranging from 2.0 to 16.0%.

5. The expandable granular composite material according to claim 4, wherein said cavities of gas and/or liquid, are included in a volumetric fraction ranging from 3.0 to 13.0%.

6. The expandable granular composite material according to claim 1, containing heterophase domains of a material, not completely miscible with the same vinyl aromatic matrix, inside which graphite material is distributed.

7. The expandable granular composite material according to claim 1, wherein said not completely miscible material ranges from 1 to 40% by weight of the vinyl aromatic matrix.

8. The expandable granular composite material according to claim 1, wherein said not completely miscible material consists of one or more of the following (co)polymers:

a. block or random vinyl aromatic copolymers selected from the group consisting of styrene-butadiene, styrene-butadiene-styrene, styrene-isoprene, styrene-isoprene-styrene, styrene-ethylene-butadiene-styrene (SEBS), styrene maleic anhydride co-polymers, styrene-butylacrylate copolymers, high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), styrene-ethylene-propylene (SEP);

b. polymers based on olefins, selected from the group consisting of poly(ethylene-vinyl acetate) (EVA), polypropylene, polyethylene (PE), polybutylene terephthalate (PBT) or polyethylene terephthalate (PET) and relative blends and interpolymers with polystyrene;

c. condensation (co)polymers selected from the group consisting of polycarbonates and polyesters, (meth)acrylic polymers, polyamides, polylactates and relative blends.

9. The expandable granular composite material according to claim 1, wherein said not completely miscible material consists of one or more of the following materials:

polyalkylene glycol, wherein the alkenyl group contains from 2 to 5 carbon atoms and has a molecular weight ranging from 400 to 10,000 and the corresponding esters;

mineral essences, petrolatum, triglycerides, petroleum oil, water, polybutylene synthetic fluids, saturated and unsaturated fatty acids with corresponding esters and salts;

esters of sorbitane.

10. The expandable granular composite material according to claim 1, wherein said expanding system consists of an expanding agent or a blend of expanding agents.

11. The expandable granular composite material according to claim 1, wherein said graphite material has a stacking height of the crystallites LC₀₀₂ of 7 to 150 nm and a coherence length of the crystallites La₁₀₀ of 10 to 200 nm.

12. The expandable granular composite material according to claim 1, wherein said graphite material essentially consists of natural or artificial graphite, graphite intercalation compounds, expanded graphite, colloidal graphite, graphitized coke or pitch, pyrolytic carbon, graphitized carbon, carbon nanofibers.

13. The expandable granular composite material according to claim 1, wherein the content of graphite material ranges from 1.0 to 30.0% by weight, calculated with respect to the overall weight of the composite material.

14. The expandable granular composite material according to claim 1, which contains up to 15% by weight of carbon black with respect to the overall weight of the composite material.

15. The expandable granular composite material according to claim 1, which contains up to 40% by weight, with respect to the overall weight of the composite material, of one or more of the following polymers or copolymers:

a. block or random vinyl aromatic copolymers selected from the group consisting of styrene-butadiene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butadiene-styrene (SEBS), styrene-butylacrylate copolymers, high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), styrene-ethylene-propylene (SEP);

b. polymers based on olefins, selected from the group consisting of poly(ethylene-vinyl acetate) (EVA), polypropylene, polyethylene (PE), polybutylene terephthalate (PBT) or polyethylene terephthalate (PET) and relative blends and interpolymers with polystyrene;

c. condensation (co)polymers selected from the group consisting of polycarbonates and polyesters, (meth)acrylic polymers, polyamides, polylactates and relative blends.

16. The expandable granular composite material according to claim 1, which contains from 0.5 to 15% by weight, calculated with respect to the overall weight of the composite material, of a brominated organic compound having a bromine content of over 30% by weight, and from 0.1 to 1.5% by weight, based on the overall weight of the composite material, of a compound having one or more labile bonds between two carbon atoms, or between two oxygen atoms, or between two nitrogen atoms.

17. The expandable granular composite material according to claim 16, wherein the brominated organic compound is hexabromocyclododecane, and the compound with a labile bond is 2,3-dimethyl-2,3-diphenyl-butane.

18. The expandable granular composite material according to claim 1, wherein granules in the granular composite material have an essentially ellipsoidal shape and a shape factor of the granules ranges from 0.6 to 0.99.

19. The expandable granular composite material according to claim 18, wherein the shape factor of the granules ranges from 0.7 to 0.98.

20. The expandable granular composite material according to claim 1, wherein content of graphite material ranges from 2.0 to 15.0% by weight, calculated with respect to the overall weight of the composite material.

21. The expandable granular composite material according to claim 1, wherein a minimal mixing area of the graphite material ranges from 35 to 3,000 μ

m².

22. The expandable granular composite material according to claim 21, wherein the minimal mixing area ranges from 45 to 1,000 μ

m².

23. The expandable granular composite material according to claim 1, wherein the graphite material has a graphitization degree, calculated by the Maire and Mering formula, ranging from 0.3 to 0.95.

24. A composite foam for thermal insulation produced from the expandable granular composite materials according to claim 1, having a density lower than 40 g/l and a content of closed cells of at least 60%, as determined according to ASTM D-2856.

25. A method for producing expandable granular composite materials according to claim 1, comprising:

a. mass/solution polymerizing a vinyl aromatic monomer and, optionally, co-monomers, together with a graphite material, whose main portion is fed as a concentrate;

b. devolatilizing said partially reacted composition in a devolatilizer;

c. cooling the resulting composition to a temperature ranging from Tc−

25°

C. to Tc+25°

C., wherein Tc is a critical temperature of an expanding system;

d. adding said expanding system to the cooled composition (b) and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating or lubricating agents, maintaining the pressure above the critical pressure of the expanding system;

e. mixing said additives and said expanding system with the polymeric composition by means of static or dynamic mixers for a selected minimum residence time;

f. optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

g. extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm;

h. reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 barg.

26. A method for producing expandable granular composite materials according to claim 1, comprising:

mass/solution polymerizing a vinyl aromatic monomer and, optionally, co-monomers;

adding a graphite material to the partially reacted mixture, whose main portion is fed as a concentrate;

devolatilizing said partially reacted composition in a devolatilizer;

cooling the resulting composition to a temperature ranging from Tc-25°

C. to Tc+25°

C., wherein Tc is a critical temperature of an expanding system;

adding said expanding system to the cooled composition (b) and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating or lubricating agents, maintaining the pressure above the critical pressure of the expanding system;

mixing said additives and said expanding system with the polymeric composition by means of static or dynamic mixers for a selected minimum residence time;

optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm; and

reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 barg.

27. A method for producing particulate, expandable composite materials according to claim 1, comprising:

i. mass/solution polymerizing a vinyl aromatic monomer and, optionally, co-monomers;

ii. devolatilizing said partially reacted composition in a devolatilizer;

iii. cooling the resulting composition to a temperature ranging from Tc-25°

C. to Tc+25°

C., wherein Tc is a critical temperature of the expanding system;

iv. preparing a side-stream comprising a graphite material whose main proportion is fed as a concentrate and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating agents and lubricating agents;

v. adding an expanding system and the side-stream (iv) to the cooled composition (iii), maintaining the pressure over the critical pressure of the expanding system;

vi. mixing said additives and said expanding system with the polymeric composition by means of static or dynamic mixers for a selected minimum residence time;

optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm; and

reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 bang.

28. A method for producing particulate, expandable composite materials according to any of the previous claim 1, comprising:

A. mass/solution polymerizing a vinyl aromatic monomer and, optionally, co-monomers;

B. devolatilizing said partially reacted composition in a devolatilizer;

C. cooling the resulting composition to a temperature ranging from Tc-25°

C. to Tc+25°

C., wherein Tc is a critical temperature of the expanding system;

D. preparing a side-stream comprising a graphite material whose main proportion is fed as a concentrate and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating agents and lubricating agents;

E. adding an expanding system and mixing it with the side-stream;

F. adding a resulting stream to the feeding of the main polymer, maintaining the pressure over a critical pressure of the expanding system; and

G. mixing said additives and said expanding system with the polymeric composition by means of static or dynamic mixers for a selected minimum residence time;

H. optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

I. extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm; and

J. reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 barg.

29. The method according to claim 25, wherein the vinyl aromatic monomer and, optionally, co-monomers, is polymerized until a conversion ranging from 60 to 90% is reached.

30. A method for producing particulate, expandable composite materials according to claim 1, comprising:

feeding a vinyl aromatic polymer to an extruder, optionally together with other (co)polymers;

cooling the resulting composition to a temperature ranging from Tc-25°

C. to Tc+25°

C., wherein Tc is a critical temperature of the expanding system;

preparing a side-stream comprising a graphite material whose main proportion is fed as a concentrate and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating agents and lubricating agents;

adding an expanding system and the side-stream to the cooled composition, maintaining the pressure over the critical pressure of the expanding system;

mixing said additives and said expanding system with the polymeric compositon by means of static or dynamic mixers for a selected minimum residence time;

optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm; and

reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 barg.

31. A method for producing particulate, expandable composite materials according to claim 1, comprising:

a1. feeding a vinyl aromatic polymer to an extruder, optionally, together with other (co)polymers;

b1. polymerizing a vinyl aromatic polymer and, optionally, co-monomers, until a conversion ranging from 60 to 90% is reached;

c1. devolatilizing said partially reacted composition (b1) in a devolatilizer;

d1. mixing the polymeric stream resulting from step (a1) with the stream resulting from step (c1), in a mass ratio (a1);

(c1) within the range of 5;

95 to 45;

55; and

e1. cooling the resulting composition to a temperature ranging from Tc-25°

C. to Tc+25°

C., wherein Tc is a critical temperature of the expanding system;

f1. preparing a side-stream comprising a graphite material whose main proportion is fed as a concentrate and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating agents and lubricating agents;

g1. adding an expanding system and the side-stream to the cooled composition, maintaining the pressure over the critical pressure of the expanding system;

h1. mixing said additives and said expanding system with the polymeric composition by means of static or dynamic mixers for a selected minimum residence time;

i1. optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

j1. extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm; and

k1. reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 barg.

32. A method for the production of particulate, expandable composite materials according to claim 30, wherein up to 50% by weight of the polymers fed to said extruder consists of particulate, expandable polystyrene, having an undesired particle size, and waste material.

33. A method for producing particulate, expandable composite materials according to claim 1, comprising:

a2. polymerizing a vinyl aromatic monomer, and optionally co-monomers, until a conversion ranging from 60 to 90% is reached;

b2. devolatilizing said partially reacted composition in a devolatilizer;

c2. feeding a graphite material whose main proportion is fed as a concentrate and, optionally, other additives, to a tank of the devolatilizer, in correspondence with discharging the devolatilized composition;

d2. cooling the resulting composition to a temperature ranging from Tc-25°

C. to Tc+25°

C., wherein Tc is a critical temperature of an expanding system;

e2. adding said expanding system to the cooled composition and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating or lubricating agents, maintaining the pressure above the critical pressure of the expanding system;

f2. mixing said additives and said expanding system with the polymeric composition by means of static or dynamic mixers for a selected minimum residence time;

g2. optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

h2. extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm; and

i2. reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 barg.

34. A method for producing particulate, expandable composite materials according to claim 1, comprising:

a3. polymerizing a vinyl aromatic monomer and, optionally, co-monomers until a conversion ranging from 60 to 90% is reached;

b3. devolatilizing said polymerized composition in a devolatilizer;

c3. adding a graphite material whose main proportion is fed as a concentrate and, optionally, other additives to the devolatilized composition (b3), in a discharge stream of a pump which collects the composition from the devolatilizer;

d3. cooling the resulting composition to a temperature ranging from Tc-25°

C. to Tc+25°

C., wherein Tc is a critical temperature of an expanding system;

e3. adding said expanding system to the cooled composition and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating or lubricating agents, maintaining the pressure above the critical pressure of the expanding system;

f3. mixing said additives and said expanding system with the polymeric composition by means of static or dynamic mixers for a selected minimum residence time;

g3. optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

h3. extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm; and

i3. reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 barn.

35. A method for producing particulate, expandable composite materials according to claim 1, comprising:

a4. mixing a graphite material with at least one filler selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, derivatives of glycols, fatty acids and corresponding esters; and

at least one additive selected from the group consisting of thickening agents, dispersing agents, lubricants, flame-retardants, antioxidants and nucleating agents;

b4. bringing the mixture to such a temperature that the resulting composition is in the molten phase and at such a pressure that the vapor phase is less than 1% by weight with respect to the total weight of the mixture; and

c4. mass/solution polymerizing a vinyl aromatic monomer and, optionally, co-monomers, together with a graphite material, whose main portion is fed as a concentrate;

d4. devolatilizing said partially reacted composition in a devolatilizer;

e4. cooling the resulting composition to a temperature ranging from Tc-25°

C. to Tc+25°

C., wherein Tc is a critical temperature of an expanding system;

f4. adding said expanding system to the cooled composition and, optionally, other additives selected from the group consisting of vinyl aromatic and non-vinyl aromatic polymers, flame-retardants, antioxidants, nucleating or lubricating agents, maintaining the pressure above the critical pressure of the expanding system;

g4. mixing said additives and said expanding system with the polymeric composition by means of static or dynamic mixers for a selected minimum residence time;

h4. optionally, cooling the resulting mixture to at least 50°

C. more than the glass transition temperature of the vinyl aromatic polymer;

i4. extruding said mixture through die holes, the diameters of said holes being within the range of 0.3 to 1.5 mm; and

j4. reducing said extruded mixture to granules having a volume ranging from 0.03 to 8 mm³ with a set of rotating knives, in an interrupted water spray granulator, pressurized at over 1.5 barg;

wherein the mixture (b4) is the concentrate of graphite material.

36. A method for producing particulate, expandable composite materials according to claim 25, wherein the graphite material is fed as a concentrate, in a proportion ranging from 80 to 100% by weight, with respect to the overall weight of the graphite material, the remaining 0-20% being fed as such.