Multiple extruder assembly and process for continuous reactive extrusion

• US 20060076705A1
• Filed: 01/31/2005
• Published: 04/13/2006
• Est. Priority Date: 10/11/2004
• Status: Abandoned Application

• Current Assignee: Orrex Plastics Company, LLC
• Original Assignee: Orrex Plastics Company, LLC
• Inventors: Phadke, Shrikant V., DeCair, John J., Fowler, J. Nicholas
• Application Number:
  US11/047,472
• Publication Number:
  US 20060076705A1
• Time in Patent Office: Days
• US Class Current: 264/211.230
• CPC Class Codes: B29C 48/0011 combined with compression moulding
• CPC Class Codes: B29C 48/022 characterised by the choice of material
• CPC Class Codes: B29C 48/03 characterised by the shape of the extruded material at extrusion
• CPC Class Codes: B29C 48/2665 allowing small relative movement, e.g. adjustments for aligning the apparatus parts or for compensating for thermal expansion
• CPC Class Codes: B29C 48/29 in liquid form
• CPC Class Codes: B29C 48/295 in gaseous form
• CPC Class Codes: B29C 48/38 using two or more serially arranged screws in the same barrel
• CPC Class Codes: B29C 48/385 using two or more serially arranged screws in separate barrels
• CPC Class Codes: B29C 48/40 using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
• CPC Class Codes: B29C 48/76 Venting , drying means; Degassing means
• CPC Class Codes: B29C 48/832 Heating
• CPC Class Codes: B29C 48/834 Cooling
• CPC Class Codes: B29C 48/875 for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
• CPC Class Codes: B29K 2021/00 Use of unspecified rubbers as moulding material
• CPC Class Codes: B29K 2023/00 Use of polyalkenes or derivatives thereof as moulding material
• CPC Class Codes: B29K 2067/00 Use of polyesters or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2075/00 Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2096/04 Block polymers
• CPC Class Codes: B29K 2101/12 Thermoplastic materials
• CPC Class Codes: B29K 2105/0005 containing compounding ingredients releasing, lubricating or separating agents B29C33/56, fibers B29K2105/08, B29K2105/12; fillers B29K2105/16, recycled material B29K2105/26
• CPC Class Codes: C08F 10/00 : Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 220/00 : Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
• CPC Class Codes: C08F 222/00 : Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
• CPC Class Codes: C08F 255/00 : Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
• CPC Class Codes: C08F 8/00 : Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C

Abstract

Methods are disclosed for a novel and useful single pass extrusion process for the reactive extrusion and compounding of polymers. Traditional extruders utilized in reactive processes are of length to diameter ratios ranging from 30 to 1 to as high as 56 to 1. The process disclosed uses a series of sequential, very closely-coupled, independently driven screw extruders having a total effective length to diameter ratio much greater than 70 to 1 and as high as 132 to 1 or greater, and providing greatly extended reaction times, separate and multiple introductions of reactive and non-reactive agents and mechanical connections allowing for convenient screw changes and differential thermal expansion. The assembly is employed to economically produce grafted polyolefins, produce ionomers without employing the use of strong caustic agents, remove large volumes of unwanted polymer processing solvents and produce other reacted polymer species in one continuous pass.

Claims

1. A multiple extruder reactor apparatus for modifying in the melt state the chemical, rheological or chemical and rheological properties of a polymer or polymers that comprises in combination:

a. two or more extruders serially connected such that the output of each extruder flows directly into the feed zone of the next extruder and such that the polymer modification and transport process in the connected extruder assembly is continuous from one extruder to the next;

b. an assembly of mechanical connections and seals between the inter-connected extruders such that no un-stirred, un-contained or unregulated temperature or pressure region exists between any two so connected extruders or anywhere along the flow path of the polymer melt;

C. an assembly of mechanical connections between the multiple individual extruders and a single continuous supporting base plate or pad such that the thermal expansion and contraction of all extruder barrel and screw assemblies is not restrained along the axis of the extruder barrel and such that all rotational movement of the extruder barrels is restrained;

d. separate and independently controlled drive motors and gear reduction assemblies for each extruder allowing for equal or differing screw rpm'"'"'s in each extruder during operation;

e. a vertical side mounted access port on the connecting zone of the downstream extruders directly opposite to the entry location of the screw shafts of the upstream extruders for the removal of the upstream extruder screw shafts and the addition or removal of liquids, solids or gases during operation; and

f. multiple ports located anywhere along the extruder apparatus for the addition or removal of liquids, solids or gases.

2. An apparatus according to claim 1 wherein said extruders are twin-screw extruders.

3. An apparatus according to claim 1 wherein said extruders are of differing or equal length or diameter.

4. An apparatus according to claim 1 wherein said extruders have individual screw length to diameter ratios greater than 1 to 1 and more preferably 68 to 1 and most preferably 44 to 1.

5. An apparatus according to claim 1 wherein each said extruder is independently capable of chemical, rheological, or chemical and Theological modifications to polymers.

6. An apparatus according to claim 1 such that the axes of the barrels and screw shafts of the connected extruders are perpendicular to and co-planer with the axes of the barrels and screw shaft of each other sequentially connected extruder and the discharge end of the up stream extruder barrel is rigidly attached to a piston that in turn when the barrel is heated or cooled slides through a piston housing. Said piston housing is also the feed region of the connected downstream extruder with the screw shafts of the upstream extruder extended through the piston and the screw tips of the upstream extruder when heated extending up to the edges of the flights of the screws in the downstream extruder so to eliminate any length or region of the combined extruder assemblies flow path wherein the polymer flow is un-stirred or subject to un-regulated temperature control and more specifically not uniformly mixed, cooled, or heated.

7. A seal assembly on the piston according to claim 6 so as to allow for either high vacuum or high pressure to be present in the piston housing of claim 6.

8. An apparatus according to claim 1 wherein the feed region of the downstream extruders are mechanically sealed at the entry points of the screw shafts of the so as to allow for either high vacuum or high pressure to be present in the entirety of the combined extruders length without unintended leakage from or to the atmosphere into any region.

9. An apparatus according to claim 7 and claim 6 wherein high vacuum is a vacuum greater than 27.0 inches of mercury and a high pressure is pressure up to 69.0 bar.

10. An apparatus according to claim 6 wherein the extruder barrels are each rigidly connected to the common base plate at the feed zone of each extruder via rigid connections to the extruder gear reduction unit and further supported along each horizontal axis on multiple horizontal slide mountings placed between the extruder barrels and the base plate.

11. An apparatus according to claim 10 wherein the barrel of the downstream extruders are rigidly connected to the gear box through a lantern frame connection that is cooled to reduce heat flow to the gear box from the extruder barrel.

12. A slide mechanism according to claim 10 wherein the mounting consists of a rigid “

ell”

or “

tee”

shaped plate attached to the extruder barrel and being supported by a multiple of linear sleeve guide bearings, rollers, or low friction bearing pads and mounted so as to restrict all movements to those that are linear and parallel to the axis of the mounted extruder barrel and shafts.

13. An apparatus according to claim 1 wherein the outlet end of only the first extruder is rigidly connected to the feed zone of the second extruder and the barrels of the first extruder are not otherwise rigidly connected to the base plate via the first extruder gear reduction unit but are supported axially along the extruder barrel length by multiple horizontal slide mountings placed between the extruder barrels and the base plate.

14. A slide mechanism according to claim 13 wherein the mounting consist of a rigid “

ell”

or “

tee”

shaped plate attached to the extruder barrel and being supported by a multiple of linear sleeve guide bearings, rollers, or low friction bearing pads and mounted so as to restrict all movements to those that are linear and parallel to the axis of the mounted extruder barrel and shafts.

15. A process wherein apparatus disclosed in claim 1 is used to graft one or more chemical constituents to and to optionally simultaneously or sequentially modify the viscosity of, add minerals, polymers, or solvents to, remove volatiles from, or substantially change the temperature of or perform a combination of any or all of these to the grafted or pre-grafted polymer melt.

16. Same as claim 15 wherein the polymer is an olefinic homo-polymer, copolymer or terpolymer.

17. Same as claim 16 wherein the chemical constituent is selected from the group consisting of di-carboxylic acids and their derivatives, such as esters and anhydrides and the graft to a homo-polymer and co-polymer is imparted in the presence of a free radical initiator and to a terpolymer in the absence of a free radical initiator.

18. Same as claim 17 wherein the copolymer is an ethylene/propylene copolymer and the terpolymer is ethylene/propylene/polyene terpolymer.

19. Same as claim 18 wherein the polymer undergoes de-watering followed by melt viscosity reduction.

20. Same as claim 19 wherein the melt viscosity reduction is preceded, succeeded or accompanied by graft functionalization with a carboxylic compound.

21. Same as claim 20 wherein the carboxylic compound is maleic anhydride and the free radical initiator is selected from one or more of organic peroxides including diacyl peroxides, dialkyl peroxides, hydroperoxides, peroxydicarbonates, peroxyesters, peroxyketals and more preferably di-tertiary butyl peroxide, 2,5-dimethyl-2,5 di(tertiary butyl peroxy)hexane and 2,5-dimethyl-2,5 di(tertiary butyl peroxy)hexyne-3.

22. Same as claim 21 wherein the final product has an insoluble content of less 0.1 weight % when dissolved in tetra hydro furan.

23. Same as claim 21 wherein the process is further continued to include capping of the anhydride functionality.

24. Same as claim 23 wherein the capping agent is selected from one or more of the following:

N-phenyl para-phenylene diamine, N-arylphenylene diamines, aminocarbazoles, aminoindoles, amino-indazolinones and aminomercaptotriazoles

25. Same as claim 21 wherein the process is continued to include dissolving the product in a solvent neutral oil to facilitate downstream amine capping reaction.

26. Same as claim 21 wherein the ethylene propylene copolymer is fed to the first extruder as a solution in an aliphatic hydrocarbon solvent.

27. Same as claim 25 wherein the process is further continued to include amine capping of the anhydride functionality.

28. Same as claim 25 wherein the process is continued to include dissolving the product in a solvent neutral oil to facilitate downstream amine capping reaction.

29. A process wherein apparatus disclosed in claim 1 is used to neutralize an acid functional copolymer.

30. Same as claim 29 wherein the acid functional copolymer is an olefin/multi-functional organic acid co-polymer including ethylene acrylic acid copolymer and ethylene methacrylic acid co-polymer and the neutralizing agent is one or more basic alkali metal salts alone or in combination.

31. Same as claim 29 wherein the acid functional copolymer is an ethylene/acrylic acid copolymer and the neutralizing agent is zinc oxide.

32. Same as claim 30 wherein the basic alkali metal salt is sodium carbonate.

33. Same as claim 32 wherein use of alkali metal salt facilitates neutralization at significantly lower temperature than that necessary with the corresponding alkali metal hydroxide thereby resulting in a product with significantly reduced gel content and negating the need to use exotic and expensive corrosion resistant materials for the construction of the reactive extrusion apparatus.

34. Same as claim 29 wherein the neutralized acid copolymer has a total gel count of less than 1,100 gels per 1.15 square meters of which fewer than 900 gels are of 0.2 mm diameter, fewer than 70 gels are of 0.3 mm diameter, fewer than 51 gels are of 0.4 mm diameter, fewer than 37 gels are of 0.6 mm diameter, fewer than 4 gels are of 0.8 mm diameter and no more than 1 gel greater than is of 0.8 mm diameter observed in 1.15 square meters as measured and counted on an Optical Control Systems, GmbH, model FT Film Scan Testing System.

35. A process wherein apparatus disclosed in claim 1 is used to combine processes disclosed above in claim 15 and claim 29.