PRODUCTION OF GRAFTED POLYETHYLENE FROM RENEW ABLE MATERIALS, THE OBTAINED POLYETHYLENE AND USES THEREOF

• US 20110152454A1
• Filed: 07/27/2009
• Published: 06/23/2011
• Est. Priority Date: 07/29/2008
• Status: Active Grant

• Current Assignee: SK Geo Centric Company Limited
• Original Assignee: Arkema France (Arkema)
• Inventors: Roussel, Thomas, Chopinez, Fabrice, Pradel, Jean-Laurent, Le, Guillaume, Devisme, Samuel
• Granted Patent: US 9,045,577 B2
• Time in Patent Office: Days
• US Class Current: 525/53
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: B32B 2270/00 Resin or rubber layer containing a blend of at least two different polymers
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/18 characterised by the use of special additives
• CPC Class Codes: B32B 27/30 comprising vinyl (co)polymers; comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/327 comprising polyolefins obtained by a metallocene or single-site catalyst
• CPC Class Codes: B32B 27/34 comprising polyamides
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 2/00 Processes of polymerisation
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/08 Low density, i.e. < 0.91 g/cm3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 255/02 on to polymers of olefins having two or three carbon atoms
• CPC Class Codes: C08F 8/46 : Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
• CPC Class Codes: C08L 2666/02 : Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/06 : grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Abstract

The invention relates to a method for production of grafted polyethylene comprising the following steps: a) fermentation of primary renewable material with optional purification to give at least one alcohol chosen from ethanol or a mixture of alcohols comprising ethanol; b) dehydration of the alcohol obtained to give in a first reactor at least one alkene selected from ethylene and mixtures of alkenes containing ethylene and optional purification of the alkene to give ethylene; c) polymerization, in a second reactor, of the ethylene to give polyethylene; d) isolation of the polyethylene obtained in step c); e) grafting the polyethylene with at least one grafting monomer selected from the unsaturated carboxylic acids or theifunctional derivatives thereof, the unsaturated dicarboxylic acids having 4-10 carbon atoms and the functional derivatives thereof being C₁-C₈ alkyl esters or glycidyl ester derivatives of the unsaturated carboxylic acids and the metal salts of the unsaturated carboxylic acids. The invention further relates to the grafted polyethylene obtained by said method, the copolymers and compositions comprising said polyethylene and the use of said polyethylene.

Claims

1. A process for the manufacture of grafted polyethylene, comprising the following stages:

a) fermenting one or more renewable starting materials optionally including purification, to produce ethanol or mixtures of alcohols comprising ethanol;

b) dehydrating of the said alcohol(s) obtained in order to produce, in a first reactor, ethylene or mixtures of alkenes comprising ethylene optionally including purification of the alkene in order to obtain ethylene;

c) polymerizing, in a second reactor, said ethylene to give polyethylene;

d) isolating said polyethylene obtained on conclusion of stage c);

e) grafting of the polyethylene with at least one grafting monomer chosen from unsaturated carboxylic acids or their functional derivatives, unsaturated dicarboxylic acids having from 4 to 10 carbon atoms and their functional derivatives, C₁-C₈ alkyl esters of unsaturated carboxylic acids or glycidyl ester derivatives of unsaturated carboxylic acids, or metal salts of unsaturated carboxylic acids.

2. The process for the manufacture of polyethylene as claimed in claim 1, wherein the renewable starting materials are plant materials chosen from sugar cane and sugar beet, maple, date palm, sugar palm, sorghum, American agave, corn, wheat, barley, rice, potato, cassava, sweet potato or algae.

3. The process for the manufacture of polyethylene as claimed in claim 1, in which the grafting monomer is maleic anhydride.

4. The process for the manufacture of polyethylene as claimed in claim 3, in which the maleic anhydride is obtained from renewable starting materials.

5. The process for the manufacture of polyethylene as claimed in claim 1, wherein a purification stage is carried out during stage a) or during stage b).

6. The process for the manufacture of polyethylene as claimed in claim 1, wherein the polyethylene prepared in stage c) is metallocene linear low-density polyethylene, “

m-LLDPE”

(m-LLDPE), prepared according to a solution method using a metallocene catalyst.

12. A coextrusion tie comprising a cografted blend of at least one cografting polymer and of a polyethylene obtained according to stages a) to d) of the process as claimed in claim 1, this blend being cografted by at least one of the grafting monomers chosen from unsaturated carboxylic acids or their functional derivatives, unsaturated dicarboxylic acids having from 4 to 10 carbon atoms and their functional derivatives, C₁-C₈ alkyl esters of unsaturated carboxylic acids or glycidyl ester derivatives of unsaturated carboxylic acids, or metal salts of unsaturated carboxylic acids.

13. The coextrusion tie as claimed in claim 12, diluted in an additional polymer.

7. (canceled)

9. A composition comprising polyethylene wherein said polyethylene grafted by at least one grafting monomer chosen from unsaturated carboxylic acids or their functional derivatives, unsaturated dicarboxylic acids having from 4 to 10 carbon atoms and their functional derivatives, C₁-C₈ alkyl esters of unsaturated carboxylic acids or glycidyl ester derivatives of unsaturated carboxylic acids, or metal salts of unsaturated carboxylic acids, wherein at least a portion of the carbon atoms in the of polyethlene backbone or the grafting monomer, or both are of renewable origin.

8. The composition of claim 9 comprising an amount of carbon resulting from renewable starting materials of greater than 20% by weight with respect to the total weight of carbon of the polyethylene.

10. The grafted polyethylene composition of claim 9 wherein said composition is a coextrusion tie.

11. The coextrusion tie as claimed in claim 10, diluted in an additional polymer.

14. The grafted polyethylene in the form of a coextrusion tie of claim 10 wherein said coextrusion tie is part of a multilayer structure.

15. The polyethylene composition of claim 9 wherein said composition is an impact modifier in polymers or a compatibilizer for inorganic fillers.

16. The composition of claim 8 comprising an amount of carbon resulting from renewable starting materials of greater than 50% by weight with respect to the total weight of carbon of the grafted polyethylene.