Composite product and a process for producing said product

1. A method of making a foamed cellulosic fiber-thermoplastic composite article comprising:

A) providing a copolymer composition that includes:

i) at least about 20 wt. % of a copolymer formed by polymerizing a mixture comprising:

a) about 51% to about 99.9% by weight of one or more primary monomers, and

b) about 0.1% to about 49% by weight of one or more anhydride containing monomers;

B) combining about 30% to about 99.9% by weight of the copolymer composition with about 0.01% to about 70% by weight of one or more cellulosic fibers based on the weight of the combination;

C) applying an amount of heat, mixing energy and pressure sufficient to:

i) mix the copolymer composition and the cellulosic fibers;

ii) react anhydride groups in the copolymer with hydroxyl groups in the cellulosic fibers; and

iii) produce a blowing agent as a byproduct of the reaction in ii) and provide a foamable mixture of the copolymer composition and the cellulosic fibers; and

D) forming the foamed article by placing the foamable mixture in a molding or extruding operation;

wherein the foamed article has a structured foam central portion and micro foamed outer portion that surrounds the structured foam portion and has a higher density than the structured foam central portion;

wherein the micro foamed outer portion comprises from about 5 to about 22 percent of an overall thickness of the foamed article;

wherein at least 10% of the cellulosic fibers of B) were thermally modified to reduce an amount of available hydroxyl groups prior to being combined with the copolymer composition and wherein at least 5% of the cellulosic fibers of B) were not thermally modified, and,

wherein the thermal modification of the cellulosic fibers is performed by heating at a temperature of from 160° C. to 250° C. at atmospheric pressure or at a temperature of from 120° C. to 230° C. at a pressure higher than atmospheric pressure.

2. A method according to claim 1 , wherein the cellulosic fibers have been thermally modified by heat treatment at a temperature from 160 to 250° C. at atmospheric pressure.

3. A method according to claim 1 , wherein at least 30% of the cellulosic fibers have been thermally modified prior to being combined with the copolymer composition.

4. A method according to claim 3 , wherein at least 50% of the cellulosic fibers have been thermally modified prior to being combined with the copolymer composition.

5. A method according to claim 3 , wherein the thermally modified cellulosic fibers are mixed with the non-thermally modified cellulosic fibers prior to being combined with the copolymer composition.

6. The method according to claim 1 , wherein the foamed article has a density of not more than 1.3 g/cm 3 .

7. The method according to claim 1 , wherein the primary monomers are selected from the group consisting of styrenic monomers and olefinic monomers and combinations thereof.

8. The method according to claim 7 , wherein the styrenic monomers are selected from the group consisting of styrene, p-methyl styrene, α-methyl styrene, tertiary butyl styrene, dimethyl styrene, nuclear brominated or chlorinated derivatives thereof and combinations thereof and the olefinic monomers are selected from the group consisting of ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene; 2-butene; 2-pentene; 2-hexene; 2-octene; and combinations thereof.

9. The method according to claim 1 , wherein the anhydride containing monomers include one or more monomers according to Formulas I and II: wherein R 1 , R 2 and R 4 are each independently H or a C 1 -C 8 linear, branched or cyclic alkyl or alkenyl radical and R 3 is a C 1 -C 8 linear or branched alkyl group—

10. The method according to claim 1 , wherein the other monomers are one or more selected from the group consisting of divinylbenzene; conjugated dienes; C 1 -C 12 linear, branched or cyclic alkyl mono- or di-esters of maleic acid, fumaric acid and itaconic acid; C 1 -C 12 linear, branched or cyclic alkyl esters of acrylic acid, C 1 -C 12 linear, branched or cyclic alkyl esters of methacrylic acid; acrylonitrile; methacrylonitrile; and combinations thereof.

11. The method according to claim 1 , wherein the weight average molecular weight of the copolymer is from about 20,000 to about 1,000,000.

12. The method according to claim 1 , wherein the elastomeric polymers are selected from the group consisting of homopolymers of butadiene or isoprene; random, block, AB diblock, or ABA triblock copolymers of a conjugated diene with a styrenic monomer and/or acrylonitrile; ABS; copolymers of C 1 -C 12 linear, branched or cyclic olefins and C 1 -C 12 linear, branched or cyclic alkyl esters of (meth)acrylic acid, diblock and triblock copolymers of styrene-butadiene, styrene-butadiene-styrene, styrene-isoprene, styrene-isoprene-styrene, partially hydrogenated styrene-isoprene-styrene and combinations thereof.

13. The method according to claim 1 , wherein the cellulosic fibers have a diameter of at least 0.1 μm.

14. The method according to claim 1 , wherein the foamable mixture comprises one or more additives selected from the group consisting of heat stabilizers, light stabilizers, plasticizers, dyes, pigments; anti-blocking agents; slip agents; lubricants; coloring agents; antioxidants; ultraviolet light absorbers; fillers; anti-static agents; impact modifiers, antimicrobial agents, and combinations thereof.

15. The method according to claim 1 , wherein the copolymer and elastomeric copolymer are combined by melt blending.

16. The method according to claim 1 , wherein the copolymer composition and cellulosic fibers are combined by melt blending.

17. The method according to claim 1 , wherein the copolymer, cellulosic fiber and optional elastomeric polymers and/or optional other additives are dry blended and added to an extruder.

18. The method according to claim 1 , wherein the copolymer and optionally the elastomeric polymer are added to a first extruder and then combined with the cellulosic fiber and optional other additives in a second extruder.

19. The method according to claim 1 , wherein the combination of the copolymer composition and cellulosic fibers is extruded by melt mixing at a temperature sufficient for the copolymer to flow and extruding the combination through an extruder die one or more times.

20. The method according to claim 1 , wherein the extruding operation comprises one or more single-screw extruders and/or twin-screw extruders.

21. The method according to claim 20 , wherein the extruding operation comprises maintaining sufficient pressure in one or more extruders to prevent the blowing agent from escaping from the foamable mixture.

22. The method according to claim 1 , wherein the byproduct blowing agent is selected from the group consisting of water vapor, carbon dioxide or combinations thereof.

23. The method according to claim 1 , wherein the extruding operation comprises discharging the foamable mixture from an extruder into a die or other shaping device that causes the foamable mixture to expand to form a foamed article having a desired shape and or dimension.

24. The method according to claim 1 , wherein the molding operation comprises:

A) feeding the foamable mixture into an extruder to form pellets;

B) placing the pellets in a mold corresponding to the desired shape of the foamed article; and

C) heating the mold and pellets to cause the pellets to expand and fuse to form the foamed article.

25. The method according to claim 1 , wherein the foamed article comprises a micro foamed portion having a density of from about 0.6 to about 1.3 g/cm 3 .

26. The method according to claim 1 , wherein the foamed article comprises a structured foamed portion having a density of from about 0.45 to about 0.80 g/cm 3 .

27. The method according to claim 1 , wherein the micro foamed portion has a density of from about 0.6 to about 1.3 g/cm 3 and the structured foamed portion has a density of from about 0.45 to about 0.80 g/cm 3 .

28. The method according to claim 1 , wherein the cellulosic fiber-thermoplastic composite is compounded or otherwise blended with one or more other polymers to form a cellulosic fiber-thermoplastic composite blend.

29. The method according to claim 1 , wherein about 30% to about 99.9% by weight of the copolymer composition is combined with about 25% to about 70% by weight of one or more cellulosic fibers that based on the weight of the combination; characterized in that the cellulosic fiber has been thermally modified prior to being combined with the copolymer composition.

30. The method according to claim 1 , wherein the thermal modification of the cellulosic fiber is performed by heating at a temperature of from 180° C. to 250° C. at atmospheric pressure or at a temperature of from 120° C. to 230° C. at a pressure higher than atmospheric pressure.

31. The method according to claim 1 , wherein the thermal modification is performed by heating at a temperature of from 200° C. to 250° C. at atmospheric pressure.

32. The method according to claim 1 , wherein the thermal modification takes place in an essentially oxygen-free environment.

33. The method according to claim 1 , wherein the copolymer formed by polymerizing a mixture further comprises

c) about 1% to about 25% by weight of one or more other polymerizable monomers.

34. The method according to claim 1 , wherein the copolymer composition further includes

ii) about 0.1% to about 30% by weight of one or more elastomeric polymers based on the weight of the copolymer.

35. The method according to claim 1 , wherein the cellulosic fibers have been thermally modified by heat treatment at a temperature from 200 to 230° C. at atmospheric pressure.

36. The method according to claim 1 , wherein the cellulosic fibers have been thermally modified by heat treatment at a temperature from 120° C. to 230° C. at elevated pressure.