Biodegradable graft copolymers

• US 4,891,404 A
• Filed: 05/27/1988
• Issued: 01/02/1990
• Est. Priority Date: 05/27/1988
• Status: Expired due to Fees

• Current Assignee: Purdue Research Foundation (Purdue University)
• Original Assignee: Purdue Research Foundation (Purdue University)
• Inventors: Narayan, Ramani, Biermann, Christopher J., Tsao, George T.
• Primary Examiner(s): Foelak, Morton
• Assistant Examiner(s): Nutter, Nathan M.
• Application Number:
  US07/199,999
• Time in Patent Office: 585 Days
• Field of Search: 525/54.2, 525/54.21, 525/54.24
• US Class Current: 525/54.2
• CPC Class Codes: C08F 251/00 Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof

Abstract

A nucleophilic displacement reaction is used to prepare biodegradable thermoplastic copolymers exhibiting a high capacity for stabilizing biodegradable blends of polysaccharides and synthetic thermoplastic polymers. The graft copolymers are characterized by consistent product uniformity and a high degree of substitution on the polysaccharide chain.

Claims

1. Method for converting a polysaccharide to a biodegradable thermoplastic graft copolymer capable of forming homogeneous blends with synthetic thermoplastic polymers, said method comprising the steps of

chemically treating said polysaccharide to form on said polysaccharide nucleophilically displaceable groups at a substitution level of about 0.1 to about 0.75 nucleophilic displaceable groups per anhydroglucose unit of said polysaccharide;

forming an anionic polymer of the formula ##STR4## wherein R₁ is C₁ -C₆ alkyl or a group of the formula ##STR5## by (1) anionic polymerization of a compound of the formula R--CR═

CH₂ and (2) treatment with a compound of the formula X═

C═

Z, wherein in the above formulas R and R'"'"' are independently hydrogen, C₁ -C₆ alkyl, phenyl, substituted phenyl or methoxycarbonyl;

X and Z are each independently O or S;

M⁺ is an alkali metal cation; and

n is an integer such that the group ##STR6## has a molecular weight between about 3000 and about 25,000;

reacting said anionic thermoplastic polymer with said polysaccharide-bearing nucleophilically displaceable groups under conditions conducive to nucleophilic displacement of said groups by said anionic polymer; and

isolating the resulting biodegradable thermoplastic graft copolymer.

2. The method of claim 1 wherein the nucleophilic displaceable group is methanesulfonyloxy or arylsulfonyloxy.

3. The method of claim 1 wherein the polysaccharide is selected from the group consisting of starch, lignin, chitin and cellulose.

4. The method of claim 1 wherein the polysaccharide is a cellulose ether or cellulose ester.

5. The method of claim 1 wherein the polysaccharide is cellulose acetate.

6. The method of claim 1 wherein X and Z are O.

7. The method of claim 1 wherein X and Z are S.

8. The biodegradable thermoplastic graft copolymer prepared in accordance with the method of claim 1.

9. The biodegradable thermoplastic graft copolymer prepared in accordance with the method of claim 5.

10. The biodegradable thermoplastic graft copolymer prepared in accordance with the method of claim 6.

11. The biodegradable thermoplastic graft copolymer prepared in accordance with the method of claim 7.

12. A biodegradable thermoplastic polymer blend comprising a synthetic thermoplastic polymer and a biodegradable thermoplastic graft copolymer prepared in accordance with the method of claim 1.

13. A homogeneous biodegradable thermoplastic polymer blend comprising a synthetic thermoplastic polymer, a polysaccharide, and a biodegradable thermoplastic graft copolymer prepared in accordance with the method of claim 1.

14. An article of manufacture comprising the biodegradable thermoplastic graft copolymer of claim 8.

15. An article of manufacture comprising the biodegradable thermoplastic raft copolymer of claim 9.

16. An article of manufacture comprising the biodegradable thermoplastic graft copolymer of claim 10.

17. An article of manufacture comprising the biodegradable polymer blend of claim 12.

18. An article of manufacture comprising the biodegradable polymer blend of claim 13.

19. Method for converting a polysaccharide to a biodegradable thermoplastic graft copolymer capable of forming homogeneous blends with synthetic thermoplastic polymers, said method comprising the steps of:

chemically treating said polysaccharide to form on said polysaccharide nucleophilically displaceable groups at a substitution level of about 0.1 to about 0.75 nucleophilically displaceable groups per anhydroglucose unit of said polysaccharide, said nucleophilic displaceable groups selected from the group consisting of halo, sulfonate, sulfate haloacetoxy, loweralkanesulfonyloxy benzylsulfonytoxy and arylsulfonyloxy;

reacting said polysaccharide bearing nucleophilic displaceable groups with an anionic thermoplastic polymer carboxylate or thiocarboxylate under conditions conducive to nucleophilic displacement of said groups by said anionic carboxylate or thiocarboxylate; and

isolating the resulting biodegradable thermoplastic graft copolymer characterized by uniformity of degree of polymerization of the grafted anionic polymer groups and a degree of substitution on the polysaccharide chain such that there is at least one anionic polymer group for every 15 to 50 anhydroglucose units in the polysaccharide.

20. The method of claim 19 wherein the anionic thermoplastic polymer is a polyamide carboxylate.

21. The method of claim 19 wherein the anionic thermoplastic polymer is polystyryl carboxylate.

22. The method of claim 19 wherein the anionic thermoplastic polymer is hydrolyzed poly(methyl methacrylate).