Stabilized PVC products and their production

• US 5,209,931 A
• Filed: 09/19/1991
• Issued: 05/11/1993
• Est. Priority Date: 09/19/1990
• Status: Expired due to Fees

• Current Assignee: Yeda Research and Development Co. Ltd. (Weizmann Institute of Science)
• Original Assignee: Yeda Research and Development Co. Ltd. (Weizmann Institute of Science)
• Inventors: Levin, Gideon
• Primary Examiner(s): Page, Thurman K.
• Assistant Examiner(s): LEVY, NEIL S
• Application Number:
  US07/762,118
• Time in Patent Office: 600 Days
• Field of Search: 525/331.5, 525/331.6, 523/122, 424/405, 424/487
• US Class Current: 424/405
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A61K 47/32 Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers , poly(meth)acrylates, or polyvinyl pyrrolidone
• CPC Class Codes: C08F 114/06 Vinyl chloride
• CPC Class Codes: C08F 8/34 Introducing sulfur atoms or sulfur-containing groups
• CPC Class Codes: C08J 2327/06 Homopolymers or copolymers of vinyl chloride
• CPC Class Codes: C08J 3/245 Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08K 5/39 Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
• CPC Class Codes: C08L 27/06 Homopolymers or copolymers of vinyl chloride
• CPC Class Codes: Y02P 20/141 Feedstock

Abstract

Crosslinked plasticized or unplasticized PVC products having gradient crosslinking density, with a high crosslinking density on the outer surface and a low or none crosslinking density at the bulk of the product, are prepared by immersing the PVC product in a hot water solution of a crosslinking material and a phase transfer catalyst. The products obtained provide controlled release of substances occluded within the PVC matrix, thus preventing leakage of plasticizers, stabilizers and other additives, and permitting controlled slow release of substances like pesticides, fertilizers, drugs and the like, into the surrounding environment.

Claims

1. A crosslinked PVC product characterized by a gradient crosslinking density, with a high crosslinking density on the outer surface and/or near the surface and a low or none crosslinking density at the bulk of the product.

2. A crosslinked PVC product according to claim 1 wherein the PVC is crosslinked with a dithiocarbamate compound.

3. A process for the preparation of a PVC product having a crosslinked outer surface characterized by a gradient crosslinking density, with a high crosslinking density on said outer surface and a lower or no crosslinking density within the bulk of the product, the process comprising

immersing an un-crosslinked PVC product in a water solution of a water-soluble crosslinking material and a phase transfer catalyst, at a temperature of at least about 60°

C., said crosslinking material being capable of reacting with chlorine containing polymers by displacing the chlorine and then further reacting with a second chlorine to form a crosslinking network, said crosslinking material being present in an amount sufficient to be capable of diffusing into the PVC product so as to displace at least one chlorine atom along polymeric chains of said PVC to provide substituted polymer molecules, and

maintaining said PVC product within said water solution at said temperature for a time sufficient to effect diffusion of said crosslinking material and said phase transfer catalyst into the PVC product so as to effect displacement of at least one chlorine atom along polymeric chains of said PVC to provide substituted polymer molecules, and triggering a chemical crosslinking of said substituted polymer molecules to produce a crosslinked outer surface characterized by a gradient crosslinking density with a high crosslinking density on said outer surface and a low or no crosslinking density within the bulk of the PVC product.

4. A process according to claim 3 wherein the crosslinking material is a dithiocarbamate compound of the formula ##STR4## wherein R₁ is alkyl, optionally substituted by hydroxy or acyloxy, or R₁ is aralkyl;

r₂ is hydrogen or R₁, or R₁ and R₂ together with the N atom form a ring optionally containing an N, S or O atom and/or a carbonyl group and optionally condensed to a benzene ring, and X⁺ is a cation.

5. A process according of claim 4 wherein the crosslinking material is sodium diethyldithiocarbamate.

6. A process according to claim 3 wherein the crosslinking material is a bifunctional or trifunctional thiol compound of the formula HS-R-SH or R-(SH)₃, in which R is alkyl, aryl, aralkyl, heterocyclyl or a residue derived from polyethylene oxide or polypropylene oxide.

7. A process according to claim 3 wherein the phase transfer catalyst is a quaternary ammonium salt, a tertiary alkyl phosphonium salt, a C₆ -C₁₅ polyethylene oxide or a cyclic crown ether.

8. A process according to claim 3 wherein the crosslinking material is sodium diethyldithiocarbamate and the phase transfer catalyst is tetrabutylammonium chloride.

9. A process according to claim 3 wherein the water solution further contains an organic or inorganic salt.

10. A process according to claim 3 wherein the crosslinked PVC product is further treated with a water solution of an inorganic or organic salt.

11. A process according to claim 3 wherein the crosslinking material is sodium diethyldithiocarbamate and the phase transfer catalyst is tetrabutylammonium chloride.

12. A process according to claim 3 wherein the crosslinked plasticized PVC product is further reacted with a water solution containing an inorganic or an organic salt.

13. A process according to claim 12 wherein the salt has a cation selected from the group of an alkali, earth alkali and a transition metal residue and an anion selected from the group of NO₃^-, SO₄^-2, PO₄^-3 and CF₃ COO^-.

14. A process according to claim 3, wherein said PVC product is placitized, said process serving to protect the plasticized PVC product from the migration of plasticizer therefrom.

15. A process according to claim 3, wherein said uncrosslinked PVC product constitutes a PVC matrix having occluded therewithin a biochemically active compound capable of being slowly released from said PVC product.

16. A process according to claim 15, wherein said biochemically active substance is selected form the group consisting of a pesticide, a fertilizer and a drug.

17. A process according to claim 3, wherein said PVC polymer is selected from the group consisting of PVC homopolymer and PVC copolymers with polyvinyl acetate, polyvinyl alcohol or polyacrylonitrile.

18. A process according to claim 3, wherein the concentration of the phase transfer catalyst in said water solution is in the rang of 0.1-0.5% said cross-linking material is in the range of 2-10%, and said temperature is 60°

-90°

C.

19. A PVC product made by the process of claim 3.

20. A PVC product made by the process of claim 14.

21. A PVC product made by the process of claim 15.

22. A process according to claim 16 wherein the crosslinked PVC product containing the occluded substance is further reacted with a water solution containing an inorganic or organic salt.

23. A process according to claim 22 wherein the salt has a cation selected from the group of an alkali, earth alkali and a transition metal residue and an anion selected from the group of NO₃^-, SO₄^-2, PO₄^-3 and CF₃ COO^-.

24. A process for the preparation of a PVC product having a crosslinked outer surface characterized by a gradient crosslinking density, with a high crosslinking density on said outer surface and a low or no crosslinking density within the bulk of the product, the process comprising

immersing an un-crosslinked PVC product in a water solution at said temperature of a water-soluble crosslinking material and a phase transfer catalyst, at a temperature of at least about 60°

C., said crosslinking material being capable of reacting with chlorine containing polymers by displacing the chlorine and then further reacting with a second chlorine to form a crosslinking network.

maintaining said PVC product within said water solution for a time sufficient to effect diffusion of said crosslinking material and said phase transfer catalyst into the PVC product so as to effect displacement of at least one chlorine atom along polymeric chains of said PVC to provide substituted polymer molecules, and triggering a chemical crosslinking of said substituted polymer molecules,

wherein the crosslinked PVC product is further treated with a water solution of an inorganic or organic salt having a cation selected form the group consisting of an alkali, earth alkali and a tradition metal residue and an anion selected from the group consisting of NO₃ -, SO₄^-2, PO₄^-3 and CF₃ COO.