Vinylidene chloride polymer composition comprising at least one allyl cinnamate

Patent metadata

Field	Value
Publication number	US-2018355147-A1
Application number	US-201615778933-A
Country	US
Kind code	A1
Filing date	Nov 25, 2016
Priority date	Nov 27, 2015
Publication date	Dec 13, 2018
Grant date	—

Abstract

The invention pertains to an improved PVDC composition including certain cinnamate dienophiles qualified for food contact, which possess an optimized balance of effectiveness in preventing discoloration upon exposure to radiation, with no negative impact on the barrier properties, in particular cinnamates of formula (I), wherein: —each of R 1 , R 2 , R 3 , equal to or different from each other, is H or a C 1 -C 12 hydrocarbon group, to layers made therefrom, to multi-layer assemblies comprising the same, and to the use of said assemblies for packaging, in particular for packaging foodstuffs.

First claim

1 . A composition (C) comprising:
a VDC polymer, wherein the VDC polymer is a vinylidene chloride polymer; and from 0.05 to 5% wt, with respect to the weight of VDC polymer, of at least one cinnamate dienophile of formula (I):

wherein:
each of R 1 , R 2 , R 3 , equal to or different from each other, is H or a C 1 -C 12 hydrocarbon group.

2 . The composition (C) of claim 1 , wherein the amount of recurring units derived from vinylidene chloride in the VDC polymer varies from 50 to 99.5 wt %, with respect to the total weight of the VDC polymer.

3 . The composition (C) of claim 1 , wherein the VDC polymer is a copolymer comprising recurring units derived from at least one ethylenically unsaturated monomer copolymerisable with vinylidene chloride selected from the group consisting of vinyl chloride, maleic anhydride, itaconic acid, styrene, styrene derivatives, and the acrylic or methacrylic monomers corresponding to general formula (I):
CH 2 ═CR 1 R 2   (I)

wherein R 1 is chosen from hydrogen and —CH 3 and R 2 is chosen from —CN and —COR 3 , wherein R 3 is chosen from —OH and —OR 4 , wherein R 4 is a C 1 -C 18 linear or branched alkyl group optionally bearing one or more —OH groups, a C 2 -C 10 epoxy alkyl group and a C 2 -C 10 alkoxy alkyl group, and wherein R 3 is also chosen from the —NR 5 R 6 radicals, in which R 5 and R 6 , same or different, are chosen from hydrogen and C 1 -C 10 alkyl groups, optionally bearing one or more —OH groups.

4 . The composition (C) of claim 3 , wherein the ethylenically unsaturated monomer copolymerisable with vinylidene chloride is selected from the group consisting of maleic anhydride, itaconic acid, acrylic or methacrylic monomers selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylamide, N-methylolacrylamide, and N,N-di(alkyl)acrylamide.

5 . The composition (C) of claim 4 , wherein the VDC polymer is selected from the group consisting of vinylidene chloride (VDC)/methyl acrylate (MA) copolymers.

6 . The composition (C) according to claim 1 , wherein said cinnamate dienophile of formula (I) is selected from the group consisting of cinnamyl cinnamate of formula (II) and allyl cinnamate of formula (III):

7 . The composition (C) according to claim 1 , wherein the amount of said cinnamate (I) in composition (C) is of at least 0.25% wt, with respect to the weight of VDC polymer; and/or at most 4% wt, with respect to the weight of VDC polymer.

8 . A method for manufacturing composition (C) according to claim 1 , wherein the VDC polymers, the cinnamate (I), and when applicable, other ingredients, are compounded together.

9 . A layer (B) made from composition (C), according to claim 1 .

10 . A method for manufacturing the layer (B) of claim 9 by extrusion-blowing process, the method comprising:
supplying composition (C) to an extruder and bringing composition (C) into the molten state by simultaneous action of heat and shear forces; and
extruding the molten composition (C) through an annular die to form a tube, and inflating the tube with a gas as it leaves the die surface, so as to obtain a layer (B).

11 . A multi-layer assembly (A) comprising at least one layer (B), according to claim 9 , said layer (B) being assembled to at least one additional layer (O).

12 . The assembly of claim 11 , wherein materials used for providing a layer (O) assembled to a layer (B) are selected from the group consisting of polyolefins, polyethylene, polypropylene, polybutylene; polystyrenes; cellulose esters, cellulose acetate, cellulose propionate, cellulose nitrate; polyvinyl acetate; polymethyl methacrylate, polybutyl methacrylate; polyvinyl alcohol; polyvinyl acetal; polyallyl alcohol; polyallyl acetate; polyesters, polyethylene terephthalate; polyamides, and nylon.

13 . The assembly of claim 12 , wherein at least one layer (O) is made from a thermoplast composition comprising a polyethylene (PE) and/or wherein at least one layer (O) is made from a thermoplast composition comprising an ethylene-vinyl acetate copolymer (EVA).

14 . The assembly of claim 11 , which is a multi-layer assembly wherein a layer (B) of composition (C) is sandwiched between an outer layer (O) and inner layer (O), optionally through the use of one or more than one additional adhesive or tie-layer (T).

15 . A method of making the assembly of claim 11 , wherein layer (B) is incorporated into an assembly created by coextrusion lamination, adhesive lamination, cast sheet extrusion, tubular water quenched extrusion, air blown extrusions or other film-making process.

16 . A package made from the assembly (A) according to claim 11 , said package being selected from the group consisting of conventional pouches, boil-in-bag pouches, turkey bags, shrinkable pouches, grease resistant pouches, rust and mold inhibiting films, pouches and bags, red meat protective film, pouches and bags, moisture control films, vacuum forming raw material, window films, improved weathering films, improved abuse resistant films at a wide range of temperatures, drum and other container liners, bread wraps, wrapping for cheese, containers which are required to be resistant to gas and liquid transmission for medicine, pharmaceuticals, cosmetics, perfumes and the like, pipe line wrapping, floor tiles, bottle cap liners, and crown cap liners.

17 . The composition (C) of claim 2 , wherein the amount of recurring units derived from vinylidene chloride in the VDC polymer varies from 60 to 98 wt %, with respect to the total weight of the VDC polymer.

18 . The composition (C) of claim 17 , wherein the amount of recurring units derived from vinylidene chloride in the VDC polymer varies from 85 to 90 wt %, with respect to the total weight of the VDC polymer.

19 . The composition (C) of claim 5 , wherein the VDC polymer is selected from the group consisting of vinylidene chloride (VDC)/methyl acrylate (MA) copolymers having a weight ratio VDC/MA of 90/10 to 94/6.

20 . The composition (C) according to claim 7 , wherein the amount of said cinnamate (I) in composition (C) is of at least 0.5% wt, with respect to the weight of VDC polymer; and at most 3% wt, with respect to the weight of VDC polymer.

Assignees

• Solvay
• Univ Aix Marseille
• Centre Nat Rech Scient

Inventors

• Chauvet Elodie
• Gigmes Didier
• Guillaneuf Yohann
• Chapotot Agnès
• Vinas Jérôme
• Dewael Pascal
• Vanderveken Yves

Classifications

• B32B27/34

  comprising polyamides · CPC title

• C07C57/44

  Cinnamic acid · CPC title

• B32B2439/80

  Medical packaging · CPC title

• C07C69/618

  having unsaturation outside the six-membered aromatic ring · CPC title

• B32B27/36

  comprising polyesters · CPC title