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EP-3529300-B1 - PLASTICIZED PVC ADMIXTURES WITH SURFACE MODIFYING MACROMOLECULES AND ARTICLES MADE THEREFROM

EP3529300B1EP 3529300 B1EP3529300 B1EP 3529300B1EP-3529300-B1

Inventors

  • CHANG, WEILUN
  • HO, JEANNETTE
  • SANTERRE, PAUL J.
  • MULLICK, SANJOY

Dates

Publication Date
20260506
Application Date
20171018

Claims (13)

  1. A blended composition comprising from 50% to 99.9% (w/w) of a polyvinyl chloride base polymer, from 0.1 % to 80% (w/w) of a plasticizer, and from 0.01% to 20% (w/w) of a surface modifying macromolecule (SMM), wherein said SMM is described by the formula: F T -[B-A] n -B-F T , where (i) A comprises poly(diethylene glycol)adipate, (neopentyl glycol-ortho phthalic anhydride) polyester, (diethylene glycol-ortho phthalic anhydride) polyester, (1,6-hexanediol-ortho phthalic anhydride) polyester, polypropylene oxide, polyethylene oxide, or polytetramethylene oxide; (ii) B comprises a urethane; (iii) F T is a polyfluoroorgano group, and (iv) n is an integer from 1 to 10; and wherein the plasticizer is selected from trimellitates, adipates, dioctyl terephthalate and orthophthalates selected from n-octyl n-decyl phthalate, di(2-propyl heptyl) phthalate, diundecyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, din-propyl phthalate, di-n-butyl phthalate, butyl cyclohexyl phthalate, di-n-pentyl phthalate, din-hexyl phthalate, butyl decyl phthalate, diisohexyl phthalate, diisoheptyl phthalate, diisooctyl phthalate, diisotridecyl phthalate, ditridecyl phthalate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, di-isotridecyl phthalate, di-C16-18 alkyl phthalate, benzyl 3-isobutyryloxy-1-isopropyl-2,2-dimethylpropyl phthalate, benzyl C7-9-branched and linear alkyl phthalate, and di-(2-ethylhexyl) phthalate.
  2. The composition of claim 1, wherein the plasticizer is 10% to 50% (w/w).
  3. The composition of claim 2, wherein the plasticizer is 20% to 45% (w/w).
  4. The composition of any of claims claim 1-3, wherein the amounts of said polyvinyl chloride base polymer, said plasticizer, and SMM provide a miscible admixture.
  5. The composition of claim 1, wherein said plasticizer is di-(2-ethylhexyl)phthalate (DEHP).
  6. The composition of claim 1, wherein said plasticizer is tri-(2-ethylhexyl)trimellitate (TOTM).
  7. The composition of claim 1, wherein said plasticizer is dioctyl terephthalate (DEHT).
  8. The composition of any of claims 1-7, said composition comprising from 60% to 80% (w/w) of said polyvinyl chloride base polymer, from 20% to 40% (w/w) of said plasticizer, and from 0.5% to 5% (w/w) of said SMM.
  9. The composition of any of claims 1-8, further comprising one or more additives selected from the group consisting of a heat stabilizer, an impact modifier, a process aid, a lubricant, a filler, a flame retardant, a pigment, a blowing agent, a biocide, a viscosity modifier, an antistatic agent, an antioxidant, a UV absorber, an antifogging agent, and a bonding agent.
  10. An article comprising the composition of any of claims 1-9.
  11. The article of claim 10, wherein said article is transparent.
  12. The article of claim 11, wherein said article is an implantable device.
  13. A method for making an article comprising the steps of: (a) preparing a blended composition of any of claims 1-9; and (b) processing said composition to form or to coat said article.

Description

Field of the Invention The present invention relates to specific polyvinvyl chloride (PVC) admixtures, in the following referred to as blended compositions as well, with plasticizers and surface modifying macromolecules, and compositions and methods of preparing articles made from the admixtures. Background One of the most common base polymers used in molded articles (e.g., medical devices, tubing) is polyvinylchloride (PVC). However, PVC is hard and brittle, and thus plasticizers are often added to make the PVC flexible and more appropriate for a particular use. Di-(2-ethylhexyl)-phthalate (DEHP) is the most widely used plasticizer in PVC and medical devices made from PVC. However, DEHP is not chemically bound to PVC and leaches from the PVC with time and use. The potential for DEHP to produce adverse effects in humans has been the subject of considerable discussion and debate in the scientific community, and thus there exists a need for PVC admixtures that exhibit reduced leaching of plasticizers. GB 1 600 600 A discloses a solid essentially homogeneous plasticiser composition, which composition consists essentially of: (a) the phthalate ester of an aliphatic alcohol containing from 5 to 12 carbon atoms in the aliphatic moiety; and, intimately mixed therewith, (b) an hydroxy terminated thermoplastic polyurethane resin having an NCO index of from 60 to 100 which is the reaction product of a di-isocyanate and a polyester polyol based on at least two dicarboxylic acids, one of which is terephthalic acid, and at least one diol. WO 2016/095042 A1 discloses specific ester-linked surface-modifying macromolecules and admixtures thereof. Summary of the Invention The invention is directed to specific PVC admixtures including one or more plasticizers and surface modifiers that reduce the amount of the leaching of plasticizing agent from the admixture as described in claim 1. In particular embodiments, the admixtures are transparent. Further preferred embodiments are set out in the dependent claims. The blended composition according to the present invention includes from 50% to 99.9% (w/w) of a polyvinyl chloride base polymer (e.g. 60% ± 10%, 70% ± 10%, or 80% ± 10%, (w/w)), from 0.1% to 80% (w/w) of a plasticizer (e.g., 5% ± 4%, 15% ± 10%, 20% ± 15%, 30% ± 10%, 40% ± 10%, 50% ± 10%, 60% ± 10%, or 70% ± 10% (w/w)), and from 0.01% to 20% (w/w) of a surface modifying macromolecule (SMM) (e.g., 0.2% ± 0.1%, 0.3% ± 0.1%, 0.4% ± 0.2%, 1.0% ± 0.5%, 1.5% ± 0.5%, 2.0% ± 0.5%, 3.0% ± 0.5%, 3.5% ± 0.5%, 4.0 % ± 0.5%, 4.5 % ± 1.5%, 5% ± 2.0%, 6% ± 2%, 7% ± 4%, 8% ± 4%, 10% t 3%, 12% ± 3%, 14% ± 3%, or 16% ± 4% (w/w)). In some embodiments, the blended composition includes from 10% to 50% (w/w) plasticizer. In still other embodiments, the blended composition includes from 20% to 45% (w/w) plasticizer. In some embodiments, the amounts of the polyvinyl chloride base polymer, the plasticizer, and the SMM in the blended composition produce a miscible admixture. The plasticizer in the blended composition is selected from trimellitates, adipates, dioctyl terephthalate and orthophthalates selected from n-octyl n-decyl phthalate, di(2-propyl heptyl) phthalate, diundecyl phthalate, diisononyl phthalate, diisodecyl phthalate, diisoundecyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, butyl cyclohexyl phthalate, di-n-pentyl phthalate, di-n-hexyl phthalate, butyl decyl phthalate, diisohexyl phthalate, diisoheptyl phthalate, diisooctyl phthalate, diisotridecyl phthalate, ditridecyl phthalate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, di-isotridecyl phthalate, di-C16-18 alkyl phthalate, benzyl 3-isobutyryloxy-1-isopropyl-2,2-dimethylpropyl phthalate, benzyl C7-9-branched and linear alkyl phthalate, and di-(2-ethylhexyl) phthalateFor example, the plasticizer can be an orthophthalate, such as di-(2-ethylhexyl)phthalate (DEHP). Alternatively, the plasticizer can be tri-(2-ethylhexyl)trimellitate (TOTM) or dioctyl terepththalate (DEHT). The SMM in the blended composition is described by the formula:         FT-[B-A]n-B-FT, wherein: (i) A comprises poly(diethylene glycol)adipate, (neopentyl glycol-ortho phthalic anhydride) polyester, (diethylene glycol-ortho phthalic anhydride) polyester, (1,6-hexanediol-ortho phthalic anhydride) polyester, polypropylene oxide, polyethylene oxide, or polytetramethylene oxide; (ii) B comprises a urethane; (iii) FT is a polyfluoroorgano group, and (iv) n is an integer from 1 to 10. In some embodiments, the blended composition includes from 60% to 80% (w/w) of the polyvinyl chloride base polymer, from 20% to 40% (w/w) of the plasticizer, and from 0.5% to 5% (w/w) of the SMM. In some embodiments, the blended composition includes one or more additives selected from the group consisting of a heat stabilizer, an impact modifier, a process aid, a lubricant, a filler, a flame retardant, a pigment, a blowing agent, a biocide, a viscosity modifier, an antistatic agent, an