DURABLE HIGH STRENGTH POLYMER COMPOSITES SUITABLE FOR IMPLANT AND ARTICLES PRODUCED THEREFROM

• US 20170239042A1
• Filed: 01/30/2017
• Published: 08/24/2017
• Est. Priority Date: 04/01/2011
• Status: Active Grant

• Current Assignee: W. L. Gore & Associates (W.L. Gore & Associates)
• Original Assignee: W. L. Gore & Associates (W.L. Gore & Associates)
• Inventors: Bruchman, William C., Gassler, Paul D., Hartman, Cody L., Walsh, Peter J., White, Charles F.
• Granted Patent: US 10,470,878 B2
• Time in Patent Office: Days
• CPC Class Codes: A61F 2/2412 with soft flexible valve members, e.g. tissue valves shaped like natural valves check valves with flexible valve members in general F16K15/14
• CPC Class Codes: A61F 2/2415 Manufacturing methods
• CPC Class Codes: A61F 2/2418 Scaffolds therefor, e.g. support stents
• CPC Class Codes: A61F 2/2472 Devices for testing
• CPC Class Codes: A61F 2220/0075 sutured, ligatured or stitched, retained or tied with a rope, string, thread, wire or cable
• CPC Class Codes: A61F 2230/0054 V-shaped
• CPC Class Codes: A61L 2430/20 for reconstruction of the heart, e.g. heart valves
• CPC Class Codes: A61L 27/26 Mixtures of macromolecular compounds
• CPC Class Codes: A61L 27/48 with macromolecular fillers
• CPC Class Codes: A61L 27/507 for artificial blood vessels apparatus for applying cells on a blood vessel prosthesis A61F2/062
• CPC Class Codes: A61L 27/56 Porous materials, e.g. foams or sponges
• CPC Class Codes: C08L 27/12 containing fluorine atoms
• CPC Class Codes: Y10T 156/10 Methods of surface bonding and/or assembly therefor

Abstract

Thin, biocompatible, high-strength, composite materials are disclosed that are suitable for use in a valve for regulating blood flow direction. In one aspect, the composite material maintains flexibility in high-cycle flexural applications, making it particularly applicable to high-flex implants such as a prosthetic heart valve leaflet. The composite material includes a porous polymer membrane and an elastomer, wherein the elastomer fills substantially all of the pores of the porous polymer membrane.

Claims

1-110. -110. (canceled)

111. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and an elastomeric material, the at least one synthetic polymer membrane comprising fibers that define space therebetween, wherein a diameter of a majority of the fibers is less than about 1 μ

m, the space between the fibers defining pores, the elastomeric material being disposed in substantially all of the pores.

112. The valve of claim 111, wherein the composite material further includes a layer of the elastomeric material.

113. The valve of claim 111, wherein the composite material comprises elastomeric material by weight in a range from about 10% to about 90%.

114. The valve of claim 111, wherein the elastomeric material is a TFE/PMVE copolymer.

115. The valve of claim 114, wherein the TFE/PMVE copolymer consists essentially of between about 40 and 80 weight percent perfluoromethyl vinyl ether and complementally 60 and 20 weight percent tetrafluoroethylene.

116. The valve of claim 111, wherein the elastomeric material is a fluoroelastomer.

117. The valve of claim 111, wherein the elastomeric material is a TFE/PMVE (tetrafluoroethylene-perfluoromethylvinyl ether) copolymer.

118. The valve of claim 111, wherein the elastomeric material is selected from the group consisting of TFE/PMVE (tetrafluoroethylene-perfluoromethylvinyl ether) copolymer, TFE-PAVE (tetrafluoroethylene-perfluoro (alkyl vinyl ether)) copolymer, FEP (fluorinated ethylene propylene), fluoroelastomers, silicones, and urethanes.

119. The valve of claim 111, wherein the at least one synthetic polymer membrane is fluoropolymer membrane.

120. The valve of claim 111, wherein the at least one synthetic polymer membrane is porous polyethylene membrane.

121. The valve of claim 120, wherein the porous polyethylene membrane has a matrix tensile strength in at least one direction greater than about 150 MPa.

122. The valve of claim 111, wherein the leaflet has a thickness of less than about 350 μ

m.

123. The valve of claim 111, wherein the pores have a pore size that is less than about 5 μ

m.

124. The valve of claim 111, wherein the pores have a pore size that is less than about 1 μ

m.

125. The valve of claim 111, wherein the pores have a pore size that is less than about 0.1 μ

m.

126. The valve of claim 111, wherein the diameter of a majority of the fibers is less than about 0.1 μ

m.

127. The valve of claim 111, wherein the at least one synthetic polymer membrane comprises substantially only of fibers.

128. The valve of claim 111, wherein the composite material comprises at least one layer of the synthetic polymer membrane.

129. The valve of claim 111, wherein the composite material comprises more than two layers of the synthetic polymer membrane.

130. The valve of claim 129, wherein the leaflet comprises a number of layers of the composite material, wherein a number of layers of the synthetic polymer membrane is defined by the number of layers of the composite material.

131. The valve of claim 130, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

132. The valve of claim 129, wherein the leaflet has at least 10 layers and the composite material comprising less than about 50% synthetic polyethylene membrane by weight.

133. The valve of claim 111, wherein the support structure is selectively diametrically adjustable for endovascular delivery and deployment at a treatment site, wherein the valve is operable to be a prosthetic heart valve.

134. The valve of claim 111, wherein the at least one synthetic polymer membrane is expanded fluoropolymer membrane, wherein the elastomeric material is a TFE/PMVE copolymer, and wherein the valve is operable to be a prosthetic heart valve.

135. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane having a plurality of pores and an elastomeric material present in substantially all of the pores, the composite material comprising elastomeric material by weight in a range from about 10% to about 90%.

136. The valve of claim 135, wherein the composite material comprises less than about 70% synthetic polymer membrane by weight.

137. The valve of claim 135, wherein the composite material comprises less than about 60% synthetic polymer membrane by weight.

138. The valve of claim 135, wherein the composite material comprises less than about 50% synthetic polymer membrane by weight.

140. The valve of claim 135, wherein the composite material further includes a layer of an elastomeric material.

141. The valve of claim 135, wherein the at least one synthetic polymer membrane is fluoropolymer membrane.

142. The valve of claim 135, wherein the synthetic polymer membrane is porous polyethylene membrane.

143. The valve of claim 142, wherein the pores are defined by a fibrous structure comprising fibers that have an average fiber diameter of less than about 1 μ

m.

144. The valve of claim 142, wherein the pores are defined by a fibrous structure comprising fibers that have an average fiber diameter of less than about 0.1 μ

m.

145. The valve of claim 135, wherein the elastomeric material is a fluoroelastomer.

146. The valve of claim 135, wherein the elastomeric material is a TFE/PMVE (tetrafluoroethylene-perfluoromethylvinyl ether) copolymer.

147. The valve of claim 135, wherein the elastomeric material is selected from the group consisting of TFE/PMVE (tetrafluoroethylene-perfluoromethylvinyl ether) copolymer, TFE-PAVE (tetrafluoroethylene-perfluoro (alkyl vinyl ether)) copolymer, FEP (fluorinated ethylene propylene), fluoroelastomers, silicones, and urethanes.

148. The valve of claim 147, wherein the TFE/PMVE copolymer consists essentially of between about 40 and 80 weight percent perfluoromethyl vinyl ether and complementally 60 and 20 weight percent tetrafluoroethylene.

149. The valve of claim 142, wherein the porous polyethylene membrane has a matrix tensile strength in at least one direction greater than about 150 MPa.

150. The valve of claim 135, wherein the leaflet has a thickness of less than about 350 μ

m.

151. The valve of claim 135, wherein the composite material comprises at least one layer of the synthetic polymer membrane.

152. The valve of claim 135, wherein the composite material comprises more than two layers of the synthetic polymer membrane.

153. The valve of claim 151, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

154. The valve of claim 142, wherein the leaflet has at least 10 layers of porous polyethylene membrane and the composite material comprising less than about 50% synthetic polyethylene membrane by weight.

155. The valve of claim 135, wherein the pores have a pore size that is less than about 5 μ

m.

156. The valve of claim 135, wherein the pores have a pore size that is less than about 1 μ

m.

157. The valve of claim 135, wherein the pores have a pore size that is less than about 0.10 μ

m.

158. The valve of claim 135, wherein the support structure is selectively diametrically adjustable for endovascular delivery and deployment at a treatment site.

159. The valve of claim 135, wherein the composite material comprises at least one layer of the synthetic polymer membrane, wherein the at least one synthetic polymer membrane is expanded fluoropolymer membrane, and wherein the elastomeric material is a TFE/PMVE copolymer.

160. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane and TFE/PMVE copolymer, the at least one synthetic polymer membrane comprising fibers that define space therebetween, wherein a diameter of a majority of the fibers is less than about 1 μ

m, the space between the fibers defining pores, the TFE/PMVE copolymer being disposed in substantially all of the pores.

161. The valve of claim 160, wherein the composite material further includes a layer of the TFE/PMVE copolymer.

162. The valve of claim 160, wherein the at least one synthetic polymer membrane is fluoropolymer membrane.

163. The valve of claim 160, wherein the at least one synthetic polymer membrane is porous polyethylene membrane.

164. The valve of claim 163, wherein the porous polyethylene membrane has a matrix tensile strength in at least one direction greater than about 150 MPa.

165. The valve of claim 160, wherein the leaflet has a thickness of less than about 350 μ

m.

166. The valve of claim 160, wherein the composite material comprises at least one layer of the synthetic polymer membrane.

167. The valve of claim 160, wherein the composite material comprises more than two layers of the synthetic polymer membrane.

168. The valve of claim 166, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

169. The valve of claim 160, wherein the support structure is selectively diametrically adjustable for endovascular delivery and deployment at a treatment site, wherein the valve is operable to be a prosthetic heart valve.

170. The valve of claim 160, wherein the pores have a pore size that is less than about 5 μ

m.

171. The valve of claim 160, wherein the pores have a pore size that is less than about 1 μ

m.

172. The valve of claim 160, wherein the pores have a pore size that is less than about 0.1 μ

m.

173. The valve of claim 160, wherein the diameter of a majority of the fibers is less than about 0.1 μ

m.

174. The valve of claim 160, wherein the at least one synthetic polymer membrane comprises substantially only of fibers.

175. The valve of claim 160, wherein the TFE/PMVE copolymer consists essentially of between about 40 and 80 weight percent perfluoromethyl vinyl ether and complementally 60 and 20 weight percent tetrafluoroethylene.

176. The valve of claim 160, wherein the composite material comprises TFE/PMVE copolymer by weight in a range from about 10% to about 90%.

177. The valve of claim 163, wherein the leaflet has at least 10 layers and the composite material comprising less than about 50% synthetic polyethylene membrane by weight.

178. A valve, comprising:

a support structure, and

at least one leaflet being supported on the support structure and movable between open and closed positions, each leaflet including a composite material comprising at least one synthetic polymer membrane having a plurality of pores and TFE/PMVE copolymer present in substantially all of the pores, the composite material comprising TFE/PMVE copolymer by weight in a range from about 10% to about 90%.

179. The valve of claim 178, wherein the composite material comprises less than about 70% synthetic polymer membrane by weight.

180. The valve of claim 178, wherein the composite material comprises less than about 60% synthetic polymer membrane by weight.

181. The valve of claim 178, wherein the composite material comprises less than about 50% synthetic polymer membrane by weight.

182. The valve of claim 178, wherein the composite material further includes a layer of TFE/PMVE copolymer.

183. The valve of claim 178, wherein the at least one synthetic polymer membrane is fluoropolymer membrane.

184. The valve of claim 178, wherein the synthetic polymer membrane is porous polyethylene membrane.

185. The valve of claim 184, wherein the pores are defined by a fibrous structure comprising fibers that have an average fiber diameter of less than about 1 μ

m.

186. The valve of claim 184, wherein the pores are defined by a fibrous structure comprising fibers that have an average fiber diameter of less than about 0.1 μ

m.

187. The valve of claim 178, wherein the TFE/PMVE copolymer consists essentially of between about 40 and 80 weight percent perfluoromethyl vinyl ether and complementally 60 and 20 weight percent tetrafluoroethylene.

188. The valve of claim 184, wherein the porous polyethylene membrane has a matrix tensile strength in at least one direction greater than about 150 MPa.

189. The valve of claim 178, wherein the leaflet has a thickness of less than about 350 μ

m.

190. The valve of claim 178, wherein the composite material comprises at least one layer of the synthetic polymer membrane.

191. The valve of claim 178, wherein the composite material comprises more than two layers of the synthetic polymer membrane.

192. The valve of claim 178, wherein the leaflet has a ratio of leaflet thickness (μ

m) to number of layers of synthetic polymer membrane of less than about 20.

193. The valve of claim 184, wherein the leaflet has at least 10 layers of porous polyethylene membrane and the composite material comprising less than about 50% synthetic polyethylene membrane by weight.

194. The valve of claim 178, wherein the pores have a pore size that is less than about 5 μ

m.

195. The valve of claim 178, wherein the pores have a pore size that is less than about 1 μ

m.

196. The valve of claim 178, wherein the pores have a pore size that is less than about 0.10 μ

m.

197. The valve of claim 178, wherein the support structure is selectively diametrically adjustable for endovascular delivery and deployment at a treatment site.