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1. WO2020113018 - NANOCAPSULES DE CONVERSION ASCENDANTE DE PHOTONS POUR L’IMPRESSION 3D ET D’AUTRES APPLICATIONS

Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

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CLAIMS

1. A system, comprising:

a liquid comprising a polymerizable entity and nanocapsules having an interior portion, the interior portion comprising an upconversion material.

2. The system of claim 1, wherein at least some of the nanocapsules are micelles.

3. The system of any one of claims 1 or 2, wherein at least some of the nanocapsules comprise a surfactant.

4. The system of any one of claims 1-3, wherein the nanocapsules have an average

diameter of less than 1 micrometer.

5. The system of any one of claims 1-4, wherein the nanocapsules have an average

diameter of less than 700 nm.

6. The system of any one of claims 1-5, wherein the nanocapsules have an average

diameter of less than about 50 nm.

7. The system of any one of claims 1-6, wherein the nanocapsules have an average

diameter of between 30 nm and 40 nm.

8. The system of any one of claims 1-7, wherein at least some of the nanocapsules are covalently cross-linked.

9. The system of any one of claims 1-8, wherein at least some nanocapsules comprise a silica shell.

10. The system of any one of claims 1-9, wherein at least some nanocapsules further comprise an outer portion.

11. The system of claim 10, wherein the outer portion is hydrophilic.

12. The system of any one of claims 10 or 11, wherein the outer portion comprises polyethylene glycol.

13. The system of any one of claims 1-12, wherein at least some of the nanocapsules comprise an amphiphilic copolymer.

14. The system of any one of claims 1-13, wherein at least some of the nanocapsules comprise an amphiphilic block copolymer.

15. The system of claim 14, wherein the amphiphilic block copolymer comprises

polyethylene glycol blocks.

16. The system of any one of claims 14 or 15, wherein the amphiphilic block copolymer comprises polypropylene glycol blocks.

17. The system of any one of claims 13-16, wherein the amphiphilic copolymer

comprises a poloxamer.

18. The system of any one of claims 13-17, wherein the amphiphilic copolymer

comprises Pluronic® FI 27.

19. The system of any one of claims 13-18, wherein the amphiphilic copolymer

comprises Pluronic® PI 05.

20. The system of any one of claims 13-19, wherein the amphiphilic copolymer has a structure:

0-CH2-CH2]a-[0-CH(CH3)-CH2]b-[0-CH2-CH2]c-*, wherein a, b, and c are each independently positive integers, and * indicates a point of attachment.

21. The system of any one of claims 1-20, wherein at least some of the nanocapsules comprise Triton™ X-100.

22. The system of any one of claims 1-21, wherein at least some of the nanocapsules comprise a compound having a structure:


wherein n is a positive integer.

23. The system of claim 22, wherein the compound has an average n of between 9 and 10.

24. The system of any one of claims 1-23, wherein at least some of the nanocapsules comprise sodium dodecyl sulfate.

25. The system of any one of claims 1-24, wherein the upconversion material is dissolved in the interior portion.

26. The system of any one of claims 1-25, wherein the interior portion is substantially nonpolar.

27. The system of any one of claims 1-26, wherein the interior portion comprises a

nonpolar solvent.

28. The system of any one of claims 1-27, wherein the interior portion is substantially immiscible in water.

29. The system of any one of claims 1-28, wherein the interior portion comprises a

carboxylic acid.

30. The system of any one of claims 1-29, wherein the interior portion comprises oleic acid.

31. The system of any one of claims 1-30, wherein the interior portion comprises

trimethylbenzene .

32. The system of any one of claims 1-31, wherein the interior portion comprises trichlorobenzene .

33. The system of any one of claims 1-32, wherein the interior portion comprises

chloroform.

34. The system of any one of claims 1-33, wherein the upconversion material comprises a sensitizer and an annihilator.

35. The system of claim 34, wherein the sensitizer absorbs incident light.

36. The system of any one of claims 34 or 35, wherein the annihilator emits light due to energy transfer from the sensitizer.

37. The system of any one of claims 34-36, wherein the sensitizer and the annihilator exhibit triplet annihilation upconversion.

38. The system of any one of claims 34-37, wherein the sensitizer comprises palladium tetraphenyl tetrabenzoporphyrin.

39. The system of any one of claims 34-38, wherein the sensitizer comprises palladium tetrabenzoporphyrin .

40. The system of any one of claims 34-39, wherein the sensitizer comprises palladium octabutoxy phthalocyanine (PdOBuPc).

41. The system of any one of claims 34-40, wherein the annihilator comprises tetra-tert- butyl perylene.

42. The system of any one of claims 34-41, wherein the annihilator comprises a quantum dot.

43. The system of any one of claims 34-42, wherein the annihilator comprises 9,10- diphenylanthracene.

44. The system of any one of claims 34-43, wherein the annihilator comprises TIPS- tetracene or a halogenated derivative thereof.

45. The system of any one of claims 1-44, wherein the nanocapsules are substantially miscible with the liquid.

46. The system of any one of claims 1-45, wherein the liquid comprises water.

47. The system of any one of claims 1-46, wherein the liquid is at least 50 wt% water.

48. The system of any one of claims 1-47, wherein the liquid is aqueous.

49. The system of any one of claims 1-48, wherein the liquid is optically transparent.

50. The system of any one of claims 1-49, wherein the liquid has a viscosity of 1 cP or more.

51. The system of any one of claims 1-50, wherein the liquid has a viscosity of 10,000 cP or more.

52. The system of any one of claims 1-51, wherein the liquid has a viscosity of less than 300,000 cP.

53. The system of any one of claims 1-52, wherein the liquid comprises toluene.

54. The system of any one of claims 1-53, wherein the liquid comprises dichloromethane.

55. The system of any one of claims 1-54, wherein the liquid comprises chloroform.

56. The system of any one of claims 1-55, wherein the polymerizable entity comprises a resin.

57. The system of claim 56, wherein the resin comprises a thermoplastic resin.

58. The system of any one of claims 56 or 57, wherein the resin comprises a thermoset resin.

59. The system of any one of claims 1-58, wherein the polymerizable entity comprises monomers.

60. The system of any one of claims 1-59, wherein the polymerizable entity comprises an acrylate.

61. The system of any one of claims 1-60, wherein the polymerizable entity comprises a methacrylate.

62. The system of any one of claims 1-61, wherein the polymerizable entity comprises methyl methacrylate.

63. The system of any one of claims 1-62, wherein the polymerizable entity comprises a acrylate or methacrylate terminated monomer or oligomer.

64. The system of any one of claims 1-63, wherein the polymerizable entity comprises an alkene.

65. The system of any one of claims 1-64, wherein the polymerizable entity comprises a vinyl monomer.

66. The system of any one of claims 1-65, wherein the polymerizable entity comprises a styrenic monomer.

67. The system of any one of claims 1-66, wherein the polymerizable entity is

photopolymerizable .

68. The system of any one of claims 1-67, wherein the polymerizable entity comprises polymers.

69. The system of any one of claims 1-68, wherein the liquid further comprises a cross- linking agent.

70. The system of claim 69, wherein the cross-linking agent is able to polymerize with the polymerizable entity.

71. The system of any one of claims 69 or 70, wherein the cross-linker comprises

ethylene glycol dimethacrylate.

72. The system of any one of claims 1-71, wherein the liquid further comprises a

photopolymerization initiator.

73. An apparatus, comprising:

a container containing the system of any one of claims 1-72; and a radiation source positioned to direct electromagnetic radiation towards at least a portion of the container.

74. The apparatus of claim 73, wherein the radiation source comprises a laser.

75. The apparatus of any one of claims 73 or 74, wherein the electromagnetic radiation is visible light.

76. A system, comprising:

a powder comprising a monomer and nanocapsules having an interior portion, the interior portion comprising an upconversion material.

77. The system of claim 76, wherein the powder has a water content of less than 5 wt%.

78. The system of any one of claims 76 or 77, wherein the powder has a water content of less than 1 wt%.

79. The system of any one of claims 76-78, wherein the powder is lyophilized.

80. The system of any one of claims 76-79, wherein at least some of the nanocapsules are micelles.

81. The system of any one of claims 76-80, wherein at least some of the nanocapsules are covalently cross-linked.

82. The system of any one of claims 76-81, wherein at least some nanocapsules comprise a silica shell.

83. The system of any one of claims 76-82, wherein at least some nanocapsules further comprise an outer portion.

84. The system of claim 83, wherein the outer portion is hydrophilic.

85. The system of any one of claims 76-84, wherein at least some of the nanocapsules comprise an amphiphilic copolymer.

86. The system of any one of claims 76-85, wherein the upconversion material is

dissolved in the interior portion.

87. The system of any one of claims 76-86, wherein the interior portion is substantially immiscible in water.

88. The system of any one of claims 76-87, wherein the upconversion material comprises a sensitizer and an annihilator.

89. The system of claim 88, wherein the sensitizer absorbs incident light.

90. The system of any one of claims 88 or 89, wherein the annihilator emits light due to energy transfer from the sensitizer.

91. The system of any one of claims 88-90, wherein the sensitizer and the annihilator exhibit triplet annihilation upconversion.

92. A system, comprising:

a polymer comprising nanocapsules having an interior portion, the interior portion comprising an upconversion material.

93. The system of claim 92, wherein the nanocapsules are embedded within the polymer.

94. The system of any one of claims 92 or 93, wherein the polymer comprises a

polyamide.

95. The system of any one of claims 92-94, wherein the polymer comprises

polypropylene.

96. The system of any one of claims 92-95, wherein the polymer comprises ABS.

97. The system of any one of claims 92-96, wherein the polymer comprises PLA.

98. The system of any one of claims 92-97, wherein the polymer comprises PVA.

99. The system of any one of claims 92-98, wherein the polymer comprises PET.

100. The system of any one of claims 92-99, wherein the polymer comprises PETT.

101. The system of any one of claims 92-100, wherein the polymer comprises HIPS.

102. The system of any one of claims 92-101, wherein the polymer comprises nylon.

103. The system of any one of claims 92-102, wherein at least some of the nanocapsules are micelles.

104. The system of any one of claims 92-103, wherein at least some of the nanocapsules are covalently cross-linked.

105. The system of any one of claims 92-104, wherein at least some nanocapsules comprise a silica shell.

106. The system of any one of claims 92-105, wherein at least some nanocapsules further comprise an outer portion.

107. The system of claim 106, wherein the outer portion is hydrophilic.

108. The system of any one of claims 92-107, wherein at least some of the nanocapsules comprise an amphiphilic copolymer.

109. The system of any one of claims 92-108, wherein the upconversion material is

dissolved in the interior portion.

110. The system of any one of claims 92-109, wherein the interior portion is substantially immiscible in water.

111. The system of any one of claims 92- 110, wherein the upconversion material

comprises a sensitizer and an annihilator.

112. The system of claim 111, wherein the sensitizer absorbs incident light.

113. The system of any one of claims 111 or 112, wherein the annihilator emits light due to energy transfer from the sensitizer.

114. The system of any one of claims 111-113, wherein the sensitizer and the annihilator exhibit triplet annihilation upconversion.

115. A method, comprising:

applying electromagnetic radiation to a liquid comprising a polymerizable entity and nanocapsules having an interior portion comprising an upconversion material, wherein the light is upconverted by the upconversion material; and

polymerizing the monomer within the liquid using the upconverted light.

116. The method of claim 115, wherein the power density of the applied electromagnetic radiation is below 1000 W/cm2.

117. The method of any one of claims 115 or 116, wherein the power density of the

applied electromagnetic radiation is below 100 W/cm2.

118. The method of any one of claims 115-117, wherein the power density of the applied electromagnetic radiation is below 10 W/cm2.

119. The method of any one of claims 115-118, wherein the power density of the applied electromagnetic radiation is below 1 W/cm2.

120. The method of any one of claims 115-119, comprising using a laser to apply the

electromagnetic radiation to the liquid.

121. The method of any one of claims 115-120, comprising polymerizing the monomer within the liquid to form a polymeric solid.

122. The method of claim 121, wherein the polymeric solid is free-floating within the liquid.

123. The method of any one of claims 115-122, wherein at least some of the nanocapsules are micelles.

124. The method of any one of claims 115-123, wherein at least some of the nanocapsules are covalently cross-linked.

125. The method of any one of claims 115-124, wherein at least some nanocapsules

comprise a silica shell.

126. The method of any one of claims 115-125, wherein at least some nanocapsules further comprise an outer portion.

127. The method of claim 126, wherein the outer portion is hydrophilic.

128. The method of any one of claims 115-127, wherein at least some of the nanocapsules comprise an amphiphilic copolymer.

129. The method of any one of claims 115-28, wherein the upconversion material is

dissolved in the interior portion.

130. The method of any one of claims 115-129, wherein the interior portion is substantially immiscible in water.

131. The method of any one of claims 115-130, wherein the upconversion material

comprises a sensitizer and an annihilator.

132. The method of claim 131, wherein the sensitizer absorbs incident light.

133. The method of any one of claims 131 or 132, wherein the annihilator emits light due to energy transfer from the sensitizer.

134. The method of any one of claims 131-133, wherein the sensitizer and the annihilator exhibit triplet annihilation upconversion.

135. The method of any one of claims 115-134, wherein the nanocapsules are substantially miscible with the liquid.

136. The method of any one of claims 115-135, wherein the liquid comprises water.

137. The method of any one of claims 115-136, wherein the liquid is at least 90 wt% water.

138. The method of any one of claims 115-137, wherein the liquid is aqueous.

139. The method of any one of claims 115-138, wherein the liquid is optically transparent.

140. The method of any one of claims 115-139, wherein the polymerizable entity comprises a resin.

141. The method of any one of claims 115-140, wherein the polymerizable entity

comprises monomers.

142. The method of any one of claims 115-141, wherein the liquid further comprises a cross-linking agent

143. The method of claim 142, wherein the cross-linking agent is able to polymerize with the polymerizable entity.

144. The method of any one of claims 115-143, wherein the liquid further comprises a photopolymerization initiator.

145. A method of making a nanocapsule, comprising:

mixing an upconversion material with an amphiphilic surfactant to form nanocapsules comprising the surfactant and containing the upconversion material therein.

146. The method of claim 145, wherein at least some of the upconversion material is contained within the nanocapsules.

147. The method of any one of claims 145 or 146, wherein the amphiphilic surfactant comprises a carboxylic acid.

148. The method of any one of claims 145-147, wherein the amphiphilic surfactant comprises oleic acid or a saturated derivative thereof.

149. The method of claim 148, wherein the saturated derivative comprises stearic acid.

150. The method of any one of claims 145-148, wherein the amphiphilic surfactant comprises oleic acid or an unsaturated derivative thereof.

151. The method of claims 150, wherein the unsaturated derivative comprises linolenic acid.

152. The method of any one of claims 145-151, wherein the amphiphilic surfactant

comprises 3-aminopropyl triethoxysilane.

153. The method of any one of claims 145-152, wherein the amphiphilic surfactant self- assembles to from the nanocapsules.

154. The method of any one of claims 145-153, wherein the amphiphilic surfactant further comprises a first silane.

155. The method of claim 154, further comprising reacting the first silane with a second silane that produces S1O2, thereby adding the S1O2 to the amphiphilic surfactant.

156. The method of claim 155, wherein the second silane comprises tetraethyl

orthosilicate.

157. The method of any one of claims 155 or 156, further comprising a third silane,

wherein the third silane comprises a polyethylene glycol.

158. The method of claim 157, wherein the polyethylene glycol has a molecular weight of at least 300 g/mol.

159. The method of any one of claims 157 or 158, wherein the polyethylene glycol has a molecular weight no greater than 10,000 g/mol.

160. The method of any one of claims 157-159, wherein the polyethylene glycol comprises methoxy polyethylene glycol tetraethyl orthosilicate.

161. The method of any one of claims 145-160, comprising mixing the upconversion

material and the amphiphilic surfactant with a substantially immiscible liquid, wherein the amphiphilic surfactant self-assembles to from the nanocapsules.

162. The method of claim 161, wherein the liquid comprises an aqueous solution.

163. The method of any one of claims 161 or 162, wherein the liquid comprises water.

164. The method of any one of claims 161-163, further comprising removing at least some of the liquid after the nanocapsules have formed.

165. The method of any one of claims 161-164, comprising removing at least some of the liquid using centrifugation.

166. The method of any one of claims 161-165, comprising removing sufficient liquid to cause the nanocapsules to form a paste.

167. The method of claim 166, further comprising mixing the paste with a solvent.

168. The method of claim 167, wherein the solvent comprises toluene.

169. The method of any one of claims 167 or 168, wherein the solvent comprises

dichloromethane .

170. The method of any one of claims 167-169, wherein the solvent comprises a

photopolymerizable entity.

171. A method comprising:

exposing a system to electromagnetic radiation, wherein the system comprises: an upconversion material;

a nanocapsule at least partially encapsulating the upconversion material; and a polymerizable entity.

172. The method of claim 171, wherein the polymerizable entity comprises a monomer.

173. The method of claim 171 or 172, wherein exposing the system to electromagnetic radiation shining a laser onto a region of the system.

174. A system comprising:

an upconversion material;

a nanocapsule at least partially encapsulating the upconversion material; and a polymerizable entity.

175. The system of claim 174, wherein the polymerizable entity comprises a monomer.

176. The system of any one of claims 174 or 175, further comprising a plurality of

nanocapsules encapsulating the upconversion material.

177. The system of any one of claims 174-176, further comprising a plurality of

monomers.

178. The system of any one of claims 174-177, wherein at least a portion of the

nanocapsule is miscible with the monomer.

179. The system of any one of claims 174-178, wherein the system is optically transparent.

180. The system of any one of claims 174-179, wherein the nanocapsule comprises an amphiphilic solution.

181. The system of any one of claims 174-180, wherein the nanocapsule comprises a

surfactant.

182. The system of any one of claims 174-181, wherein the upconversion material

comprises an annihilator, and the system further comprises a second upconversion material comprising a sensitizer.

183. The system of claim 182, wherein the second upconversion material is at least

partially encapsulated by the nanocapsule.

184. A system comprising:

an upconversion material;

a nanocapsule having an interior portion,

wherein the interior portion comprises

the upconversion material and

a solvent; and

a polymerizable entity.

185. The system of claim 184, wherein the polymerizable entity comprises a monomer.

186. The system of any one of claims 184 or 185, wherein the solvent comprises a

nonpolar solvent.

187. The system of any one of claims 184-186, wherein the solvent comprises

trimethylbenzene or trichlorobenzene or a combination thereof.

188. A system, comprising:

an upconversion material;

an amphiphilic surfactant;

a nanocapsule having an interior portion, an exterior portion, and an interface between the interior portion and the exterior portion,

wherein the interior portion contains the upconversion material, wherein the interface comprises a silicate and at least a portion of the amphiphilic surfactant, and

wherein the exterior portion comprises a hydrophilic component.

189. The system of claim 188, wherein the amphiphilic surfactant comprises a carboxylic acid.

190. The system of any one of claims 188 or 189, wherein the amphiphilic surfactant comprises oleic acid or a saturated derivative thereof.

191. The system of claim 190, wherein the saturated derivative comprises stearic acid.

192. The system of any one of claims 188-190, wherein the amphiphilic surfactant

comprises oleic acid or an unsaturated derivative thereof.

193. The system of claims 192, wherein the unsaturated derivative comprises linolenic acid.

194. The system of any one of claims 188-193, wherein the amphiphilic surfactant

comprises 3-aminopropyl triethoxysilane.

195. The system of any one of claims 188-194, wherein the amphiphilic surfactant further comprises a first silane.

196. The system of any one of claims 188-195, wherein the amphiphilic surfactant

comprises Si02.

197. The system of any one of claims 188-196, wherein the amphiphilic surfactant further comprises a second silane.

198. The system of claim 197, wherein the second silane comprises tetraethyl orthosilicate.

199. The system of any one of claims 188-198, wherein the hydrophilic component

comprises a third silane, further comprising a polyethylene glycol.

200. The system of claim 199, wherein the polyethylene glycol has a molecular weight of at least 300 g/mol.

201. The system of any one of claims 199 or 200, wherein the polyethylene glycol has a molecular weight no greater than 30,000 g/mol.

202. The system of any one of claims 199-201, wherein the polyethylene glycol comprises methoxy polyethylene glycol tetraethyl orthosilicate.

203. The system of any one of claims 188-202, further comprising a photopolymerizable entity.