High impact poly (urethane urea) polysulfides

• US 20060241273A1
• Filed: 02/22/2006
• Published: 10/26/2006
• Est. Priority Date: 11/16/2001
• Status: Abandoned Application

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Sawant, Suresh G., Rao, Chandra B., Bojkova, Nina V., Smith, Robert A., Graham, Marvin J., Herold, Robert D., McDonald, William H., Yu, Phillip C., Nagpal, Vidhu J., Okoroafor, Michael O.
• Application Number:
  US11/360,011
• Publication Number:
  US 20060241273A1
• Time in Patent Office: Days
• US Class Current: 528/44
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/3237 aromatic C08G18/3234 takes precedence
• CPC Class Codes: C08G 18/324 containing only one aromatic ring
• CPC Class Codes: C08G 18/3874 containing heterocyclic rings having at least one sulfur atom in the ring
• CPC Class Codes: C08G 18/3876 containing mercapto groups
• CPC Class Codes: C08G 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/4202 Two or more polyesters of different physical or chemical nature C08G18/44 takes precedence
• CPC Class Codes: C08G 18/4277 Caprolactone and/or substituted caprolactone
• CPC Class Codes: C08G 18/4837 and other oxyalkylene units
• CPC Class Codes: C08G 18/52 Polythioethers
• CPC Class Codes: C08G 18/6611 having at least three hydroxy groups
• CPC Class Codes: C08G 18/6644 having at least three hydroxy groups
• CPC Class Codes: C08G 18/6685 with compounds of group C08G18/3225 or polyamines of C08G18/38
• CPC Class Codes: C08G 18/722 Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
• CPC Class Codes: C08G 18/724 Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08L 75/04 Polyurethanes
• CPC Class Codes: C08L 81/00 : Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
• CPC Class Codes: G02B 1/041 : Lenses

Abstract

The present invention relates to a sulfur-containing polyureaurethane and a method of preparing said polyureaurethane. In an embodiment, the sulfur-containing polyureaurethane adapted to have a refractive index of at least 1.57,an Abbe number of at least 32 and a density of less than 1.3 grams/cm³, when at least partially cured.

Claims

1-151. -151. (canceled)

152. A sulfur-containing polyureaurethane adapted to have a refractive index of at least 1.57, an Abbe number of at least 32 and a density of less than 1.3 grams/cm³, when at least partially cured.

153. The sulfur-containing polyureaurethane of claim 152 that is prepared by the reaction of:

(a) a sulfur-containing polyurethane prepolymer; and

(b) an amine-containing curing agent.

154. The sulfur-containing polyureaurethane of claim 153 wherein the sulfur-containing polyurethane prepolymer comprises the reaction product of:

(a) a sulfur-containing polyisocyanate, polyisothiocyanate, or mixture thereof; and

(b) an active hydrogen-containing material.

155. The sulfur containing polyurethane of claim 154, wherein the active hydrogen-containing material comprises a polyol, and/or a polythiol.

156. The sulfur-containing polyureaurethane of claim 154 wherein the active hydrogen-containing material is a hydroxyl functional polysulfide.

157. The sulfur-containing polyureaurethane of claim 156 wherein said hydroxyl functional polysulfide further comprises SH-functionality.

158. The sulfur-containing polyureaurethane of claim 155 wherein said prepolymer has a polyisocyanate plus polyisothiocyanate to hydroxyl equivalent ratio of from 2.0:

1.0 to less than 5.5;

1.0.

159. The sulfur-containing polyureaurethane of claim 155 wherein said polyol comprises a polyether polyol.

160. The sulfur-containing polyureaurethane of claim 153 wherein said sulfur-containing polyurethane prepolymer and said amine-containing curing agent are present such that the equivalent ratio of (NH+SH+OH) to (NCO+NCS) is from 0.80:

1.0 to 1.1;

1.0.

161. The sulfur-containing polyureaurethane of claim 153, wherein said sulfur-containing polyurethane prepolymer comprises the reaction product of:

i. a polyisocyanate; and

ii. a sulfur-containing active hydrogen material.

162. The sulfur-containing polyureaurethane material of claim 161 wherein said polyisocyanate is chosen from 4,4′

-methylenebis(cyclohexyl isocyanate) and isomeric mixtures thereof.

163. The sulfur-containing polyureaurethane of claim 155 wherein said polythiol comprises an oligomer which is the reaction product of at least two different dienes and at least one dithiol;

and wherein the stoichiometric ratio of the sum of the number of equivalents of dithiol to the sum of the number of equivalents of diene is greater than 1.0;

1.0.

164. The sulfur-containing polyureaurethane of claim 155, wherein said polythiol comprises an oligomer which is the reaction product of at least two different dienes, at least one dithiol, and at least one trifunctional or higher-functional polythiol;

wherein the stoichiometric ratio of the sum of the number of equivalents of polythiol to the sum of the number of equivalents of diene is greater than 1.0;

1.0.

165. The sulfur-containing polyureaurethane of claim 153 wherein said amine-containing curing agent comprises amine-containing material and at least one material comprising polythiol and/or polyol.

166. The sulfur-containing polyureaurethane of claim 152 comprising the reaction product of:

i. polyisocyanate, polyisothiocyanate or mixture thereof;

ii. an active hydrogen-containing material; and

iii. an amine-containing curing agent.

167. The sulfur-containing polyureaurethane of claim 152 comprising the reaction product of:

(a) polyisocyanate;

(b) sulfur-containing active hydrogen material; and

(c) amine-containing curing agent.

168. The sulfur-containing polyureaurethane of claim 153 wherein said amine-containing curing agent comprises a polyamine having at least two functional groups independently chosen from primary amine (—

NH₂), secondary amine (—

NH—

) , or combinations thereof.

169. The sulfur-containing polyureaurethane of claim 168 wherein said polyamine is represented by the following structural following formula and mixtures thereof:

170. The sulfur-containing polyureaurethane of claim 153 wherein said amine-containing curing agent comprises 4,4′

-methylenebis(3-chloro-2,6-diethylaniline).

171. The sulfur-containing polyureaurethane of claim 153 wherein said amine-containing curing agent comprises 2,4-diamino-3,5-diethyl-toluene;

and/or 2,6-diamino-3,5-diethyl-toluene.

172. The sulfur-containing polyureaurethane of claim 153 wherein said prepolymer and amine-containing curing agent are present in amounts such that the NCO/NH₂ equivalent ratio is from 1.0 NCO/0.60 NH₂ to 1.0 NCO/1.20 NH₂.

173. The sulfur-containing polyureaurethane of claim 152, comprising the reaction product of:

(a) a polyurethane prepolymer; and

(b) an amine-containing curing agent, wherein at least one of (a) and (b) is a sulfur-containing material.

181. An optical article comprising the sulfur-containing polyureaurethane of claim 152.

182. An ophthalmic lens comprising the sulfur-containing polyureaurethane of claim 152.

174. A method of preparing a sulfur-containing polyureaurethane comprising:

(a) reacting polyisothiocyanate or a mixture of polyisocyanate and polyisothiocyanate, and an active hydrogen-containing material to form polyurethane prepolymer; and

(b) reacting said polyurethane prepolymer with amine-containing curing agent, wherein the polyueaurethane is adapted to have a refractive index of at least 1.57, an Abbe number of at least 32 and a density of less than 1.3 grams/cm³.

175. The method of claim 174 further comprising reacting said polyurethane prepolymer in step (a) with an episulfide-containing material.

176. The method of claim 174 wherein said active hydrogen-containing material comprises polyol free of sulfur and/or polythiol.

177. A method of preparing a sulfur-containing polyureaurethane comprising:

(a) reacting polyisocyanate with sulfur-containing active hydrogen-containing material to form polyurethane prepolymer; and

(b) reacting said polyurethane prepolymer with amine-containing curing agent,

wherein said polyureaurethane is adapted to have a refractive index of at least 1.57, an Abbe number of at least 32 and a density of less than 1.3 grams/cm³.

178. The method of claim 177 wherein said sulfur-containing active hydrogen-containing material comprises a hydroxyl functional polysulfide.

179. The method of claim 177 wherein said amine-containing curing agent comprises a sulfur-containing amine-containing curing agent.

180. The method of claim 177 wherein said amine-containing curing agent comprises amine-containing material and at least one polythiol, and optionally polyol.

183. The optical article of claim 190 comprising at least a photochromic amount of photochromic substance.

184. The optical article of claim 190, wherein the sulfur-containing polyureaurethane is prepared from a polyurethane prepolymer comprising the reaction product of:

(a) polyisocyanate and/or polyisothiocyanate; and

(b) active hydrogen-containing material, with the proviso that at least one of (a) and (b) is sulfur-containing.

185. A method of preparing a sulfur-containing polyureaurethane containing disulfide linkages comprising:

(a) reacting polyisocyanate and/or polyisothiocyanate, with active hydrogen-containing material to form polyurethane prepolymer; and

(b) reacting said polyurethane prepolymer with amine-containing curing agent,

wherein at least one of said polyurethane prepolymer and amine-containing curing agent comprises disulfide linkages.