Polythiourethane-based casting resin having high fracture resistance and low specific weight
The invention has as subject matter a method for producing a polyurethane cast resin, wherein the production comprises the steps of mixing at least one thiol component with at least one isocyanate component, degassing of the mixture and hardening of the polyurethane polymer in a one-stage process. Cast resins for electronic or optoelectronic components of for the production of optical lenses are obtained by the method of the invention that have good mechanical properties and very good optical properties at the same time by a suitable combination of polythiols as hardening component with commercially available isocyanates. The addition of special isocyanates is also not very necessary, as is the case for carrying out the method in several stages. The method in accordance with the invention results in an economical, one-stage process in the properties of the cast resin that are necessary for the application range.
1. A method for the production of a polyurethane cast resin, wherein the production takes place in a one-stage process and the steps comprise:
a) Mixing 5-30 wt % of at least one thiol component (A) selected from the group consisting of ethane-1,2-dithiol, 2,2′-dimercaptodiethyl sulfide, and 1,11-dimercapto-3,6,9-trithiaundecane, 15-45 wt % of one or more thiols of the group (I) and/or group (II), and 30-70 wt % of at least one isocyanate component (B),
a) Degassing of the mixture and
b) Hardening of the polyurethane polymer,
wherein thiols of group (I) are selected from the group consisting of pentaerythrithol-tetrakis-3-mercaptopropionate, pentaerythrithol-tetrakis-thioglycolate, trimethylolpropane-tris-3-mercaptopropionate, trimethylolpropane-tris-thioglycolate, pentaerythrithol-tetrakis-2-mercaptopropionate, trimethylolpropane-tris-2-mercaptopropionate, ditrimethylolpropane-tetrakis-3-mercaptopropionate, ditrimethylolpropane-tetrakis-thioglycolate, ditrimethylolpropane-tetrakis-2-mercaptopropionate, dipentaerythrithol-hexakis-3-mercaptopropionate, dipentaerythrithol-hexakis-thioglycolate, dipentaerythrithol-hexakis-2-mercaptopropionate, tris[3-mercaptopropionyloxy)-ethyl]-isocyanurate, tris[mercaptoethyloxy)-ethyl]-isocyanurate, tris[2-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythrithol-tetrakis-4-mercaptobutyrate, trimethylolpropane-tris-4-mercaptobutyrate, trimethylolpropane-tris-4-mercaptobutyrate, pentaerythrithol-tetrakis-3-mercaptobutyrate, trimethylolpropane-tris-3-mercaptobutyrate, trimethylolpropane-tris-3-mercaptobutyrate, tris[3-mercaptobutyloxy)-ethyl]-isocyanurate, tris[4-mercaptobutyloxy)-ethyl]-isocyanurate and acetic acid, 2,2′,2″,2″″-[1,2-ethane diylidene tetrakis(thio)]tetrakis-,tetrakis(2-mercaptoethyl) ester,
and wherein thiols of group (II) are selected from the group consisting of 4-mercaptothiolmethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercapatomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis(mercaptomethyl)methane, 1,1,3,3,-tetrakis(mercaptomethylthio)propane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(mercaptomethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, tris(mercaptomethylthio)methane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(mercaptoethylthio)propane, tetrakis(mercaptomethylthio)methane, tetrakis(mercaptoethylthiomethyl)methane, tetrakis(mercaptopropylthiomethyl)methane, and 2,5-dimercapato-1,4-dithian, 2,5-Bismercaptomethyl-1,4-dithiane, and
wherein the only isocyanate component (B) present consists of, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, α.α,α′,α′-tetramethyl-xylylene diisocyanate, xylylene diisocyanate or a mixture of them,
and wherein the polyurethane cast resin has a high impact resistance in the Drop Ball test, measured with the FDA Drop Ball test with a 16 g ball and a fall height of 127 cm and an expanded test with a 67 g ball and a fall height of 127 cm), and a density ≤1.23 g/cm 3 .
2. The method according to claim 1 , characterized in that thiol component (A) comprises one or more thiols of the group (I) selected from the group consisting of pentaerythrithol-tetrakis-3-mercaptopropionate, pentaerythrithol-tetrakis-thioglycolate, trimethylolpropane-tris-3-mercaptopropionate, trimethylolpropane-tris-thioglycolate, ditrimethylolpropane-tetrakis-2-mercaptopropionate, dipentaerythrithol-hexakis-3-mercaptopropionate and acetic acid, 2,2′,2″,2″″-[1,2-ethane diylidene tetrakis(thio)]tetrakis-,tetrakis(2-mercaptoethyl) ester.
3. The method according to claim 1 , characterized in that thiol component (A) comprises one or more thiols of the group (I) selected from the group consisting of pentaerythrithol-tetrakis-3-mercaptopropionate, trimethylolpropane-tris-3-mercaptopropionate and acetic acid, 2,2′,2″,2″″-[1,2-ethane diylidene tetrakis(thio)]tetrakis-,tetrakis(2-mercaptoethyl) ester.
4. The method according to claim 1 , characterized in that thiol component (A) further comprises one or more thiols, selected from the group consisting of 4-mercaptomethyl-3,6-dithia-1,8-octandithiol, 5,7-dimercapatomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercapatomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercapatomethyl-1,11-dimercapto-3,6,9-trithiaundecane and their mixtures.
5. The method according to claim 1 , characterized in that thiol component (A) further comprises 4-mercaptomethyl-3,6-dithia-1,8-octandithiol.
6. The method according to claim 1 , characterized in that the isocyanate component (B) is one or more diisocyanate(s) selected from the group consisting of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, α.α,α′,α′-tetramethyl-xylylene diisocyanate, xylylene diisocyanate and mixtures thereof, and that the polyurethane cast resin does not contain any other isocyanates.
7. The method according to claim 1 , characterized in that the polyurethane cast resin has a refraction index of n D ≥1.60, determined with an Abbe refractometer, and an Abbe number of ≥38, determined with an Abbe refractometer.
8. The method according to claim 1 , wherein thiol of the group (I) is acetic acid 2,2′,2″,2″″-[1,2-ethane diylidene tetrakis(thio)]tetrakis-,tetrakis(2-mercaptoethyl) ester, and the thiol of group (II) is 4-mercaptothiolmethyl-1,8-dimercapto-3,6-dithiaoctane.