High impact poly(urethane urea) polysulfides

• US 20100048852A1
• Filed: 11/02/2009
• Published: 02/25/2010
• 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: McDonald, William H., Yu, Phillip C., Nagpal, Vidhu J., Okoroafor, Michael O., Sawant, Suresh G., Rao, Chandra B., Bojkova, Nina V., Smith, Robert A., Graham, Marvin J., Herold, Robert D.
• Application Number:
  US12/590,085
• Publication Number:
  US 20100048852A1
• Time in Patent Office: Days
• US Class Current: 528/60
• 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 the polyureaurethane. The sulfur-containing polyureaurethane has 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 cured. The sulfur-containing polyureaurethane is prepared by the reaction of:

• (a) a sulfur-containing, isocyanate functional polyurethane prepolymer derived from:
  • (i) a polyisocyanate; and
  • (ii) a polythiol oligomer produced by the reaction of at least two or more different dienes with one or more dithiols and in certain embodiments at least one trifunctional or higher-functional polythiol; and
• (b) an amine-containing curing agent.

Claims

1. A sulfur-containing polyureaurethane having 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 cured, wherein the sulfur-containing polyureaurethane is prepared by the reaction of:

(a) a sulfur-containing, isocyanate functional polyurethane prepolymer derived from;

(i) a polyisocyanate; and

(ii) a polythiol oligomer produced by the reaction of at least two or more different dienes with one or more dithiols; and

(b) an amine-containing curing agent.

2. The sulfur-containing polyureaurethane of claim 1 wherein one of the dienes is a cyclic diene.

3. The sulfur-containing polyureaurethane of claim 2 wherein said two or more different dienes comprise:

a) at least one non-cyclic diene and at least one cyclic diene selected from non-aromatic ring-containing dienes;

or

b) at least one aromatic ring-containing diene and at least one diene selected from non-aromatic cyclic dienes;

or

c) at least one non-aromatic diene containing a non-aromatic monocyclic group, and at least one non-aromatic diene containing a polycyclic non-aromatic group.

4. The sulfur-containing polyureaurethane of claim 1 wherein said polythiol oligomer is produced by the reaction of one of the following combinations of dienes and polythiol:

(a) 5-vinyl-2-norbornene (VNB), diethylene glycol divinyl ether (DEGDVE) and dimercaptodiethylsulfide (DMDS);

(b) VNB, butanediol divinylether (BDDVE), and DMDS;

(c) VNB, DEGDVE, BDDVE, and DMDS;

(d) 1,3-diisopropenylbenzene (DIPEB), DEGDVE and DMDS;

(e) DIPEB, VNB and DMDS;

(f) DIPEB, 4-vinyl-1-cyclohexene (VCH), and DMDS;

(g) allylmethacrylate (AM), VNB, and DMDS;

(h) VCH, VNB, and DMDS;

(i) Limonene (L), VNB and DMDS;

(j) Ethylene glycol dimethacrylate (EGDM), VCH and DMDS;

(k) Diallylphthalate (DAP), VNB, and DMDS;

(l) Divinylbenzene (DVB), VNB, and DMDS; and

(m) DVB, VCH, and DMDS.

5. The sulfur-containing polyureaurethane of claim 1 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.

6. The sulfur-containing polyureaurethane claim 1 wherein said polyisocyanate is chosen from 4,4′

-methylenebis(cyclohexyl isocyanate) and isomeric mixtures thereof.

7. The sulfur-containing polyureaurethane of claim 1 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.

8. The sulfur-containing polyureaurethane of claim 1 wherein said amine-containing curing agent includes a combination of polyamine and material selected from polyol, polythiol, polythiol oligomer, materials containing both hydroxyl and SH groups, and mixtures thereof.

9. The sulfur-containing polyureaurethane of claim 1 wherein said amine-containing curing agent comprises a polyamine having at least two functional groups comprising primary amine (—

NH₂) and/or secondary amine (—

NH—

).

10. The sulfur-containing polyureaurethane of claim 1 wherein said polyamine is represented by the following structural following formula:

11. The sulfur-containing polyureaurethane of claim 10 wherein said amine-containing curing agent comprises 4,4′

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

12. The sulfur-containing polyureaurethane of claim 1 wherein said amine-containing curing agent comprises 2,4-diamino-3,5-diethyl-toluene;

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

13. The sulfur-containing polyureaurethane of claim 1 wherein said sulfur-containing, isocyanate functional polyurethane 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.

14. The sulfur-containing polyureaurethane of claim 1 wherein said sulfur-containing, isocyanate functional polyurethane prepolymer is prepared in the presence of a mixture of catalysts comprising a tin compound and a phosphine.

17. An optical article comprising the sulfur-containing polyureaurethane of claim 1.

18. The optical article of claim 17 comprising at least a photochromic amount of photochromic substance.

19. An ophthalmic lens comprising the sulfur-containing polyureaurethane of claim 1.

15. A sulfur-containing polyureaurethane having 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 cured, wherein the sulfur-containing polyureaurethane is prepared by the reaction of:

(a) a sulfur-containing, isocyanate functional polyurethane prepolymer derived from;

(i) a polyisocyanate; and

(ii) a polythiol 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; and

(b) an amine-containing curing agent.

16. The sulfur-containing polyureaurethane of claim 15 wherein said sulfur-containing, isocyanate functional polyurethane prepolymer is prepared in the presence of a mixture of catalysts comprising a tin compound and a phosphine.