Urethane polymers and sealant compositions containing the same

• US 4,067,844 A
• Filed: 12/22/1976
• Issued: 01/10/1978
• Est. Priority Date: 12/22/1976
• Status: Expired due to Term

• Current Assignee: Tremco Incorporated (RPM International Incorporated)
• Original Assignee: Tremco Incorporated (RPM International Incorporated)
• Inventors: Barron, Larry R., Turk, Herbert M.
• Primary Examiner(s): Jacobs, Lewis T.
• Application Number:
  US05/753,370
• Time in Patent Office: 384 Days
• Field of Search: 260/77.5 TB, 260/77.5 AM, 260/75 TN, 260/75 NH, 260/37 N
• US Class Current: 525/453
• 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 18/289 containing silicon

Abstract

Novel, curable polyurethane polymers in which a proportion of the NCO terminations are reacted with certain amino silanes, or with the residual on reaction of a mercaptosilane with a monoepoxide, or with the residual on reaction of an epoxysilane with a secondary amine.

Sealant compositions formed with the novel polymers are stable in storage, moisture curable and adhere well to various substrates, obviating the need for a primer.

Claims

1. A curable organic polymeric material having an average molecular weight within the range of about 1000 to about 15,000 and having at least 2 functional groups per average molecular weight not more than 99% of which are NCO, and the balance being selected from the group consisting of ##STR6##where R is an alkylene of 2- 18 carbon atoms

R₁ is a lower alkyl of 1-6 carbon atoms

R₂ is --H or --CH₃

R₃ is --C.tbd.N or ##STR7## and, R₄ is an alkyl of 1-18 carbon atoms, an epoxyalkyl of 3-8 carbon atoms, an alkoxyalkyl of 2-12 carbon atoms, or --C.tbd.N, and ##STR8## where R₅ is the residual on reaction of a mercaptosilane with a monoepoxide or an epoxysilane with a secondary amine.

2. The curable organic polymeric material of claim 1 wherein about 75-98% of said functional groups are NCO.

3. The curable organic polymeric material of claim 2 wherein the balance of said functional groups are the residual on reaction of an NCO group with the reaction product of gamma-aminopropyltrimethoxysilane and butyl acrylate.

4. The curable organic polymeric material of claim 2 wherein the balance of said functional groups are the residual on reaction of an NCO group with the reaction product of gamma-aminopropyltrimethoxysilane and ethyl acrylate.

5. The curable organic polymeric material of claim 2 wherein the balance of said functional groups are the residual on reaction of an NCO group with the reaction product of gamma-mercaptopropyltrimethoxysilane and butylene oxide.

6. The curable organic polymeric material of claim 2 wherein the balance of said functional groups are the residual on reaction of an NCO group with the reaction product of gamma-glycidoxypropyltrimethoxysilane and di-n-butyl amine.

7. The curable organic polymeric material of claim 2 wherein the balance of said function groups are the residual on reaction of an NCO group with the reaction product of gamma-aminopropyltrimethoxysilane and acrylonitrile.

10. A sealant composition comprising the curable organic polymeric material according to claim 1.

11. A sealant composition according to claim 10 further comprising fillers and pigments.

14. A cured sealant according to claim 10.

15. A cured sealant according to claim 11.

8. A curable organic polymeric material formed by reacting a polyol having a hydroxyl functionality in excess of 2 and an average molecular weight within the range of about 1000 to 15,000 with a stoichiometric excess of a polyisocyanate to provide an NCO terminated polyurethane prepolymer, and reacting at least 1% of said NCO terminations with a material selected from the group consisting of ##STR9##where R is an alkylene of 2- 18 atoms

R₁ is a lower alkyl of 1-6 carbon atoms

R₂ is --H or --CH₃

R₃ is --C.tbd.N or ##STR10## and R₄ is an alkyl of 1-18 carbon atoms, an epoxyalkyl of 3-8 carbon atoms, an alkoxyalkyl of 2-12 carbon atoms, or --C.tbd.N,

b. the reaction product of a mercaptosilane with a monoepoxide, and

c. the reaction product of an epoxysilane with a secondary amine.

9. The curable organic polymeric material of claim 8 wherein from about 2-25% of said NCO terminations are so reacted.

12. A sealant composition comprising the curable organic polymeric material according to claim 8.

13. A sealant composition according to claim 12 further comprising fillers and pigments.

16. A cured sealant according to claim 12.

17. A cured sealant according to claim 13.

18. A method of forming a sealant composition having improved adhesion comprising the steps of reacting a polyol having a hydroxyl functionality in excess of 2 and an average molecular weight within the range of about 1000 to 15,000 with a stoichiometric excess of a polyisocyanate to provide an NCO terminated polyurethane prepolymer, reacting at least 1% of said NCO terminations with a material selected from the group consisting of ##STR11##where R is an alkylene of 2-18 carbon atoms

R₁ is a lower alkyl of 1-6 carbon atoms

R₂ is --H or --CH₃

R₃ is --C.tbd.N or ##STR12## and R₄ is an alkyl of 1- 18 carbon atoms, an epoxyalkyl of 3-8 carbon atoms, an alkoxyalkyl or 2-12 carbon atoms, or --C.tbd.N,

b. the reaction product of a mercaptosilane with a monoepoxide, and

c. the reaction product of an epoxysilane with a secondary amine, thereby forming a silane modified polyurethane polymer, and with fillers and pigments to form a sealant composition.

19. The method defined in claim 18 wherein said material is (b) and it is present during the reaction of said polyol and said polyisocyanate.

20. The method defined in claim 18 wherein said material is (c) and it is present during the reaction of said polyol and said polyisocyanate.

21. The method defined in claim 18 wherein said material is (a) and it is added after reaction of the polyol and the polyisocyanate is substantially complete.