WATER-CLEAR ALIPHATIC POLYURETHANE PULTRUSION FORMULATIONS AND PROCESSES

• US 20140265000A1
• Filed: 03/14/2013
• Published: 09/18/2014
• Est. Priority Date: 03/14/2013
• Status: Abandoned Application

• Current Assignee: Covestro LLC (Covestro AG)
• Original Assignee: Bayer Materialscience LLC (Covestro AG)
• Inventors: Magnotta, Albert, Harasin, Stephen J.
• Application Number:
  US13/826,524
• Publication Number:
  US 20140265000A1
• Time in Patent Office: Days
• US Class Current: 264/137
• CPC Class Codes: B29C 48/05 Filamentary, e.g. strands
• CPC Class Codes: B29C 70/52 Pultrusion, i.e. forming and compressing by continuously pulling through a die
• CPC Class Codes: B29C 70/521 and impregnating the reinforcement before the die
• CPC Class Codes: B29C 70/527 Pulling means
• CPC Class Codes: B29K 2075/00 Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2309/08 Glass
• CPC Class Codes: C08G 18/2063 having two nitrogen atoms in the condensed ring system
• CPC Class Codes: C08G 18/24 of tin
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/3281 containing three hydroxy groups
• CPC Class Codes: C08G 18/3284 containing four hydroxy groups
• CPC Class Codes: C08G 18/4804 Two or more polyethers of different physical or chemical nature
• CPC Class Codes: C08G 18/4816 mixtures of two or more polyetherpolyols having at least three hydroxy groups
• CPC Class Codes: C08G 18/482 Mixtures of polyethers containing at least one polyether containing nitrogen
• CPC Class Codes: C08G 18/4829 Polyethers containing at least three hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/751 containing only one cycloaliphatic ring
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 18/7664 containing alkylene polyphenyl groups
• CPC Class Codes: C08G 18/7831 containing biuret groups
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/8016 : Masked aliphatic or cycloaliphatic polyisocyanates
• CPC Class Codes: C08J 2375/04 : Polyurethanes
• CPC Class Codes: C08J 2375/08 : from polyethers
• CPC Class Codes: C08J 5/04 : Reinforcing macromolecular compounds with loose or coherent fibrous material
• CPC Class Codes: C08K 3/40 : Glass
• CPC Class Codes: C08K 7/14 : Glass

Abstract

Clear polyurethane fiber reinforced composites are produced by a pultrusion process with a polyurethane-forming system that includes: (a) a clear, aliphatic polyisocyanate having a viscosity at 25° C. of no more than 1000 centipoise, (b) a colorless polyol component comprising an amine-initiated polyol having a molecular weight of from about 150 to about 400 and an OH functionality greater than or equal to 3, and (c) a catalyst. These fiber-reinforced composites are characterized by both excellent weathering characteristics and excellent physical properties.

Claims

1. A clear polyurethane-forming system for the preparation of a fiber reinforced composite by a pultrusion process comprising:

(a) a clear, aliphatic polyisocyanate having a viscosity at 25°

C. of no more than 1000 centipoise, and

(b) a colorless polyol component comprising an amine-initiated polyol having a molecular weight of from about 150 to about 400 and an OH functionality greater than or equal to 3, and

(c) a catalyst.

2. The system of claim 1 in which (a) is HMDI.

3. The system of claim 1 in which the amine-initiated polyol has an OH functionality of at least 4.

4. The system of claim 1 in which (a) is IPDI.

5. The system of claim 1 in which (b) further comprises a colorless, short-chained polyether polyol that is not amine-initiated having an OH functionality of at least 3.

6. A reaction system for the preparation of a fiber reinforced composite by a pultrusion process comprising:

(a) a clear, aliphatic polyisocyanate having a viscosity at 25°

C. of no more than 1000 centipoise,

(b) a colorless polyol component comprising an amine-initiated polyol having a molecular weight of from about 150 to about 400 and an OH functionality greater than or equal to 3,

(c) a catalyst, and

(d) a fiber reinforcing material.

7. The reaction system of claim 6 in which (d) is selected from the group consisting of single strands, braided strands, woven mat structures, non-woven mat structures and combinations thereof.

8. The reaction system of claim 6 in which (d) comprises one or more of glass fibers, glass mats, carbon fibers, polyester fibers, natural fibers, aramid fibers, basalt fibers and nylon fibers.

9. The reaction system of claim 6 in which (d) comprises glass fibers.

10. The reaction system of claim 6 in which (a) is selected from the group consisting of ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (“

isophorone diisocyanate”

), 2,4- and 2,6-hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4′

-diisocyanate (“

hydrogenated MDI”

, or “

HMDI”

), isocyanate-terminated prepolymers and mixtures thereof.

11. The reaction system of claim 6 in which (a) is HMDI.

12. The reaction system of claim 6 in which the amine-initiated polyol has an OH functionality of at least 4.

13. The reaction system of claim 6 in which (a) is IPDI.

14. The reaction system of claim 6 in which (b) further comprises a colorless, short-chained polyether polyol that is not amine-initiated having an OH functionality of at least 3.

15. A pultrusion process for preparing a fiber reinforced polyurethane composite comprising:

(a) continuously pulling a roving or tow of continuous fiber reinforcing material successively through an impregnation chamber and a die;

(b) continuously feeding the polyurethane-forming system of claim 1 to the impregnation chamber;

(c) contacting the fiber reinforcing material with the polyurethane-forming system in the impregnation chamber such that substantially complete wetting of the material by the formulation occurs;

(d) directing the fiber reinforcing material through a die heated to reaction temperature to form a solid composite; and

(e) drawing the composite from the die,

wherein conditions in the impregnation chamber are such that substantially no polymerization takes place.

16. The pultrusion process of claim 15 in which the fiber reinforcing material is selected from the group consisting of single strands, braided strands, woven mat structures, non-woven mat structures and combinations thereof.

17. The pultrusion process of claim 15 in which the fiber reinforcing material comprises one or more of glass fibers, glass mats, carbon fibers, polyester fibers, natural fibers, aramid fibers, basalt fibers and nylon fibers.

18. The pultrusion process of claim 15 in which the fiber reinforcing material comprises glass fibers.

19. The pultrusion process of claim 15 in which (a) is chosen from 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (“

isophorone diisocyanate”

) and dicyclohexylmethane-4,4′

-diisocyanate (“

hydrogenated MEN”

, or “

HMDI”

).

20. A fiber reinforced polyurethane composite made by the process of claim 15.