Filament winding processes using polyurethane resins and systems for making composites

Patent metadata

Field	Value
Publication number	US-2016332390-A1
Application number	US-201514708538-A
Country	US
Kind code	A1
Filing date	May 11, 2015
Priority date	May 11, 2015
Publication date	Nov 17, 2016
Grant date	—

Abstract

Disclosed are filament winding processes that use a low viscosity polyurethane-forming composition, systems for making a composites and the composites so made.

First claim

What is claimed is:

1 . A process for making a composite, comprising:
a) impregnating a plurality of aligned continuous fibers by passing the aligned fibers through a channel having a polyurethane-forming composition disposed therein, wherein the aligned fibers are contacted with the composition as the fibers pass through the channel; and b) winding the aligned fibers coated thereby about a mandrel which pulls the aligned fibers through the channel, wherein the polyurethane-forming composition comprises a mixture of components comprising:
(i) an isocyanate-functional component comprising an organic polyisocyanate, and (ii) an isocyanate-reactive component comprising:
(A) at least 50% by weight based on total weight of (ii), of an amine-initiated polyether polyol having a functionality of at least 3 and a number average molecular weight of from 100 gram/mole to 4000 gram/mole, and
(B) 10 to 50% by weight, based on total weight of (ii), of a hydroxyl-functional hydrophobic vegetable oil or hydroxyl-functional hydrophobic modified vegetable oil,

with the proviso that:
(1) the isocyanate-reactive component comprises no more than 10% by weight of a polyether polyol produced from an initiator other than an amine, based on the total weight of polyether polyol in the polyurethane-forming composition, or
(2) the isocyanate-reactive component comprises no more than 35% by weight of a poly ether polyol produced from an initiator other than an amine, based on the total weight of polyether polyol in the polyurethane-forming composition, and the isocyanate-reactive component comprises at least 5% by weight, based on the total weight of the isocyanate-reactive component of the polyurethane-forming composition, of anon-reactive hydrophobic oil.

2 . The process of claim 1 , wherein the polyurethane-forming composition has a viscosity, at 25° C., of no more than 1000 mPa·s for at least 30 minutes after mixture of the isocyanate-functional component and the isocyanate-reactive component.

3 . The process of claim 1 , wherein the isocyanate-functional component and the isocyanate-reactive component are mixed in amounts such that the NCO Index is at least 90.

4 . The process of claim 1 , wherein the isocyanate-functional component comprises a modified polymeric diphenylmethane diisocyanate prepolymer.

5 . The process of claim 4 , wherein the a modified polymeric diphenylmethane diisocyanate prepolymer has an NCO content of 31.8-32.6 wt % and a viscosity at 25° C. of 30-50 mPa·s.

6 . The process of claim 1 , wherein the amine-initiated polyether polyol having a functionality of at least 3 comprises a tri-functional polyether polyol and/or a tetra-functional polyether polyol.

7 . The process of claim 6 , wherein the polyurethane-forming composition comprises at least 50% by weight of an amine-initiated polyether triol, based on the total weight of amine-initiated polyether polyol in the composition.

8 . The process of claim 6 , wherein the polyurethane-forming composition comprises:
(1) a tri-functional polyether polyol, and (2) a tetra-functional polyether polyol, wherein the weight ratio of (1) to (2) in the composition is at least 1:2.

9 . The process of claim 6 , wherein the polyurethane-forming composition comprises
(1) an amine-initiated tetra-functional polyether polyol that has a number average molecular weight of from 1000 to 4000, and/or (2) an amine-initiated tetra-functional polyether polyol that has a number average molecular weight of from 100 to 600.

10 . The process of claim 9 , wherein (1) is present in an amount of 75 to 85% by weight, based on the total weight of amine-initiated tetra-functional polyether polyol used in the polyurethane-forming composition, and (2) is present in an amount of 15 to 25% by weight, based on the total weight of amine-initiated tetra-functional polyether polyol used in the polyurethane-forming composition.

11 . The process of claim 1 , wherein, at least some of the amine-initiated polyether polyol has an overall renewables content of from 20% to 85%.

12 . The process of claim 1 , wherein the isocyanate-reactive component comprises no more than 10% by weight of a polyether polyol produced from an initiator other than an amine, based on the total, weight of polyether polyols in the polyurethane-forming composition.

13 . The process of claim 1 , wherein the hydroxyl-functional hydrophobic vegetable oil and/or hydroxyl-functional hydrophobic modified vegetable oil comprises castor oil, a hydroxylated soybean oil and/or a cashew oil-based polyol.

14 . The process of claim 13 , wherein, the hydroxyl-functional hydrophobic vegetable oil comprises a cashew oil-based polyol having a viscosity at 25° C. of less than 9000 mPa·s, an OH number of 175 to 550, and a functionality of from 2 to 5.

15 . The process of claim 1 , wherein the polyurethane-forming composition comprises a non-reactive hydrophobic oil having a viscosity of 10 to 50 Saybolt universal seconds at 37.8° C. measured according to ASTM D2161.

16 . The process of claim 15 , wherein the non-reactive hydrophobic oil is present in an amount of at least 5% by weight and up to 20% by weight, based on the total weight of the isocyanate-reactive component of the polyurethane-forming composition.

17 . A system for making a composite, comprising:
(a) a source of a plurality of continuous fibers; (b) means for aligning the plurality of continuous fibers provided from the source; (c) a resin, injection chamber comprising:
(i) a fiber inlet configured to supply the plurality of aligned fibers to an interior of the chamber;
(ii) a fiber outlet configured to withdraw the plurality of fibers from the chamber;
(iii) a channel extending through, the chamber from the inlet to the outlet, wherein the channel has a tapered vertical measurement, wherein the vertical measurement decreases ill size along the fiber flow path through the channel; and
(iv) a polyurethane-forming composition inlet configured to supply a polyurethane-forming composition to the channel, wherein the inlet comprises a center portion and at least at least two arms extending from the center portion, such that the composition contacts all of the plurality of fibers in the channel,
wherein the polyurethane-forming composition comprises a mixture of components comprising:
(A) an isocyanate-functional component comprising an organic polyisocyanate, and
(B) an isocyanate-reactive component; and

(d) a mandrel configured to form the composite by winding the plurality of fibers withdrawn from the chamber.

18 . The system of claim 17 , wherein the arms extend from the center portion at an angle of at an angle of from 30° to 60°.

19 . The system of claim 17 , wherein the chamber comprises the connection in an abutting relationship one side of a first plate with a side of a second, plate.

20 . The system of claim 17 , wherein the comprising a V-shaped resin polyurethane-forming composition inlet.

21 . The system of claim 19 , wherein the second plate comprises a recessed portion through which the fibers pass, to be impregnated with the polyurethane-forming composition.

22 . The system of claim 19 , wherein the chamber comprises a wiper plate which removes excess resinous material from the fibers as they exit the chamber.

23 . The system of claim 17 , wherein the wherein the polyurethane-forming composition comprises an isocyanate-reactive component comprising:
(A)

Assignees

• Bayer Materialscience Llc

Inventors

• Harasin Stephen J
• Symosko Gene
• Magnotta Albert
• Rocco David P

Classifications

• C08G18/36

  Hydroxylated esters of higher fatty acids · CPC title

• C08G18/482

  Mixtures of polyethers containing at least one polyether containing nitrogen · CPC title

• B29C70/521

  and impregnating the reinforcement before the die · CPC title

• C08J2375/04

  Polyurethanes · CPC title

• B29K2105/25

  Solid · CPC title