Process for the production of storage-stable polyurethane prepregs and mouldings produced therefrom from dissolved polyurethane composition

Patent metadata

Field	Value
Publication number	US-10029427-B2
Application number	US-201113825728-A
Country	US
Kind code	B2
Filing date	May 30, 2011
Priority date	Sep 23, 2010
Publication date	Jul 24, 2018
Grant date	Jul 24, 2018

Abstract

The invention relates to a method for producing storage-stable polyurethane prepregs and molding bodies produced therefrom (composite components), which can be obtained by a method using a polyurethane composition in solution and by impregnation of fiber-reinforced materials such as of woven fabrics and laid scrim using reactive polyurethane compositions.

First claim

The invention claimed is:

1. A process of producing a prepreg, the process comprising, in the following order:
directly impregnating a fibrous support with a solution comprising a reactive polyurethane composition and a solvent, to obtain a prepreg intermediate; and then
removing the solvent from the prepreg intermediate at a temperature less than 100° C., to obtain a prepreg comprising the fibrous support and a crosslinkable matrix comprising the reactive polyurethane composition and less than 0.5% by weight of the solvent,
wherein the reactive polyurethane composition comprises (1) a polymer comprising a functional group reactive towards an isocyanate and (2) at least one internally blocked di- or polyisocyanate,
wherein the polymer comprising a functional group reactive towards an isocyanate functions as a binder and is at least one member selected from the group consisting of polyesters, polyacrylates, and polycarbonates,
wherein the internally blocked di- or polyisocyanate functions as a curing agent, and
wherein the matrix in the prepreg is not crosslinked.

2. The process according to claim 1 , wherein the matrix has a Tg of at least 40° C.

3. The process according to claim 1 , wherein the fibrous support comprises a glass, carbon, plastic, natural fiber, or mineral fiber.

4. The process according to claim 1 , wherein the fibrous support is a planar textile body comprising a non-woven material, a knitted good, or a non-knitted skein.

5. The process according to claim 1 , wherein the polymer comprises at least one functionality selected from the group consisting of a hydroxyl group, an amino group, and a thiol group.

6. The process according to claim 1 , wherein the di- or polyisocyanate is selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (H 12 MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl-hexamethylene diisocyanate, norbornane diisocyanate (NBDI), and an isocyanurate.

7. The process according to claim 1 , wherein the reactive polyurethane composition further comprises a catalyst in an amount of from 0.001 to 1 wt. %.

8. The process according to claim 1 , wherein the fibrous support comprises a fibrous support of a glass, carbon, or aramid fiber.

9. A process of producing a composite, comprising:
producing a prepreg according to claim 1 ; and
crosslinking the matrix,
wherein the composite is suitable for boat and shipbuilding, aerospace technology, automobile manufacturing, bicycle manufacturing, automotive, construction, or medical engineering technology, sport fields, electrical and electronics industries, or power generation plants.

10. The process according to claim 1 , wherein the polymer comprising a functional group reactive towards an isocyanate has an OH number of from 20 to 500 mg KOH/gram and an average molecular weight of from 250 to 6000 g/mol.

11. The process according to claim 1 , wherein the polymer comprising a functional group reactive towards an isocyanate is a polyacrylate.

12. The process according to claim 1 , wherein the polymer comprising a functional group reactive towards an isocyanate is a polyester.

13. The process according to claim 1 , wherein the di- or polyisocyanate is internally blocked with a uretdione.

14. The process according to claim 1 , wherein:
the polymer comprising a functional group reactive towards an isocyanate is a hydroxyl group-containing polymer, wherein the hydroxyl group-containing polymer is a solid below 40° C. and a liquid above 125° C. and has an OH number between 20 and 200 mg KOH/gram,
the internally blocked di- or polyisocyanate is a polyisocyanate containing uretdione groups, wherein the polyisocyanate containing uretdione groups is a polyaddition compound of an aliphatic, (cyclo)aliphatic, or cycloaliphatic polyisocyanate containing uretdione groups and a hydroxyl group-containing compound, wherein the polyisocyanate containing uretdione groups is solid below 40° C. and a liquid above 125° C., has a free NCO content of less than 5wt. %, and a uretdione content of from 3 to 25 wt. %,
the hydroxyl groups of the hydroxyl group containing-containing polymer reacts with the uretdione groups of the polyisocyanate containing uretdione groups and for every hydroxyl group of the hydroxyl group-containing polymer, 0.3 to 1 uretdione groups of the polyisocyanate containing uretdione groups is consumed, and
the matrix optionally further comprises at least one component selected from the group consisting of a catalyst, an auxiliary substance, and an additive.

15. The process, according to claim 1 , wherein:
the matrix is a highly reactive powdery polyurethane composition comprising uretdione groups,
the internally blocked di- or polyisocyanate comprises a uretdione group,
the matrix further comprises 0.1 to 5 wt. % of at least one catalyst selected from the group consisting of a quaternary ammonium salt and a quaternary phosphonium salt, wherein the quaternary ammonium salt and the quaternary phosphonium salt comprise a halogen, a hydroxide, an alcoholate, an organic acid anion, or an inorganic acid anion as a counter-ion,
the matrix further comprises 0.1 to 5 wt. % of at least one cocatalyst selected from the group consisting of an epoxide, a metal acetylacetonate, a quaternary ammonium acetylacetonate, and a quaternary phosphonium acetylacetonate, and
the matrix optionally further comprises an auxiliary substance, an additive, or a mixture thereof.

16. The process according to claim 1 , wherein:
the matrix is a highly reactive powdery polyurethane composition comprising uretdione groups,
the matrix further comprises 0.1 to 5 wt. % of at least one catalyst selected from the group consisting of a quaternary ammonium salt and a quaternary phosphonium salt, wherein the quaternary ammonium salt and the quaternary phosphonium salt comprise a halogen, a hydroxide, an alcoholate, an organic acid anion, or an inorganic acid anion as a counter-ion,
the matrix farther comprisies 0.1 to 5 wt. % of at least one cocatalyst selected from the group consisting of an epoxide, a metal acetylacetonate, a quaternary ammonium acetylacetonate, and a quaternary phosphonium acetylacetonate,
the polymer comprising a functional group reactive towards an isocyanate is a hydroxyl group-containing polymer, wherein the hydroxyl group-containing polymer is a solid below 40° C. and a liquid above 125° C. and has an OH number between 20 and 200 mg KOH/gram,
the internally blocked di- or polyisocyanate is a polyisocyanate containing uretdione groups, wherein the polyisocyanate containing uretdione groups is a polyaddition compound of an aliphatic, (cyclo)aliphatic, or cycloaliphatic polyisocyanate containing uretdione groups and a hydroxyl group-containing compound, wherein the polyisocyanate containing uretdione groups is solid below 40° C. and a liquid above 125° C., has a free NCO content of less than 5wt. %, and a uretdione content of from 3 to 25 wt. %, and
the hydroxyl groups of the hydroxyl group containing-containing polymer reacts with the uretdione groups of the polyisocyanate containing uretdione groups and for every hydroxyl group of the hydroxyl group-containing polymer, 0.3 to 1 uretdione groups of the polyisocyanate containing uretdione groups is consumed.

Assignees

• Schmidt Friedrich Georg
• Lomoelder Rainer
• Ortelt Martina
• Kohlstruk Britta
• Spyrou Emmanouil
• Loesch Holger
• Fuchsmann Dirk
• Evonik Degussa Gmbh

Inventors

• Schmidt Friedrich Georg
• Lomoelder Rainer
• Ortelt Martina
• Kohlstruk Britta
• Spyrou Emmanouil
• Loesch Holger
• Fuchsmann Dirk

Classifications

• B29C70/50 Primary

  for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] · CPC title

• D06N3/147

  characterised by the isocyanates used · CPC title

• Y10T442/20

  Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer · CPC title

• B29C70/52

  Pultrusion, i.e. forming and compressing by continuously pulling through a die · CPC title

• C08G18/798

  containing urethdione groups · CPC title