Storage-stable polyurethane prepregs and mouldings produced therefrom composed of a polyurethane composition with liquid resin components

Patent metadata

Field	Value
Publication number	US-10633519-B2
Application number	US-201214007585-A
Country	US
Kind code	B2
Filing date	Mar 21, 2012
Priority date	Mar 25, 2011
Publication date	Apr 28, 2020
Grant date	Apr 28, 2020

Abstract

Provided is a storage-stable polyurethane prepegs and mouldings produced therefrom composed of polyurethane compositions with liquid resin components, preferably liquid polyols. A prepeg contains(A)a fibrous support and (B)a matrix material containing a reactive polyurethane composition. The polyurethane composition contains a mixture of a liquid resin component(b)having a functional group reactive towards an isocyanate and having a glass transition temperature(Tg)or melting point below 25° C., with a hydroxyl number of 50 to 2000 mg KOH/gram, and a curing agent(a)comprising a di- or polyisocyanate internally blocked or blocked with a blocking agent. In addition, the polyurethane composition contains 0.6 to NCO equivalents or 0.3 to 1 uretdione group in (a) for each functional group of (b).

First claim

The invention claimed is:

1. A prepreg, comprising:
A) a fibrous support and
B) a reactive polyurethane composition comprising:
a) a curing agent containing uretdione groups, based on polyaddition compounds from aliphatic, (cyclo)aliphatic or cycloaliphatic polyisocyanates containing uretdione groups and hydroxyl group-containing compounds, where the curing agent exists in solid form below 40° C. and in liquid form above 110° C., and has a free NCO content of less than 5 wt.% and a uretdione content of 3-25 wt.%,
b) at least one hydroxyl group-containing liquid resin component b) having a glass transition temperature (Tg) or melting point below 25° C. and an OH number between 50 and 2000 mg KOH/gram,
c) optionally at least one catalyst,
d) optionally auxiliary substances and additives,
wherein components a) and b) are present in a ratio such that there is from 0.3 to 1 uretdione group of component a) for each hydroxyl group of component b) and

the curing agent does not comprise an external blocking agent.

2. The prepreg of claim 1 , wherein a melting point of the reactive polyurethane composition is at least 30° C.

3. The prepreg of claim 1 , wherein a glass transition temperature (Tg) of the reactive polyurethane composition is at least 30° C.

4. The prepreg of claim 1 , wherein the fibrous support comprises a glass fiber, a carbon fiber, a plastic fiber, a natural fiber or a mineral fiber.

5. The prepreg of claim 1 , wherein the fibrous support comprises a planar textile body of non-woven material, a knitted good, or a non-knitted skein.

6. The prepreg of claim 1 , wherein the aliphatic, (cyclo)aliphatic or cycloaliphatic polyisocyanate is at least one member 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 (TMDI), and norbornane diisocyanate (NBDI).

7. The prepreg of claim 1 , wherein the aliphatic, (cyclo)aliphatic or cycloaliphatic polyisocyanate comprises an isophorone diisocyanate adduct comprising an isocyanurate grouping.

8. The prepreg of claim 1 , wherein the reactive polyurethane composition comprises the at least one catalyst c) and a content of the catalyst c) is from 0.001 to 1 wt.% based on the total weight of the reactive polyurethane composition.

9. The prepreg of claim 1 , wherein the prepreg comprises the at least one catalyst c):
a content of the catalyst c) is from 0.1 to 5 wt.%, based on the total weight of the reactive polyurethane composition,
the catalyst c) comprises a quaternary ammonium salt or a quaternary phosphonium salt, having a halogen, a hydroxide, an alcoholate, or an organic or inorganic acid anion as a counter-ion; and the prepeg comprises
at least one cocatalyst as additive d),
a content of the at least one cocatalyst is from 0.1 to 5 wt.%, based on the total weight of the reactive polyurethane composition, and
the at least one cocatalyst is selected from the group consisting of d1) and d2):
d1) an epoxide

and
d2) a metal acetylacetonate, a quaternary ammonium acetylacetonate, or a quaternary phosphonium acetylacetonate; and

the prepeg further optionally comprises e) an auxiliary substance or additive.

10. The prepreg of claim 1 , which comprises the at least one catalyst c) and the catalyst c) is selected from the group consisting of tetramethylammonium fotimiate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylannnonium benzoate, tetraethylaminoniumn formate, tetraethylammoniinn acetate, tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrapropylammonium benzoate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate and tetrabutyl-ammonium benzoate and tetrabutylphosphonium acetate, tetrabutylphosphonium formate and ethyltriphenylphosphonium acetate, tetrabutylphosphonium benzotriazolate, tetraphenyl-phosphonium phenolate and trihexylletradecylphosphonium decanoate, methyltributyl-ammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetrabutyl-ammonium hydroxide, tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethyl-ammonium hydroxide, trimethylvinylammonium hydroxide, methyltributylammonium methanolate, methyltriethylammonium methanolate, tetramethylammonium methanolate, tetraethylammonium methanolate, tetrapropylammonium methanolate, tetrabutylammonium methanolate, tetrapentylammonium methanolate, tetrahexylammonium methanolate, tetraoctylammonium methanolate, tetradecylammonium methanolate, tetradecyltrihexyl-ammonium methanolate, tetraoctadecylammonium methanolate, benzyltrimethylammonium methanolate, benzyltriethylammonium methanolate, trimethylphenylammonium methanolate, triethylmethylammonium methanolate, trimethylvinylammonium methanolate, methyltributyl-ammonium ethanolate, methyltriethylammonium ethanolate, tetramethylammonium ethanolate, tetraethylammonium ethanolate, tetrapropylammonium ethanolate, tetrabutyl-ammonium ethanolate, tetrapentylammonium ethanolate, tetrahexylammonium ethanolate, tetraoctylammonium methanolate, tetradecylammonium ethanolate, tetradecyltrihexyl-ammonium ethanolate, tetraoctadecylammonium ethanolate, benzyltrimethylammonium ethanolate, bertzyltriethylammonium ethanolate, trimethylphenylammonium ethanolate, triethylmethylammonium ethanolate, trimethylvinylammonium ethanolate, methyltributyl-ammonium benzylate, methyltriethylammonium benzylate, tetramethylammonium benzylate, tetraethylammonium benzylate, tetrapropylammonium benzylate, tetrabutylammonium benzylate, tetrapentylanamonium benzylate, tetrahexylanmionium benzylate, tetraoctyl-ammonium benzylate, tetradecylammonium benzylate, tetradecyltrihexylammonium benzylate, tetraoctadecylammonium benzylate, benzyltrimethylammonium benzylate, benzyhriethylammonium benzylate, trimethylpheitylammonium benzylate, triethylmethyl-ammonium benzylate, trimethylvinylarnmonium benzylate, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride, benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide, tetrabutyiphosphonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethyl-ammonium iodide, benzyltrimethylammonium chloride, benzyltriethylarnmonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, methyltributyl-ammonium chloride, methyltripropylammonium chloride, methyltriethylammonium chloride, methyltriphenylammoniurn chloride, phenyltrimethylammonium chloride, benzyltrimethyl-ammonium bromide, benzyltriethylammonium bromide, benzyltripropylammonium bromide, benzyltributylammonium bromide, methyltributylammonium bromide, methyltripropyl-ammonium bromide, methyltriethylammonium bromide, methyltriphenylammonium bromide, phenyltrimethylammonium bromide, benzyltrimethylammonium iodide, benzyltriethyl-ammonium iodide, benzyltripropylammonium iodide, benzyltributylammonium iodide

Assignees

• Spyrou Emmanouil
• Schmidt Friedrich Georg
• Langkabel Eike
• Cielaszyk Katharina
• Reemers Sandra
• Loesch Holger
• Gollan Elke
• Grammenos Marina
• Evonik Operations Gmbh

Inventors

• Spyrou Emmanouil
• Schmidt Friedrich Georg
• Langkabel Eike
• Cielaszyk Katharina
• Reemers Sandra
• Loesch Holger
• Gollan Elke
• Grammenos Marina

Classifications

• 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

• B29B15/10

  Coating or impregnating {independently of the moulding or shaping step}(applying liquids in general B05) · CPC title

• C08K7/14 Primary

  Glass · CPC title

• C08J2375/08

  from polyethers · CPC title

• C08K5/315

  Compounds containing carbon-to-nitrogen triple bonds · CPC title