Composite semifinished products, molded parts produced therefrom, and molded parts produced directly based on hydroxy-functionalized (meth)acrylates, which are cross-linked by means of uretdiones in a thermosetting manner

Patent metadata

Field	Value
Publication number	US-9878500-B2
Application number	US-201113978059-A
Country	US
Kind code	B2
Filing date	Dec 1, 2011
Priority date	Jan 4, 2011
Publication date	Jan 30, 2018
Grant date	Jan 30, 2018

Abstract

Provided is a prepreg composed of a fibrous substrate impregnated with a reactive or highly reactive polymer composition as a matrix material. The reactive or highly reactive polymer composition contains a (meth)acrylate-based resin comprising at least one of a hydroxyl group, an amine group, a thiol group, an initiator and/or accelerator, and a di- or polyisocyanate which has been internally capped, capped with a capping agent, or a combination thereof. The (meth)acrylate-based resin contains from 20% by weight to 70% by weight of at least one (meth)acrylate monomer and from 1% by weight to 50% by weight of at least one prepolymer.

First claim

The invention claimed is:

1. A prepreg, consisting of a fibrous substrate impregnated with a reactive or highly reactive polymer composition as a matrix material,
wherein the reactive or highly reactive polymer composition comprises:
at least one (meth)acrylate-based resin comprising at least one of a hydroxyl group, an amine group, or a thiol group;
at least one initiator and/or accelerator; and
at least one di- or polyisocyanate which has been internally capped, capped with a capping agent, or a combination thereof,

wherein the (meth)acrylate-based resin comprises from 20% by weight to 70% by weight of at least one (meth)acrylate monomer and from 1% by weight to 50% by weight of at least one prepolymer;
wherein the di- or polyisocyanate is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (H 12 MDI), 2-methylpentane diisocyanate (MPDI), trimethylhexamethylene 2,2,4-diisocyanate/trimethylhexamethylene 2,4,4-diisocyanate (TMDI), norbornane diisocyanate (NBDI), an isocyanurate, or any combination thereof.

2. The prepreg of claim 1 , wherein a weight ratio of the (meth)acrylate-based resin to the di- or polyisocyanate is from 90:10 to 50:50.

3. The product of claim 1 , wherein the (meth)acrylate-based resin comprises:
from 0% by weight to 30% by weight of at least one crosslinking agent,
from 30% by weight to 60% by weight of the (meth)acrylate monomer, and
from 5% by weight to 40% by weight of the prepolymer.

4. The prepreg of claim 1 , wherein the (meth)acrylate-based resin comprises:
from 0% by weight to 30% by weight of at least one crosslinking agent,
from 30% by weight to 60% by weight of the (meth)acrylate monomer,
from 0% by weight to 20% by weight of at least one urethane (meth)acrylate, and
from 5% by weight to 40% by weight of the prepolymer.

5. The prepreg of claim 1 , wherein the reactive or highly reactive polymer composition further comprises (1) at least one initiator selected from the group consisting of dilauroyl peroxide, a permaleate, dibenzoyl peroxide, or any combination thereof and (2) at least one accelerator selected from the group consisting of tertiary, aromatically substituted amines.

6. The prepreg of claim 1 , wherein the fibrous substrate comprises glass, carbon, plastic, natural fiber or a mineral fiber material.

7. The prepreg of claim 6 , wherein the fibrous substrate is a textile sheet comprising a non-woven fabric, a knitted fabric, or a non-knitted structure, and wherein the fibrous substrate is a long-fiber material or a short-fiber material.

8. A prepreg, consisting of a fibrous substrate impregnated with a reactive or highly reactive polymer composition as a matrix material,
wherein the reactive or highly reactive polymer composition comprises:
at least one (meth)acrylate-based resin comprising at least one of a hydroxyl group, an amine group, or a thiol group;
at least one initiator and/or accelerator; and
at least one di- or polyisocyanate which has been internally capped, capped with a capping agent, or a combination thereof,

wherein the (meth)acrylate-based resin comprises from 20% by weight to 70% by weight of at least one (meth)acrylate monomer and from 1% by weight to 50% by weight of at least one prepolymer;
wherein the di- or polyisocyanate has been capped with at least one of ethyl acetoacetate, diisopropylamine, methyl ethyl ketoxime, diethyl malonate, ε-caprolactam, 1,2,4-triazole, phenol, substituted phenol and 3,5-dimethylpyrazole.

9. The prepreg of claim 1 , wherein the reactive or highly reactive polymer composition further comprises from 0.1 to 5.0% by weight of at least one catalyst.

10. The prepreg of claim 1 , wherein the di- or polyisocyanate which has been internally capped, capped with a capping agent or a combination thereof is a uretdione produced from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (H 12 MDI), 2-methylpentane diisocyanate (MPDI), trimethylhexamethylene 2,2,4-diisocyanate/trimethylhexamethylene 2,4,4-diisocyanate (TMDI), norbornane diisocyanate (NBDI), or any combination thereof.

11. A prepreg, consisting of a fibrous substrate impregnated with a reactive or highly reactive polymer composition as a matrix material,
wherein the reactive or highly reactive polymer composition comprises:
at least one (meth)acrylate-based resin comprising at least one of a hydroxyl group, an amine group, or a thiol group;
at least one initiator and/or accelerator; and
at least one di- or polyisocyanate which has been internally capped, capped with a capping agent, or a combination thereof,

wherein the (meth)acrylate-based resin comprises from 20% by weight to 70% by weight of at least one (meth)acrylate monomer and from 1% by weight to 50% by weight of at least one prepolymer;
wherein the di- or polyisocyanate which has been internally capped, capped with a capping agent is solid below 40° C. and liquid above 125° C., and has less than 5% by weight free NCO content and has from 3 to 25% by weight uretdione content.

12. The prepreg of claim 1 , wherein the reactive or highly reactive polymer composition further comprises from 0.1 to 5% by weight of at least one catalyst selected from the group consisting of a quaternary ammonium salt and a quaternary phosphonium salt, and
wherein the catalyst comprises a halogen, hydroxide, alcoholate, or organic or inorganic acid anion as a counterion.

13. The prepreg of claim 1 , wherein the reactive or highly reactive polymer composition further comprises 0.1 to 5% by weight of at least one co-catalyst, selected from the group consisting of an epoxide, a metal acetylacetonate, a quaternary ammonium acetylacetonate, a and quaternary phosphonium acetylacetonate.

14. The prepreg of claim 1 , wherein the (meth)acrylate-based resin contains hydroxyl groups and wherein the ratio of a number of uretdione groups, externally capped isocyanate groups, or both of the isocyanate component to the number of hydroxy groups of the (meth)acrylate-based resin is at least 0.3:1 and at most 1.0:1.

15. A method of preparing the prepreg of claim 1 , comprising:
impregnating the fibrous substrate with the reactive or highly reactive polymer composition.

16. The method of claim 15 , further comprising:
hardening the (meth)acrylate-based resin,
shaping the prepreg to obtain a molding, and
hardening the di- or polyisocyanate which has been internally capped, capped with a capping agent, or a combination thereof.

17. The method of claim 15 , wherein the di- or polyisocyanate is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (H 12 MDI), 2-methylpentane diisocyanate (MPDI), trimethylhexamethylene 2,2,4-diisocyanate/trimethylhexamethylene 2,4,4-diisocyanate (TMDI), norbornane diisocyanate (NBDI), an isocyanurate, or any combination thereof.

18. The method of claim 15 , wherein the hardening the isocyanate component is at a temperature of from 60 to 120° C.

19. A molding obtained by crosslinking the reactive or highly reactive polymer composition in the prepreg of claim 1 .

Assignees

• Schmitt Guenter
• Reemers Sandra
• Spyrou Emmanouil
• Heeb Heike
• Kohlstruk Stephan
• Schmidt Friedrich Georg
• Gollan Elke
• Evonik Degussa Gmbh

Inventors

• Schmitt Guenter
• Reemers Sandra
• Spyrou Emmanouil
• Heeb Heike
• Kohlstruk Stephan
• Schmidt Friedrich Georg
• Gollan Elke

Classifications

• Y02B10/30

  Wind power · CPC title

• B29C70/06 Primary

  Fibrous reinforcements only · CPC title

• Y10T442/2992

  Coated or impregnated glass fiber fabric · CPC title

• C08J5/24 Primary

  Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs · CPC title

• Y10T442/2984

  Coated or impregnated carbon or carbonaceous fiber fabric · CPC title