Cured composition having high impact strength and temperature resistance, based on an epoxy resin and a polyisocyanate

Patent metadata

Field	Value
Publication number	US-11566113-B2
Application number	US-201816217697-A
Country	US
Kind code	B2
Filing date	Dec 12, 2018
Priority date	Jun 20, 2016
Publication date	Jan 31, 2023
Grant date	Jan 31, 2023

Abstract

The invention relates to a method for producing a cured composition which has at least one oxazolidinone ring and at least one isocyanurate ring and is cross-linked by the same, starting from a liquid reactive mixture which, based on the total weight thereof, contains at least one epoxy resin, at least one polyisocyanate, at least one polyol, and at least one catalyst composition. The invention further relates to the cured composition obtainable thereby.

First claim

The invention claimed is:

1. A method for preparing a cured polymer composition which comprises at least one oxazolidinone ring and at least one isocyanurate ring, wherein the method comprises the steps of:
(1) providing a liquid reaction mixture comprising, based on the total weight thereof:
(a) 30 to 50 wt. % of at least one liquid, aromatic epoxy resin;
(b) 35 to 70 wt. % of at least one liquid, aromatic polyisocyanate;
(c) 4 to 20.0 wt. % of at least one polyol; and
(d) 0.01 to 10.0 wt. % of a catalyst wherein all of the catalyst in the reaction mixture consist of 1-methylimidazole, 2,4-ethylmethylimidazole (EMI), 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[3.4.0]non-5-ene (DBN) and mixtures thereof,
wherein the at least one epoxy resin, based on the at least one polyisocyanate, is used in such amounts that the molar equivalent ratio of isocyanate groups to epoxide groups is between 1.4 and 10; and

(2) curing the reaction mixture in order to obtain a cured polymer composition which comprises at least one oxazolidinone ring and at least one isocyanurate ring.

2. The method according to claim 1 , wherein the at least one epoxy resin is a glycidyl ether.

3. The method according to claim 1 , wherein the at least one epoxy resin is a bisphenol diglycidyl ether.

4. The method according to claim 1 , wherein the at least one polyisocyanate is a methylene diphenyl diisocyanate (MDI).

5. The method according to claim 1 , wherein the at least one polyol is selected from the group consisting of polyether polyol, polyester polyol and mixtures thereof.

6. The method according to claim 1 , wherein the at least one polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol and mixtures thereof.

7. The method according to claim 1 , wherein:
(a) the reaction mixture is free of epoxy curing agents which enter into a polyaddition reaction;
(b) the reaction mixture has a viscosity of <100 mPas at a temperature of 80° C.;
(c) the cured polymer composition has a modulus of elasticity of more than 2500 N/mm 2 ; and/or
(d) the cured polymer composition has a glass transition temperature of more than 100.

8. The method according to claim 1 , wherein:
(a) the reaction mixture in step (2) is cured at a temperature of between 10° C. and 230° C. for 0.01 to 10 hours; or
(b) the reaction mixture in step (2) is first cured at a temperature of between 50° C. and 130° C. for 0.1 hours to 3 hours and then at a temperature of between 110° C. and 190° C. for 0.1 hours to 3 hours.

9. The method according to claim 1 , wherein the method is a transfer molding (RTM) method and the reaction mixture is a reactive injection resin.

10. The method according to claim 9 , wherein step (1) comprises injecting the reactive injection resin into a die in which fibers or semi-finished fiber products are disposed.

11. The cured polymer composition of claim 1 .

12. A resin composition, wherein the resin composition comprises, based on the total weight thereof:
(a) 45.0 to 82.5 wt. % of at least one liquid, aromatic epoxy resin;
(b) 35 to 60 wt. % of at least one liquid, aromatic polyisocyanate;
(c) 1.0 to 20.0 wt. % of at least one polyol; and
(d) 0.01 to 10.0 wt. % of at least one catalyst;
wherein the at one epoxy resin, based on the at least one polyisocyanate, being used in such amounts that the molar equivalent ratio of isocyanate groups to epoxide groups is greater than 1.2.

13. Cured reaction products of the polymer composition according to claim 12 .

14. A fiber-reinforced molded article comprising cured reaction products of the polymer composition according to claim 12 .

15. The resin composition according to claim 12 , wherein all of the catalyst is a tertiary amine of formula (I) NR 1 R 2 R 3 and/or an imine of formula (II) N(═R 4 )R 5 ,
R 1 to R 3 and R 5 are each independently selected from the group consisting of substituted or unsubstituted, linear or branched alkyl having 1 to 20 carbon atoms, substituted or unsubstituted, linear or branched alkenyl having 3 to 20 carbon atoms and substituted or unsubstituted aryl having 5 to 20 carbon atoms, or at least two of R 1 to R 3 form, together with the nitrogen atom to which they are bonded, a 5- to 10-membered heteroalicyclic ring or heteroaryl ring, which optionally contains one or more additional nitrogen atoms,
R 4 is a substituted or unsubstituted, linear or branched alkylenyl having 3 to 20 carbon atoms, or R 4 and R 5 form, together with the nitrogen atom to which they are bonded, a 5- to 10-membered heteroalicyclic ring or heteroaryl ring, which optionally contains additional nitrogen atoms.

16. The resin composition according to claim 15 , wherein R 4 and R 5 form, together with the nitrogen atom to which they are bonded, a 5- to 10-membered heteroalicyclic ring or heteroaryl ring, which optionally contains additional nitrogen atoms.

17. The resin composition according to claim 12 , further comprising (e) one or more of solvent, a modified resin, toughener, filler, softener, reactive diluent, nonreactive diluent, coupling agent, adhesion promoter, wetting agent, release agents flame retardant, thixotropic agent, rheological auxiliary, ageing inhibitor, corrosion inhibitor, stabilizer and dye.

18. The resin composition according to claim 12 , wherein all of the catalyst in the resin composition consists of a mixture of 2,4-ethylmethylimidazole (EMI) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

Assignees

• Henkel Ag & Co Kgaa

Inventors

• Holtgrewe Christian
• Kuester Harald
• Bachon Thomas
• Sanchis Otero Guadalupe

Classifications

• C08G59/4028

  Isocyanates; Thioisocyanates · CPC title

• C08J2375/08

  from polyethers · CPC title

• C08G18/2081

  containing at least two non-condensed heterocyclic rings · CPC title

• C08G18/2063

  having two nitrogen atoms in the condensed ring system · CPC title

• C08G18/4895

  prepared from polyepoxy compounds · CPC title