Cross-linking agents containing isocyanate groups for nitrile rubbers

Patent metadata

Field	Value
Publication number	US-10597467-B2
Application number	US-201113640775-A
Country	US
Kind code	B2
Filing date	Apr 15, 2011
Priority date	Apr 15, 2010
Publication date	Mar 24, 2020
Grant date	Mar 24, 2020

Abstract

By the use of special cross-linkers that contain at least two isocyanate groups, hydroxyl group-containing optionally hydrogenated nitrile rubber polymers can be successfully cross-linked. Preferred cross-linkers contain allophanate, biuret, uretdione, uretonimine, bridged carbamate, carbodiimide, isocyanurate, iminooxadiazinedione or oxadiazinetrione structural elements.

First claim

What is claimed is:

1. Vulcanized molded articles produced by a process comprising cross-linking, with warming, a vulcanizable composition comprising:
at least one hydroxyl group-containing (H)NBR rubber having a Mooney viscosity ML(1+4)100° C. of 15 to 160 Mooney units, and containing repeating units derived from at least one conjugated diene, at least one α,β-unsaturated nitrile, and at least one copolymerizable hydroxyl group-containing monomer, wherein C═C double bonds in the case of the HNBR are completely or partially hydrogenated;
at least one compound of the general formula (I) as cross-linkers,

wherein
R 1 is O—[M] p —R 3 or NH—[M] p —R 3
R 2 is H
or R 1 and R 2 together yield a single bond or one of the following groups

R 3 , R 4 and R 5 are in each case identical or different and denote H or a radical that contains one or more of the following groups, a saturated, mono- or polyunsaturated carbo- or heterocyclyl radical, straight-chain or branched alkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, alkoxy, aryloxy, heteroaryloxy, amino, amido, hydroxyimino, carbamoyl, alkoxycarbonyl, F, Cl, Br, I, hydroxyl, phosphonato, phosphinato, alkylthio, arylthio, thiocarboxy, sulphinyl, sulphono, sulphino, sulpheno, sulphonic acids, sulphamoyl, silyl, silyloxy, nitrile, sulphanyl, hydroperoxycarbonyl, hydroperoxy, thiocarboxy, dithiocarboxy, hydroxyimino, nitro, nitrosyl, carbonyl, carboxy, oxycarbonyl, oxysulphonyl, oxo, thioxo, borate, selenate, epoxy, cyanate, thiocyanate, isocyanate, thioisocyanate or isocyanide,
M represents repeating units of one or more mono- or polyunsaturated monomers, selected from the group consisting of conjugated or non-conjugated dienes, alkynes, vinyl compounds, and a divalent structural element, which is derived from polymers selected from the group consisting of polyethers, polyalkylene oxides, polysiloxanes, polyols, polycarbonates, polyurethanes, polyisocyanates, polysaccharides, polyesters and polyamides, and
p, q and r are identical or different and are 0 to 10,000;

the compounds of the general formula (I) in each case contain at least two isocyanate groups;
the composition contains either no solvents at all, or not more than 15% by weight solvents, based on the hydroxyl group-containing (H)NBR rubber, and the composition is not in liquid form; and
the composition comprises at least one mold-release agent.

2. The vulcanized molded articles according to claim 1 , wherein the compounds of the general formula (I) contain at least one allophanate, biuret, uretdione, uretonimine, bridged carbamate, carbodiimide, isocyanurate, iminooxadiazinedione or oxadiazinetrione structure.

3. The vulcanized molded articles according to claim 1 , wherein the at least one compound of the general formula (I) comprises one or more compounds of the general formulae (I-1) to (I-6) as cross-linkers,

where, in the general formulae (I-1) to (I-6), the radicals R 1 , R 2 , R 3 , R 4 , R 5 and M and also p, q, r have the same meanings as in claim 1 .

4. The vulcanized molded articles according to claim 1 , wherein the compound of the general formula (I) is a dimer or trimer of diisocyanates.

5. The vulcanized molded articles according to claim 1 , wherein, in the (H)NBR rubber, the copolymerizable hydroxyl group-containing monomer is selected from the group consisting of hydroxyalkyl (meth)acrylates.

6. The vulcanized molded articles according to claim 1 , wherein the (H)NBR rubber additionally comprises repeating units of a copolymerizable cross-linking monomer.

7. The vulcanized molded articles according to claim 6 , wherein the copolymerizable cross-linking monomer is a triacrylate.

8. The vulcanized molded articles according to claim 1 , wherein the composition is free of tin-containing compounds.

9. The vulcanized molded articles according to claim 1 , wherein:
the composition contains at least 33% by weight of the hydroxyl group-containing (H)NBR rubber, based on the weight of the total composition;
the composition contains, based on the hydroxyl group-containing (H)NBR rubber, not more than 10% by weight of solvents during and after the mixing, and
the (H)NBR rubber composition is produced by mixing the hydroxyl group-containing (H)NBR rubber with the compound of the general formula (I) in the presence of not more than 10% by weight of solvents, based on the hydroxyl group-containing (H)NBR rubber.

10. The vulcanized molded articles according to claim 1 , wherein:
the composition contains at least 40% by weight of the hydroxyl group-containing (H)NBR rubber, based on the weight of the total composition, and the Mooney viscosity ML(1+4)100° C. is 25 to 145 Mooney units, and
the composition contains, based on the hydroxyl group-containing (H)NBR rubber, not more than 1% by weight of solvents during and after the mixing, and
the (H)NBR rubber composition is produced by mixing the hydroxyl group-containing (H)NBR rubber with the compound of the general formula (I) in the presence of not more than 1% by weight of solvents, based on the hydroxyl group-containing (H)NBR rubber.

11. A process for the production of vulcanized molded articles according to claim 1 , wherein the process comprises, without predissolving the (H)NBR in a solvent, mixing the (H)NBR rubber and the at least one cross-linker, as is defined in claim 1 .

12. The vulcanized molded articles according to claim 1 , wherein:
the composition, during and after the mixing, contains not more than 5% by weight solvents, based on the hydroxyl group-containing (H)NBR rubber; and
the HNBR rubber and crosslinker are mixed in the presence of not more than 5% by weight of solvents, based on the hydroxyl group-containing (H)NBR rubber.

13. The vulcanized molded articles according to claim 1 , wherein:
the composition, during and after the mixing, contains not more than 1% by weight solvents, based on the hydroxyl group-containing (H)NBR rubber; and
the HNBR rubber and crosslinker are mixed in the presence of not more than 1% by weight of solvents, based on the hydroxyl group-containing (H)NBR rubber.

14. The vulcanized molded articles according to claim 1 , wherein:
the composition contains no solvents at all during and after the mixing; and
the HNBR rubber and crosslinker are mixed in the presence of no solvents at all.

Assignees

• Brandau Sven
• Klimpel Michael
• Magg Hans
• Arlanxeo Deutschland Gmbh

Inventors

• Brandau Sven
• Klimpel Michael
• Magg Hans

Classifications

• C08K5/29 Primary

  Compounds containing {one or more} carbon-to-nitrogen double bonds · CPC title

• C08C19/22 Primary

  Incorporating nitrogen atoms into the molecule · CPC title

• C08C19/38 Primary

  with hydroxy radicals · CPC title

• C08K5/34

  Heterocyclic compounds having nitrogen in the ring · CPC title

• C08L15/00

  Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) · CPC title