Partially hydrogenated nitrile rubbers

Patent metadata

Field	Value
Publication number	US-9428592-B2
Application number	US-201113814074-A
Country	US
Kind code	B2
Filing date	Aug 5, 2011
Priority date	Aug 9, 2010
Publication date	Aug 30, 2016
Grant date	Aug 30, 2016

Abstract

Provided are new partially hydrogenated nitrile rubbers which are distinguished by a specific ratio of viscosity to molecular weight, and also vulcanizable mixtures and vulcanizates based on said rubbers, and also the associated preparation processes. The partially hydrogenated nitrile rubbers lead to compounded formulations having advantageous processing properties in conjunction with excellent vulcanizate properties.

First claim

What is claimed is:

1. A partially hydrogenated nitrile rubber comprising:
a degree of hydrogenation of 50% to 97%, and
a ratio of solution viscosity (SV) to weight average of the molecular weight (Mw) of 4*10 −3 to 30*10 −3 Pa*s mol/kg.

2. The partially hydrogenated nitrile rubbers according to claim 1 , wherein the degree of hydrogenation is 52.5% to 96.5%.

3. The partially hydrogenated nitrile rubbers according to claim 1 , wherein the ratio of solution viscosity (SV) to the weight average of the molecular weight (Mw) is 5*10 −3 to 30*10 −3 Pa*s*mol/kg.

4. The partially hydrogenated nitrile rubbers according to claim 1 or 3 , comprising repeating units derived from at least one conjugated diene and at least one α,β-unsaturated nitrile, wherein C═C double bonds of the copolymerized diene repeating units are 55% to 96% hydrogenated.

5. A process for preparing partially hydrogenated nitrile rubbers having a degree of hydrogenation of 50% to 97%, and a ratio of solution viscosity (SV) to weight average of the molecular weight (Mw) of 4*10 −3 to 30*10 −3 Pa*s*mol/kg, the process comprising subjecting partially hydrogenated nitrile rubbers having degrees of hydrogenation of 50% to 97% to a metathesis reaction in the presence of a complex catalyst based on a metal from transition group 6 or 8 of the Periodic Table and comprising at least one ligand attached carbenically to the metal, wherein the metathesis takes place substantially free from C 2 -C 16 olefins.

6. The process according to claim 5 , wherein the complex catalyst is a catalyst selected from the group consisting of:
(i) catalysts of the general formula (A)

in which
M is osmium or ruthenium,
X 1 and X 2 are identical or different and represent two ligands,
L represents identical or different ligands, and
R is identical or different at each occurrence and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, or alkylsulphinyl, optionally substituted in each case by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, or alternatively both radicals A are bridged with incorporation of the common C atom to which they are attached, to form a cyclic group, which may be aliphatic or aromatic in nature, is optionally substituted and may contain one or more heteroatoms,
(ii) a catalyst which possesses the structure (IV) (Grubbs (I) catalyst) or (V) (Grubbs (II) catalyst), where Cy stands for cyclohexyl,

(iii) catalysts of the general formula (B)

in which
M is ruthenium or osmium,
X 1 and X 2 are identical or different ligands,
Y is oxygen (O), sulphur (S), a radical N—R 1 or a radical P—R 1 , where R 1 possesses the definitions identified below,
R 1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, optionally substituted in each case by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,
R 2 , R 3 , R 4 and R 5 are identical or different and are hydrogen or organic or inorganic radicals,
R 6 is H or an alkyl, alkenyl, alkynyl or aryl radical, and
L is a ligand having the same definitions as stated for formula (A),

(iv) a catalyst of the formula (VII)-(XVII), where Mes in each case stands for 2,4,6-trimethylphenyl,

(v) catalysts of the general formula (G), (H) or (K),

in which
M is osmium or ruthenium,
X 1 and X 2 are identical or different and represent two ligands,
L represents a ligand,
Z 1 and Z 2 are identical or different and represent neutral electron donors,
R 21 and R 22 independently of one another are hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamine, alkylthio, alkylsulphonyl or alkylsulphinyl, optionally substituted by one or more radicals selected from alkyl, halogen, alkoxy, aryl or heteroaryl, and

(vi) a catalyst of the following formula, where Mes in each case stands for 2,4,6-trimethylphenyl

7. The process according to claim 5 or 6 , wherein an amount of catalyst used, based on the partially hydrogenated nitrile rubber used, is 5 to 1000 ppm of noble metal.

8. The process according to claim 5 or 6 , wherein a concentration of the partially hydrogenated nitrile rubber in the reaction mixture is 1% to 20% by weight.

9. The process according to claim 5 or 6 , wherein the metathesis reaction is carried out at a temperature of 20° C. to 150° C.

10. A vulcanizable mixture comprising:
(i) at least one partially hydrogenated nitrile rubber having a degree of hydrogenation of 50% to 97%, and a ratio of solution viscosity (SV) to weight average of the molecular weight (Mw) of 4*10 −3 to 30*10 −3 Pa*s*mol/kg, and
(ii) at least one peroxidic crosslinking system.

11. The vulcanizable mixture according to claim 10 , further comprising (iii) at least one filler and/or (v) one or more further, different additives.

12. A process for preparing the vulcanizable mixtures according to claim 10 or 11 , the process comprising mixing the partially hydrogenated nitrile rubber (i) with at least one peroxidic crosslinking system (ii), optionally at least one filler (iii) and/or one or more further, different additives (iv).

13. A process for producing vulcanizates, the process comprising crosslinking the vulcanizable mixture according to claim 10 or 11 by temperature increase.

14. A vulcanizate obtained by the process according to claim 13 .

15. The partially hydrogenated nitrile rubbers according to claim 1 , wherein the degree of hydrogenation is 55% to 96%, and the ratio of solution viscosity (SV) to the weight average of the molecular weight (Mw) is 5*10 −3 to 30*10 −3 Pa*s*mol/kg.

16. The partially hydrogenated nitrile rubbers according to claim 1 , wherein the degree of hydrogenation is 57.5% to 95.5%, and the ratio of solution viscosity (SV) to the weight average of the molecular weight (Mw) is 6*10 −3 to 30*10 −3 Pa*s*mol/kg.

17. The partially hydrogenated nitrile rubbers according to claim 1 , comprising repeating units derived from at least one conjugated diene and at least one α,β-unsaturated nitrile, wherein C═C double bonds of the copolymerized diene repeating units are 60% to 95% hydrogenated, and the ratio of solution viscosity (SV) to the weight average of the molecular weight (Mw) is 6.5*10 −3 to 30*10 −3 Pa*s*mol/kg.

18. The vulcanizable mixture according to claim 10 , wherein the at least one partially hydrogenat

Assignees

• Obrecht Werner
• Müller Julia Maria
• Nuyken Oskar
• Schneider Martin
• Lanxess Deutschland Gmbh

Inventors

• Obrecht Werner
• Müller Julia Maria
• Nuyken Oskar
• Schneider Martin

Classifications

• C08K5/14

  Peroxides · CPC title

• C08L15/005

  Hydrogenated nitrile rubber · CPC title

• C08J2309/02

  Copolymers with acrylonitrile · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08C19/02 Primary

  Hydrogenation · CPC title