Functionalized nitrile rubbers and the production thereof

Patent metadata

Field	Value
Publication number	US-10011664-B2
Application number	US-201213982520-A
Country	US
Kind code	B2
Filing date	Jan 25, 2012
Priority date	Feb 4, 2011
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

Provided are new functionalized nitrile rubbers, which may optionally also be in partially or wholly hydrogenated form, and also a process for preparing them by metathesis of nitrile rubbers in the presence of a metathesis catalyst and at least one functionalized allyl compound. The new functionalized nitrile rubbers are suitable for producing vulcanizable mixtures and allow the production of vulcanizates having very stable networks. Also made possible, in particular, is the synthesis of block copolymers.

First claim

What is claimed is:

1. A process for preparing functionalized nitrile rubbers comprising end groups X, or Y and Z as set forth below, the process comprising contacting a nitrile rubber with a metathesis catalyst, which is a complex catalyst based on a metal from transition group 6 or 8 of the Periodic Table which has at least one ligand attached carbenically to the metal, in the presence of at least one compound of the general formula (I) or (II),
H 2 C═CH—CH 2 —X  (I)

Y—CH 2 —CH═CH—CH 2 —Z  (II)

where
X is
OR 1 , in which R 1 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl,
O—(CH 2 —CH 2 —O) n —R 2 , in which R 2 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20,
O—(CH 2 —CH(CH 3 )—O) n —R 3 , in which R 3 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20,
O—C(═O)—R 4 , in which R 4 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl,
C 6 -C 18 aryl, which is substituted by at least one radical OR 5 , in which R 5 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl, or
NH—C(═O)—OR 6 , in which R 6 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl, and

Y and Z are identical or different and
OR 7 , in which R 7 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl,
O—(CH 2 —CH 2 —O) n —R 8 , in which R 8 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20,
O—(CH 2 —CH(CH 3 )—O) n —R 9 , in which R 9 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl and n is 1 to 20,
O—C(═O)—R 10 , in which R 10 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl,
C 6 -C 18 aryl, which is substituted by at least one radical OR 11 , in which R 11 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl, or
NH—C(═O)—OR 12 , in which R 12 is H, C 1 -C 18 alkyl, C 7 -C 24 aralkyl, phenyl, naphthyl or fluorenyl.

2. The process according to claim 1 , wherein the metathesis catalyst is:
(i) a catalyst 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,
R is identical or different at each occurrence and represents hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl, or alkylsulphinyl, it being possible for all of these radicals to be substituted in each case optionally by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals, or alternatively both radicals R 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 of the general formula (A1),

 in which
X 1 , X 2 and L can have the same general definitions as in the general formula (A),
n is 0, 1 or 2,
m is 0, 1, 2, 3 or 4, and
R′ is identical or different at each occurrence and denotes alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radicals, all of which may be substituted in each case by one or more alkyl, halogen, alkoxy, aryl or heteroaryl radicals,

(iii) a catalyst 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 stated below,
R 1 is an alkyl, cycloalkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, arylthio, alkylsulphonyl or alkylsulphinyl radical, which may all be substituted in each case optionally 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 represent hydrogen or organic or inorganic radicals,
R 6 is H or an alkyl, alkenyl, alkynyl or aryl radical, and
L is a ligand which possesses the same definitions as stated for the formula (A),

(iv) a catalyst of the general formula (B1),

 in which
M, L, X 1 , X 2 , R 1 , R 2 , R 3 , R 4 and R 5 can possess the definitions stated for the general formula (B),

(v) a catalyst of the general formula (B2),

 in which
M, L, X 1 , X 2 , R 1 and R 6 have the general definitions for the formula (B),
R 12 is identical or different at each occurrence and possesses the definitions stated for the radicals R 2 , R 3 , R 4 and R 5 in the formula (B), with the exception of hydrogen, and
n is 0, 1, 2 or 3,

(vi) a catalyst of the general formula (B3),

 in which D 1 , D 2 , D 3 and D 4 each have a structure of the general formula (XVIII) shown below, which is attached via the methylene group shown on the right to the silicon of the formula (B3),

 in which
M, L, X 1 , X 2 , R 1 , R 2 , R 3 , R 5 and R 6 may possess the definitions stated for the general formula (B),

(vii) a catalyst of the general formula (B4), in which the symbol ● stands for a support,

(viii) a catalyst of the general formula (C),

 in which
M is ruthenium or osmium,
X 1 and X 2 are identical or different and represent anionic ligands,
R″ is identical or different at each occurrence and represents organic radicals,
Im represents an optionally substituted imidazolidine radical, and
An represents an anion,

(ix) a catalyst of the general formula (D),

 in which
M is ruthenium or osmium,
R 13 and R 14 independently of one another are hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 6 -C 24 aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 6 -C 24 aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 20 akylsulphonyl or C 1 -C 20 alkylsulphinyl,
X 3 is an anionic ligand,
L 2 is a neutral π-bonded ligand, irrespective of whether it is monocyclic or polycyclic,
L 3 is a ligand from the group of the phosphines, sulphonated phosphines, fluorinated phosphines, functionalized phosphines having up to three aminoalkyl, ammonioalkyl, alkoxyalkyl, alkoxycarbonylalkyl, hydrocarbonylalkyl, hydroxyalkyl or ketoalkyl groups, phosphites, phosphinites, phosphonites, phosphinamines, arsines, stibines, ethers, amines, amides, imines, sulphoxides, thioethers and pyridines,
Y − is a non-coordinating anion, and
n is 0, 1, 2, 3, 4 or 5,

(x) a

Assignees

• Obrecht Werner
• Jeschko Julia Maria
• Nuyken Oskar
• Schneider Martin
• Arlanxeo Deutschland Gmbh

Inventors

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

Classifications

• C08C19/00

  Chemical modification of rubber · CPC title

• C08C19/08 Primary

  Depolymerisation · CPC title

• C08C2019/09

  Chemistry & Metallurgy · mapped topic

• B01J31/2404

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title

• B01J31/2291

  Olefins · CPC title