Vulcanizable compositions based on nitrile rubbers containing epoxy groups

Patent metadata

Field	Value
Publication number	US-9650452-B2
Application number	US-201113995268-A
Country	US
Kind code	B2
Filing date	Dec 29, 2011
Priority date	Dec 29, 2010
Publication date	May 16, 2017
Grant date	May 16, 2017

Abstract

There are provided novel vulcanizable compositions based on optionally fully or partly hydrogenated nitrile rubbers containing epoxy groups, and specific crosslinkers, which no longer require use of conventional crosslinkers, more particularly sulphur. The vulcanizates producible therefrom possess very good compression sets at room temperature, 100° C. and 150° C., and additionally exhibit high tensile strength combined with good elongation at break.

First claim

What is claimed is:

1. A vulcanizable composition comprising:
(i) at least one nitrile rubber containing epoxy groups and comprising repeat units derived from at least one conjugated diene, at least one α,β-unsaturated nitrile, and at least one monomer which contains epoxy groups, but not from a nonconjugated cyclic polyene, wherein the monomer which contains epoxy groups is selected from the group consisting of 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate, 2-(n-propyl)glycidyl acrylate, 2-(n-propyl)glycidyl methacrylate, 2-(n-butyl)glycidyl acrylate, 2-(n-butyl)glycidyl methacrylate, glycidyl methacrylate, glycidylmethyl methacrylate, glycidyl acrylate, (3′,4′-epoxyheptyl)-2-ethyl acrylate, (3′,4′-epoxyheptyl)-2-ethyl methacrylate, 6′,7′-epoxyheptyl acrylate, 6′,7′-epoxyheptyl methacrylate, allyl glycidyl ether, allyl 3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl glycidyl ether, vinyl 3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3-vinylcyclohexene oxide;
(ii) at least one crosslinker comprising at least one of:
at least one Lewis acid selected from the group consisting of aluminium trichloride, indium(III) chloride, zinc chloride, iron(II) oxide, iron(III) oxide, iron(III) chloride, silicon tetrachloride, lithium bromide, lithium chloride, magnesium chloride, scandium(III) triflate, and rhodium(III) chloride and
at least one Brønsted acid selected from the group consisting of potassium hydrogensulphate, ammonium hydrogensulphate, tetraalkylammonium hydrogensulphates, potassium dihydrogenphosphate, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium chloride, ammonium sulphate, ammonium carbonate, ammonium hydroxide, dodecylbenzylsulphonic acid, p-toluenesulphonic acid, ascorbic acid, acetic acid, acrylic acid, fumaric acid, maleic acid, benzoic acid, abietic acid, and oleic acid; and

(iii) crosslinkers other than those specified under (ii) in an amount of 0 to 2.5 parts by weight, based on 100 parts by weight of the nitrile rubber (i).

2. The vulcanizable composition according to claim 1 , wherein the vulcanizable composition contains no other crosslinkers other than those specified under (i).

3. The vulcanizable composition according to claim 1 , wherein the composition includes the at least one additional crosslinker (iii) in an amount less than 2.5 parts by weight, based on 100 parts by weight of the nitrile rubber (i).

4. The vulcanizable composition according to claim 3 , wherein the at least one additional crosslinker (iii) is present in an amount of less than 1 part by weight, based on 100 parts by weight of the nitrile rubber (i).

5. A vulcanizable composition comprising:
(i) at least one nitrile rubber containing epoxy groups, wherein the nitrile rubber is fully hydrogenated or partially hydrogenated and comprises repeat units derived from at least one conjugated diene, at least one α,β-unsaturated nitrile, and optionally one or more further copolymerizable monomers, but not from a nonconjugated cyclic polyene;
(ii) at least one crosslinker comprising at least one of:
at least one Lewis acid selected from the group consisting of boron trihydride, aluminium trichloride, indium(III) chloride, copper(II) chloride, copper(I) triflate, gold(III) chloride, gold(I) chloride, zinc chloride, tin(IV) oxide, tin(IV) chloride, copper(II) oxide, iron(II) oxide, iron(III) oxide, iron(III) bromide, iron(III) chloride, sulphur trioxide, silicon tetrachloride, lithium bromide, lithium chloride, magnesium chloride, scandium(III) triflate, rhodium(III) chloride, and complexes of the following elements in the following oxidation states: Co(III), Al(III), Fe(III), Fe(II), Sn(IV), Co(II), Ni(0), Ni(II), Cu(II), Cu(I), Pb(II), Sn(II), Sn(IV), Ag(I), Au(I), Au(III), Pd(II), Pt(II), Sc(III), Ir(III), Rh(III) and In(III), and
at least one Brønsted acid selected from the group consisting of sulphuric acid, hydrogensulphates, sulphurous acid, hydrogensulphites, hydrogen sulphide, hydrogensulphides, dipotassium hydrogenphosphate, potassium dihydrogenphosphate, disodium hydrogenphosphate, sodium dihydrogenphosphate, calcium hydrogenphosphate, trisodium hydrogendiphosphate, disodium hydrogendiphosphate, diphosphonic acid and the partial esters thereof, metaphosphoric acid, triphosphonic acid and the partial esters thereof, hydrogen carbonates, acids of the halogens, hypohalous acids, halous acids, halic acids, perhalic acids, ammonium chloride, ammonium sulphate, ammonium carbonate, ammonium hydroxide, inorganic and organic sulphonic acid, ascorbic acid, acetic acid, propionic acid, acrylic acid, fumaric acid, maleic acid, benzoic acid, abietic acid, oleic acid, phosphonic acid, and the mono- or diesters thereof; and

at least one additional crosslinker (iii) other than those specified under (ii), in an amount of 0 to 2.5 parts by weight, based on 100 parts by weight of the nitrile rubber (i).

6. The vulcanizable composition according to claim 5 , wherein:
the at least one crosslinker comprises at least one of:
at least one Lewis acid selected from the group consisting of aluminium trichloride, indium(III) chloride, zinc chloride, iron(II) oxide, iron(III) oxide, iron(III) chloride, silicon tetrachloride, lithium bromide, lithium chloride, magnesium chloride, scandium(III) triflate, and rhodium(III) chloride, and
at least one Brønsted acid selected from the group consisting of potassium hydrogensulphate, ammonium hydrogensulphate, tetraalkylammonium hydrogensulphates, potassium dihydrogenphosphate, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium chloride, ammonium sulphate, ammonium carbonate, ammonium hydroxide, dodecylbenzylsulphonic acid, p-toluenesulphonic acid, ascorbic acid, acetic acid, acrylic acid, fumaric acid, maleic acid, benzoic acid, abietic acid, and oleic acid.

7. The vulcanizable composition according to claim 5 , wherein the nitrile rubber (i) is at least one of:
a nitrile rubber in which the epoxy groups are applied to the nitrile rubber by subsequent grafting of compounds containing epoxy groups, and
a nitrile rubber having repeat units of at least one nitrile, of at least one conjugated diene, of at least one monomer containing epoxy groups, and optionally of one or more further copolymerizable monomers, but none of any nonconjugated cyclic polyenes.

8. The vulcanizable composition according to claim 5 , wherein the nitrite rubber (i) has repeat units derived from a monomer which contains epoxy groups, wherein the monomer which contains epoxy groups is at least one of o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 3-vinylcyclohexene oxide, and monomers of the general formula (I)

in which
m is 0 or 1 and
X is O, O(CR 2 ) p , (CR 2 ) p O, C(═O)O, C(═O)O(CR 2 ) p , C(═O)NR, (CR 2 ) p , N(R), N(R)(CR 2 ) p , P(R), P(R)(CR 2 ) p , P(═O)(R), P(═O)(R)(CR 2 ) p , S, S(CR R ), S(═O), S(═O)(CR 2 ) p , S(═O) 2 (CR 2 ) p or S(═O) 2 ,
Y represents repeat units of one or more mono- or polyunsaturated monomers, comprising conjugated or nonconjugated dienes, alkynes and vinyl compounds, or a structural element which derives from polymers comprising polyethers, especially polyalkylene glycol ethers and polyalkylene oxides, polysiloxanes, polyols, polycarbonates, polyurethanes, polyisocyanates, polysaccharides, polyesters and polyamides,
n and p are the same or different and are each in the range from 0 to 10 000, and
R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and are each H, a linear or branched, saturated or mono- or

Assignees

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

Inventors

• Brandau Sven
• Klimpel Michael
• Magg Hans
• Welle Achim

Classifications

• C08K5/19

  Quaternary ammonium compounds · CPC title

• C08L9/02 Primary

  Copolymers with acrylonitrile · CPC title

• C08K5/0091 Primary

  Complexes with metal-heteroatom-bonds · CPC title

• C08K3/20

  Oxides; Hydroxides {(graphene oxides C08K3/042)} · CPC title

• C08K5/09

  Carboxylic acids; Metal salts thereof; Anhydrides thereof · CPC title