Nitrile rubbers having low emission values
View Patent ↗An improved polymerization process using a specific molecular weight regulator makes it possible to produce new nitrile rubbers featuring particularly low emission values and giving vulcanizates which have an advantageous profile of properties and which are of outstanding quality, in particular in odor-sensitive applications.
1. A nitrile rubber comprising repeating units of acrylonitrile and 1,3-butadiene, prepared in the presence of tertiary nonyl mercaptan, wherein said nitrile rubber has an emission quotient E according to general formula (I) of less than or equal to 0.25 mg/(kg*Mooney units)
E
=
[
volatile
constituents
]
[
Mooney
viscosity
]
⨯
[
nitrile
content
]
100
(
I
)
where
[volatile constituents] is the volatile constituents concentration in mg/kg of nitrile rubber determined by TDS GC-MS analysis according to VDA recommendation 278 (version September 2002) between 28.4 min and 34.0 min,
[Mooney viscosity] is the Mooney viscosity ML 1+4 at 100° C. of the nitrile rubber in Mooney units determined according to ASTM D 1646 and
[nitrile content] is the dimensionless α,β-unsaturated nitrile content in the nitrile rubber, wherein such content is determined in % by weight pursuant to DIN 53 625 according to Kjeldahl.
2. The nitrile rubber according to claim 1 , wherein the emission quotient E according to formula (I) is less than or equal to 0.22 mg/(kg*Mooney units).
3. The nitrile rubber according to claim 2 , wherein the emission quotient E according to formula (I) is less than or equal to 0.20 mg/(kg*Mooney units).
4. The nitrile rubber according to claim 1 or 2 , further comprising repeating units of one or more additional copolymerizable monomers.
5. The nitrile rubber according to claim 1 having a Mooney viscosity ML 1+4 at 100° C. of 20 to 100 Mooney units (MU).
6. A process for producing nitrile rubbers according to claim 1 comprising polymerizing acrylonitrile and 1,3-butadiene in emulsion in the presence of tertiary nonyl mercaptan, wherein the emulsion polymerization is carried out up to a conversion of at least 60% by weight, based on the sum of the monomers.
7. The process according to claim 6 , wherein the emulsion polymerization is carded out up to a conversion of from 60% to 98%, based on the sum of the monomers used.
8. The process according to claim 7 , wherein the emulsion polymerization is carried out up to a conversion of from 62% to 95%, based on the sum of the monomers used.
9. The process according to claim 7 , wherein the emulsion polymerization is carried out up to a conversion of from 65% to 95%, based on the sum of the monomers used.
10. The process according to claim 6 , wherein the tertiary nonyl mercaptan is used either
a) in the form of tert-nonyl mercaptan at a purity of at least 95% by weight, or else
b) in the form of a mixture comprising (i) at least 50% by weight but less than 95% by weight of tert-nonyl mercaptan and (ii) the remainder being one or more further isomeric nonyl mercaptans and/or one or more further C 10 -C 16 alkylthiols.
11. The process according to claim 10 , wherein the tertiary nonyl mercaptan the tertiary nonyl mercaptan is used
a) in the form of tert-nonyl mercaptan at a purity of at least 97% by weight.
12. The process according to claim 6 , wherein the tertiary nonyl mercaptan is used in an amount of from 0.05 to 3 parts by weight, based on 100 parts by weight of the monomer mixture.
13. The process according to claim 12 , wherein the tertiary nonyl mercaptan is used in an amount of from 0.1 to 1.5 parts by weight, based on 100 parts by weight of the monomer mixture.
14. The nitrile rubber according to claim 1 , having a Mooney viscosity ML 1+4 at 100° C. of 10 to 150 Mooney units (MU).