Alkyl hydroxylamine compounds and their use for shortstopping free radical polymerizations
View Patent ↗This invention provides a method for shortstopping free radical polymerization reactions using combinations of N-isopropylhydroxylamine (IPHA) or salts thereof with either primary or secondary alkyl hydroxylamines, or with at least two primary alkyl hydroxylamines. A method for producing elastomers using the aforesaid shortstopping agents is also provided.
1. A method for terminating a free radical initiated emulsion polymerization reaction comprising adding, to an emulsion comprising at least one monomer, a shortstopping agent comprising N-isopropylhydroxylamine (IPHA) or salts thereof and at least one alkyl hydroxylamine compound which is different from said IPHA or salts thereof and is selected from the group consisting of a primary alkyl hydroxylamine, a secondary alkyl hydroxylamine, and mixtures thereof, wherein said at least one alkyl hydroxylamine comprises N-tertiary-butylhydroxylamine (TBHA).
2. The method according to claim 1 , wherein said at least one alkyl hydroxylamine is a primary alkyl hydroxylamine selected from the group consisting of N-methylhydroxylamine (MHA), N-ethylhydroxylamine (EHA), N-propylhydroxylamine (PHA), and mixtures thereof.
3. The method according to claim 1 , wherein said IPHA or its salts and said at least one alkyl hydroxylamine are present in said shortstopping agent in a molar ratio of IPHA:alkyl hydroxylamine of from 40:1 to 1:1.
4. The method according to claim 1 , wherein IPHA or its salts and TBHA are present in said shortstopping agent in a molar ratio of IPHA:TBHA of 5:1.
5. The method according to claim 1 , wherein said at least one alkyl hydroxylamine further comprises at least a second primary alkyl hydroxylamine selected from the group consisting of N-methylhydroxylamine (MHA), N-ethylhydroxylamine (EHA), N-propylhydroxylamine (PHA), and mixtures thereof.
6. The method according to claim 5 , wherein said second primary alkyl hydroxylamine is N-ethylhydroxylamine (EHA).
7. The method according to claim 5 , wherein said IPHA or its salts and TBHA and said second primary alkyl hydroxylamine are present in said shortstopping agent in a molar ratio of IPHA:(TBHA and said second alkyl hydroxylamine) of from 0.02:1 to 0.1:1.
8. The method according to claim 1 , wherein said shortstopping agent comprises from 30-90% by weight of a solvent, based on the total weight of the shortstopping agent.
9. The method of claim 1 , wherein said shortstopping agent is added to said emulsion in an amount of from 0.01 to 0.1 parts per hundred parts of said monomer (phm).
10. The method of claim 1 , wherein the shortstopping agent comprises 1-20 wt % IPHA, 50-70 wt % EHA, and 29-49 wt % TBHA, based on the total weight of all the alkyl hydroxylamines present.
11. A method for producing an elastomer comprising the steps of:
1) conducting a free-radical polymerization of a latex comprising a conjugated diene;
2) adding a shortstopping agent comprising N-isopropylhydroxylamine (IPHA) or salts thereof and at least one alkyl hydroxylamine compound, which is different from said IPHA or salts thereof, and is selected from the group consisting of a primary alkyl hydroxylamine, a secondary alkyl hydroxylamine, and mixtures thereof, wherein said at least one alkyl hydroxylamine comprises the primary alkyl hydroxylamine N-tertiary-butylhydroxylamine (TBHA); and
3) processing the polymerized material to form said elastomer.
12. The method according to claim 11 , wherein said elastomer is a rubber selected from the group consisting of styrene-butadiene rubber, butadiene rubber and acrylonitrile-butadiene rubber.