Method for making amine-terminated polyarylene polyethers
View Patent ↗A method for making an amine-terminated polyarylene polyether thermoplastic in which a liquid/solid slurry reaction mixture is formed in an oxygen-free atmosphere. The reaction mixture is composed of a dihydroxyaromatic compound, a dihaloaromatic compound, an amino-hydroxyaromatic compound, a weak base, an aprotic polar solvent and a non-aromatic azeotrope former which is substantially imiscible with the aprotic polar solvent, said azeotrope former consisting of a molecule which has from 6 to 10 carbon atoms. The reaction mixture is refluxed at an elevated temperature to eventually produce a solution of the amine-terminated polyarylene polyether in the polar solvent. The method is designed for use in producing large amounts of thermoplastic in a simple, efficient and reliable manner.
1. A method for making an amine-terminated polyarylene polyether comprising the steps of:
forming a liquid/solid slurry reaction mixture in an oxygen-free atmosphere, said reaction mixture consisting essentially of a dihydroxyaromatic compound, a dihaloaromatic compound, an amino-hydroxyaromatic compound, a weak base, an aprotic polar solvent and a non-aromatic azeotrope former which has from 6 to 10 carbon atoms and is substantially non-miscible with the aprotic polar solvent;
heating said liquid/solid slurry reaction mixture to an elevated temperature that is sufficient to form a heated reaction mixture and a vapor mixture consisting essentially of said aprotic polar solvent, water, and said non-aromatic azeotrope former;
separating said vapor mixture from said heated reaction mixture;
replenishing said heated reaction mixture with said non-aromatic azeotrope former:
maintaining said heated reaction mixture at said elevated temperature for a time that is sufficient to form a product mixture that comprises said amine-terminated polyarylene polyether, said aprotic polar solvent and said non-aromatic azeotrope former;
separating said non-aromatic azeotrope former and any solid salts from said product mixture to provide a solution of said amine-terminated polyarylene polyether in said aprotic polar solvent.
2. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said dihydroxyaromatic compound is selected from the group consisting of bisphenol-A, bisphenol F, bisphenol S, bisphenol C, resorcinol, a dihydroxynaphthalene, 4,4′-biphenol, hexafluorobisphenol A, and halo- and alkyl derivatives of said dihydroxyaromatic compounds.
3. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said dihaloaromatic compound is selected from the group consisting of dichlorodiphenylsulfone and dichlorodiphenylketone.
4. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said amino-hydroxyromatic compound is selected from the group consisting of p-aminophenol, m-aminophenol, or aminonaphthol.
5. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said weak base is selected from the group consisting of sodium carbonate and potassium carbonate.
6. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said aprotic polar solvent is selected from the group consisting of dimethylsulfoxide, dimethylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene 1,1′-dioxide, tetrahydrothiophene-1 monoxide and blends thereof.
7. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said non-aromatic azeotrope former is selected from the group consisting of heptane, octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane, and lower alkyl derivatives of these compounds such that the total number of carbon atoms in the compound is from six to ten.
8. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said dihydroxyaromatic compound is bisphenol A, said dihaloaromatic compound is dichlorodiphenylsulfone, said amino-hydroxyaromatic compound is p-aminophenol, said weak base is potassium carbonate, said aprotic polar solvent is dimethylsulfoxide and said non-aromatic azeotrope former is octane.
9. A method for making an amine-terminated polyarylene polyether according to claim 7 wherein said non-aromatic azeotrope former is trimethylcyclohexane.
10. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said elevated temperature is between 120° C. and 135° C.
11. A method for making an amine-terminated polyarylene polyether according to claim 1 that includes the additional step of separating said non-aromatic azeotrope former from said aprotic polar solvent and said water in said vapor mixture to form a recyclable azeotrope former.
12. A method for making an amine-terminated polyarylene polyether according to claim 11 that includes the step of replenishing said reaction mixture with said recyclable azeotrope former.
13. A method for making an amine-terminated polyarylene polyether according to claim 1 wherein said liquid/solid slurry reaction mixture includes from 2 to 12 parts by weight of said dihydroxyaromatic compound, from 4 to 14 parts by weight of said dihaloaromatic compound, from 0.1 to 1 parts by weight of said amino-hydroxyaromatic compound, from 4 to 14 parts by weight of said weak base, from 50 to 69 parts by weight of said aprotic polar solvent and from 5 to 15 parts by weight of said non-aromatic azeotrope former.
14. A method for making an amine-terminated polyarylene polyether according to claim 13 wherein said dihydroxyaromatic compound is bisphenol A, said dihaloaromatic compound is dichlorodiphenylsulfone, said amino-hydroxyaromatic compound is p-aminophenol, said weak base is potassium carbonate, said aprotic polar solvent is dimethylsulfoxide and said non-aromatic azeotrope former is octane.
15. A method for making an amine-terminated polyarylene polyether according to claim 14 wherein said liquid/solid slurry reaction mixture includes about 7 parts by weight of said dihydroxyaromatic compound, about 9 parts by weight of said dihaloaromatic compound, about 0.6 parts by weight of said amino-hydroxyaromatic compound, about 9 parts by weight of said weak base, about 64 parts by weight of said aprotic polar solvent and about 10 parts by weight of said non-aromatic azeotrope former.