Process for polymerizing acrylic acid with inhibitor and retarder present and the use of resultant polyacrylic acids

• US 3,948,867 A
• Filed: 08/15/1974
• Issued: 04/06/1976
• Est. Priority Date: 07/03/1970
• Status: Expired due to Term

• Current Assignee: Deutsche Gold- und Silber-Scheideanstalt vormals Roessler
• Original Assignee: Deutsche Gold- und Silber-Scheideanstalt vormals Roessler
• Inventors: Haschke, Heinz, Bader, Erich
• Primary Examiner(s): Henderson, Jr., Christopher A.
• Application Number:
  US05/497,645
• Time in Patent Office: 600 Days
• Field of Search: 260/80 M, 260/80 P, 260/85.7, 260/88.1 PC, 260/86.1 R, 260/86.1 E
• US Class Current: 526/79
• CPC Class Codes: C02F 1/54 using organic material
• CPC Class Codes: C02F 5/10 using organic substances
• CPC Class Codes: C08F 20/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C11D 3/3761 in solid compositions

Abstract

Process of manufacturing bead-shaped polymers from acrylic acid by the polymerization of monomeric acrylic acid under slow addition of the monomer to a powerfully stirred, boiling hydrophobic reaction medium and in the presence of a free radical catalyst as well as polymerization regulator and/or cross-linking agents which comprises carrying out the polymerization in the presence of a polymerization inhibitor and/or polymerization retarder.

Claims

1. A process for the production of a polyacrylic acid in the form of small beads consisting predominantly of beads having an average diameter between 0.05 and 5 millimeters by the polymerization of monomeric acrylic acid in a vigorously stirred liquid hydrophobic reaction medium that is maintained at its boiling point in the presence of (a) a free-radical hydrophobic polymerization catalyst in an amount equivalent to between 0.05 and 5% by weight of the acrylic acid, (b) a polymerization inhibitor in an amount equivalent to between 0.02 and 0.2% by weight of the acrylic acid, and (c) a polymerization retarder in an amount equivalent to between 0.2 and 1.0% by weight of the acrylic acid, the said polymerization being effected by slowly adding to the vigorously stirred liquid hydrophobic reaction medium that is maintained at its boiling point, a solution in the liquid hydrophobic reaction medium of the monomeric acrylic acid, the said solution of monomeric acrylic acid including the free-radical catalyst (a), the polymerization inhibitor (b), and the polymerization retarder (c), or by slowly adding, to the vigorously stirred liquid hydrophobic reaction mixture containing the polymerization inhibitor (b), a solution in the liquid hydrophobic reaction medium of a stabilizer-free monomeric acrylic acid containing the free-radical polymerization catalyst (a) and the polymerization retarder (c), and subsequently recovering the resulting small beads of polyacrylic acid from the reaction medium.

2. A process as defined in claim 1 in which the monomeric acrylic acid, the free-radical polymerization catalyst (a), the polymerization inhibitor (b), and the polymerization retarder (c) are added to the vigorously stirred boiling hydrophobic reaction mixture in the form of a solution in the hydrophobic reaction medium.

3. A process as defined in claim 1 in which the vigorously stirred boiling liquid hydrophobic reaction mixture initially contains at most one-third of the amount of the free-radical polymerization catalyst (a) that is to be added for polymerization of all the monomeric acrylic acid that is to be polymerized in the reaction medium in that operation of the process, and the remainder of the polymerization catalyst (a) is added in the form of a solution in the acrylic acid monomer.

4. A process as defined in claim 1 in which the free-radical polymerization catalyst (a) is present in an amount between 0.1 and 2.0% by weight of the monomeric acrylic acid.

5. A process as defined in claim 1 in which the free-radical polymerization catalyst (a) is present in an amount between 0.2 and 1.0 % by weight of the monomeric acrylic acid.

6. A process as defined in claim 1 in which the hydrophobic reaction medium is n-heptane or a mixture of n-heptane with decahydronaphthalene, xylene, n-hexane or chloroform.

7. A process as defined in claim 1 in which the free-radical polymerization catalyst (a) is benzoyl peroxide, 2,2'"'"'-azobis(2-methylpropionitrile), lauroyl peroxide, or acetylcyclohexylsulfonyl peroxide.

8. A process as defined in claim 1 in which the polymerization inhibitor (b) is hydroquinone or pyrocatechol.

9. A process as defined in claim 1 in which the polymerization retarder (c) is o-dinitrobenzene, vinyl acetate, triphenylchloromethane, hexamethylparafuchsin, allyl alcohol or α

-methylstyrene.

10. A process as defined in claim 1 for the production of a polyacrylic acid in the form of beads having an average diameter of 1.5 millimeters which comprises slowly adding to a vigorously stirred body of n-heptane mantained at its boiling point a solution of acrylic acid in n-heptane containing 0.005 gram of benzoyl peroxide as a free-radical polymerization catalyst (a), 0.0003 gram of hydroquinone as a polymerization inhibitor (b), and 0.005 milliliter of vinyl acetate as a polymerization retarder (c) for each milliliter of acrylic acid in the solution, and recovering the polyacrylic acid beads thus formed.