Polycarboxylic acids with small amount of residual monomer

• US 4,758,641 A
• Filed: 02/24/1987
• Issued: 07/19/1988
• Est. Priority Date: 02/24/1987
• Status: Expired due to Term

• Current Assignee: Noveon, Inc. (Berkshire Hathaway Incorporated)
• Original Assignee: Goodrich Corporation (Raytheon Technologies Corporation d/b/a RTX)
• Inventors: Hsu, Chin C.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): SAROFIM, NABIL F
• Application Number:
  US07/017,966
• Time in Patent Office: 511 Days
• Field of Search: 526/240, 526/230.5, 526/923, 526/208, 526/216, 526/317.1
• US Class Current: 526/208
• CPC Class Codes: C08F 20/04 Acids, Metal salts or ammonium salts thereof

Abstract

A polymer of an olefinically unsaturated carboxylic acid containing 3 to 5 carbon atoms is prepared which contains less than 0.2% by weight unreacted monomer in a solvent selected from acetone and lower alkyl acetates also in the presence with less than 5% of a crosslinker selected from polyalkenyl polyethers of polyhydric alcohols containing more than one alkenyl group per molecule wherein the polyhydric alcohol contains at least 4 carbon atoms and at least 3 hydroxyl groups and initiator selected from peroxides and peroxydicarbonates. Polymerization temperature is 40° to 85° C. and viscosity of the mixture after completing polymerization is less than 1000 cps. About 1 to 10% of the carboxyl groups on the polymer are neutralized.

Claims

1. A process conducted in the presence of less than about 1% of water for preparing a polymer from carboxylic monomer containing less than 0.2% of unreacted monomer having greater than 1% and less than 10% of the carboxyl groups of said monomer neutrialized comprising polymerizing a monomer charge containing at least 90% of an olefinically unsaturated carboxylic acid monomer of 3 to 5 carbon atoms, a partially neutralized salt thereof, and mixtures thereof, in the presence of a solvent in which said carboxylic acid monomer, or a salt thereof, is soluble but in which said polymer is insoluble, said solvent is selected from the group consisting essentially of acetone, alkyl acetates of 1 to 6 carbon atoms in the alkyl group, and mixtures thereof;

in the presence of 0.2 to 2.0 weight percent of monomer charge of a crosslinker; and

in the presence of 0.4 to 1.0 weight percent of monomer charge of lauroyl peroxide initiator wherein reaction temperature is about 70°

to 80°

C. or in the presence of less than 2 weight percent of monomer charge of an initiator selected from the group consisting essentially of peroxydicarbonates wherein reaction temperature is about 45°

to 55°

C.

2. Process of claim 1 wherein amount of said solvent used is such that said monomer charge content in said solvent is less than 30% by weight;

Brookfield viscosity of said polymer in said solvent after completion of polymerization is less than 1000 cps, measured at 60 rpm and at 22°

C.; and

amount of said peroxydicarbonate initiators is 0.4 to 1.0 weight percent.

3. Process of claim 1 wherein said monomer charge contains at least 95 weight percent of said carboxylic acid monomer or its salt;

wherein said solvent is selected from acetone, ethyl acetate, isopropyl acetate, propyl acetate, butyl acetates, and mixtures thereof; and

wherein said initiator is selected from lauroyl peroxide, di(2-ethylhexyl) peroxydicarbonate, di(sec-bytyl) peroxydicarbonate, di(isopropyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, dicetyl peroxydicarbonate, di(n-propyl) peroxydicarbonate, and mixtures thereof.

4. Process of claim 1 wherein amount of said solvent used is such that said monomer charge content in said solvent is 10 to 20% by weight and Brookfield viscosity of said polymer in said solvent after completion of polymerization is less than 1000 cps, measured at 60 rpm and at 22°

C.

5. Process of claim 1 wherein said carboxylic acid monomer is selected from acrylic acid or its salt, methacrylic acid or its salt, maleic acid or its salt, maleic anhydride or its salt, itaconic acid or its salt, and mixtures thereof;

and wherein said monomer charge contains at least 95% by weight of said carboxylic acid or its salt with remainder selected from alkyl acrylates containing 1 to 30 carbon atoms in the alkyl group.

6. Process of claim 5 wherein said monomer charge contains up to 10% by weight of a comonomer selected from alkyl acrylates containing 2 to 20 carbon atoms in the alkyl group, and mixtures thereof.

7. Process of claim 6 wherein said polymer contains less than 0.1% by weight of unreacted monomer;

wherein said solvent is ethyl acetate;

wherein said crosslinker is selected from allyl sucrose, trimethylol propane diallyl ether, diallyl ethers of polyether diols with molecular weight of 50 to 1000, allyl pentaerythritol, and mixtures thereof; and

wherein said polymerization is carried out in a 30 gallon reactor or larger.