Benign Processing of Polymers Plasticized with Absorbed Carbon Dioxide

EPA Grant Number: R829555
Title: Benign Processing of Polymers Plasticized with Absorbed Carbon Dioxide
Investigators: Baird, Donald G.
Institution: Virginia Polytechnic Institute and State University
EPA Project Officer: Richards, April
Project Period: January 1, 2002 through December 31, 2004 (Extended to July 31, 2005)
Project Amount: $325,000
RFA: Technology for a Sustainable Environment (2001) RFA Text |  Recipients Lists
Research Category: Sustainability , Nanotechnology , Pollution Prevention/Sustainable Development


There has been considerable interest over the last decade in the use of super critical (sc) and high pressure (hp) carbon dioxide for replacing highly toxic organic solvents and plasticizers used in the synthesis and processing of polymeric materials. CO2 is non-toxic, non-flammable, chemically inert, completely recoverable, and inexpensive. It has solubilization characteristics similar to organic solvents like CFCs and is known to plasticize amorphous and some semi-crystalline (with low degrees of crystallinity) polymers. To date hp- and sc-CO2 have been used primarily as solvents and non-solvents for polymerization, to generate micro-cellular plastics, to impregnate polymers with various additives and to extract impurities and low molecular weight polymers from a polymer. This work is concerned with the use of carbon dioxide as a processing aid to render polymers, which must ordinarily be processed in the presence of environmentally unfriendly solvents, melt processable.

The first goal of this research is to develop a general procedure for melt spinning polymers using the exemplary acrylic copolymer system plasticized with carbon dioxide in such a way that foaming is eliminated or at least minimized. The second goal of the work is to devise a technique for rapidly saturating the acrylic copolymers with CO2 and to optimize the copolymer structure to accelerate the saturation.


An exemplary system chosen here is the commercially prevalent (about 6 billion pounds are produced annually) acrylic copolymers consisting of acrylonitrile (AN) and methylacrylate (MA) which are solution spun using highly toxic solvents to form fibers for use in textiles and as precursors to carbon fibers. Solution spinning is necessary as these materials with levels of AN greater than 85 to 90 mole % crosslink and cyclize (degrade) rapidly at temperatures where they might be melt processable (e.g. 220 oC). Initial studies in our laboratory have revealed that low levels of absorbed CO2 (<12 wt %) significantly reduce the glass transition temperature of AN/MA copolymers and thereby allow them to be extruded at temperatures low enough that significant degradation can be avoided. However, capitalizing on this effect to produce melt spun fibers and films is extremely difficult as foaming of the polymer occurs immediately as the melt exits the die (i.e. spinneret hole or film die). A chamber will be designed for controlling the pressure and temperature of the environment into which the fibers exit in order to control the release of CO2 in such a way as to avoid flashing and yet allow continuous passage of the fibers from the controlled environment to ambient conditions. Numerical simulation techniques will be used to select appropriate processing conditions, i.e. temperature and pressure, to control the release of the CO2 according to spinning speed, melt temperature, and fiber diameter. Saturating the copolymers with CO2 at rates which are commercially acceptable will also present a challenge. Two approaches will be investigated: one a batch process involving high pressure saturation; the other a continuous process using scCO2 injected into the polymer in the screw extruder. Although we will concentrate on the spinning of AN/MA copolymers, the knowledge gained here is expected to be translated to other polymer systems.

Expected Results:

The successful spinning of AN/MA copolymers in the presence of CO2 will play a significant role in reducing environmental pollution and costs associated with solvent processing of these commercially important high volume materials. The toxic solvents presently used must be recovered, but some amounts escape into ground water and rivers. CO2 is extracted from the air and released back to the air with no net addition of CO2.

Publications and Presentations:

Publications have been submitted on this project: View all 25 publications for this project

Journal Articles:

Journal Articles have been submitted on this project: View all 7 journal articles for this project

Supplemental Keywords:

RFA, Scientific Discipline, Air, Sustainable Industry/Business, Chemical Engineering, air toxics, cleaner production/pollution prevention, Sustainable Environment, Technology for Sustainable Environment, Chemistry and Materials Science, New/Innovative technologies, Engineering, supercritical carbon dioxide (SCCO2) technology, stratospheric ozone, clean technologies, recovery, environmentally benign solvents, polymer formulation, alternative solvents, polymerization chemistry, supercritical carbon dioxide, carbon dioxide, polymers, plastic, alternatives to CFCs, environmentally benign alternative, plastics, solvent replacements, organic solvents, pollution prevention, polymer design, environmentally-friendly chemical synthesis, solvents

Progress and Final Reports:

  • 2002 Progress Report
  • 2003 Progress Report
  • 2004
  • Final Report