Carbon dioxide-philic compounds and methods of synthesis...

Details Carbon dioxide-philic compounds and methods of synthesis... Carbon dioxide-philic compounds and methods of synthesis...

2000-09-22

2004-02-03

Boykin, Terressa M. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From phenol, phenol ether, or inorganic phenolate

C528S198000

Reexamination Certificate

active

06686438

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to compounds that are soluble in or miscible in carbon dioxide and to methods of synthesizing such compounds.
BACKGROUND OF THE INVENTION
Various publications are referenced herein to, for example, clarify the general state of the art. Reference to a publication herein is not an admission that the publication is prior art or relevant to the patentability of the present invention.
The feasibility of using carbon dioxide or CO
2
as a process solvent has been extensively investigated in both academic and industrial circles because CO
2
is considered to be an environmentally benign solvent. Previous solubility parameter calculations using equation of state information suggested that the solvent power of CO
2
was similar to that of short n-alkanes, leading to hopes that CO
2
could replace a wide variety of non-polar organic solvents. King, J. W., Poly. Mat. Sci. Eng. Prepr. (1984), 51, 707. Although such solubility parameter values precluded the use of CO
2
for processing of polar or hydrophilic materials, it was believed that addition of conventional alkyl-functional surfactants could effectively deal with the problem. However, early attempts to employ conventional surfactants in CO
2
failed as a result of the poor solubility of the amphiphiles, despite the fact that these same molecules exhibited adequate solubility in ethane and propane. Consani, K. A.; Smith, R. D.; J. Supercrit. Fl. (1990), 3, 51. It was later discovered that the early solubility parameter calculations, while mathematically correct, failed to note that the absolute value was inflated by as much as 20% by the strong quadropole moment of CO
2
(which also inflates its critical pressure). Myers, A. L.; Prausnitz, J. M., Ind. Eng. Chem. Fundam. (1965), 4, 209.
Johnston and colleagues suggested polarizability/volume as a better quantity by which to judge solvent power. O'Shea, K.; Kirmse, K.; Fox, M. A.; Johnston, K. P.; J. Phys. Chem. (1991), 95, 7863 (b) McFann, G. J.; Howdle, S. M.; Johnston, K. P.; AIChE J. (1994), 40, 543 (c) Johnston, K. P.; Lemert, R. M.; in Encyclopedia of Chemical Processing and Design, McKetta, J. J., Ed; Marcel Dekker: New York (1996), 1. On the basis of polarizability/volume, CO
2
is a poor solvent compared to short n-alkanes. As the 1980's drew to a close, a number of research groups began to explore the design of CO
2
-philic materials, (that is, compounds which dissolve in or are miscible in CO
2
at significantly lower pressures than alkyl functional analogs). For example, Harrison et al. generated a hybrid alkyl/fluoroalkyl surfactant that both dissolved in CO
2
and solubilized significant amounts of water. Harrison, K.; Goveas, J.; Johnston, K. P.; O'Rear, E. A.; Langmuir (1994), 10, 3536. DeSimone and coworkers generated homo- and copolymers of fluorinated acrylates which exhibit complete miscibility with CO
2
at moderate pressures. DeSimone, J. M.; Guan, Z.; Elsbernd, C. S.; Science (1992), 257, 945. Block copolymers featuring fluorinated acrylate monomers were used to support dispersion polymerization in CO
2
, allowing generation of micron-size monodisperse spheres. Hsiao, Y. L.; Maury, E. E.; DeSimone, J. M.; Mawson, S. M.; Johnston, K. P.; Macromolecules (1995), 28, 8159. Fluoroether-functional amphiphiles have been used to support emulsion polymerization as described in Adamsky, F. A.; Beckman, E. J.; Macromolecules (1994), 27, 312, solubilize proteins as described in (a) Ghenciu, E.; Russell, A. J.; Beckman, E. J.; Biotech. Bioeng (1998), 58, 572 (b) Ghenciu, E.; Beckman, E. J.; Industr. Eng. Chem. Res. (1997), 36, 5366; and Johnston, K. P.; Harrison, K. L.; Clarke, M. J.; Howdle, S.; Heitz, M. P.; Bright, F. V.; Carlier, C. Randolph, T. W.; Science (1996), 271, 624, and extract heavy metals from soil and water as described in (Yazdi, A. V.; Beckman, E. J.; Ind. Eng. Chem. (1997), 36, 2368; and Li, J.; Beckman, E. J.; Industr. Eng. Chem. Res. (1998), 37, 4768.
In general, compounds not soluble or miscible in CO
2
(that is, CO
2
-phobic compounds) can be made soluble or miscible in CO
2
by synthesizing analogs of such compounds incorporating one or more CO
2
-philic groups. Processes and reactions that are normally not possible in CO
2
, are thereby made possible. For example, surfactants, chelating agents and reactants for use in carbon dioxide can be synthesized in this manner. CO
2
-phobic compounds that can be modified with CO
2
-philic groups to create CO
2
-philic analogs for processing in CO
2
are disclosed, for example, in U.S. patent application Ser. No. 09/106,480, entitled Synthesis of Hydrogen Peroxide and filed Jun. 29, 1998, the disclosure of which is incorporated herein by reference, in which hydrogen peroxide is synthesized in CO
2
using a CO
2
-philic functionalized anthraquinone reactant. Moreover, CO
2
-philic chelating agents for extraction of metals in carbon dioxide are disclosed U.S. Pat. No. 5,641,887 and U.S. Pat. No. 5,872,257, the disclosures of which are incorporated herein by reference. Other CO
2
-philic functionalized compounds are disclosed in U.S. Pat. No. 5,589.105, U.S. Pat. No. 5,789,505, U.S. Pat. No. 5,639,836, U.S. Pat. No. 5,679,737, U.S. Pat. No. 5,733,964, U.S. Pat. No. 5,780,553, U.S. Pat. No. 5,858,022, U.S. Pat. No. 5,676,705, U.S. Pat. No. 5,683,977, and U.S. Pat. No. 5,683,473, the disclosures of which are incorporated herein by reference.
It has been theorized that only molecules with very low solubility parameters (that is, fluorine-containing and silicon-containing molecules) are sufficiently CO
2
-philic to synthesize CO
2
-philic analogs or amphiphiles suitable for commercial processing in CO
2
. O'Neill, M. L., Cao, Q.; Fang, M.; Johnston, K. P.; Wilkinson, S. P.; Smith, C. D.; Kerschner, J. L.; Jureller, S. H.; Ind. Eng. Chem. Res. (1998), 37, 3067. Indeed, it is the common belief in the art that only fluorine-containing and silicon-containing molecules are viable solutions in synthesizing commercially viable CO
2
-philic analogs. The most successful CO
2
-philic modifiers or moieties to date are fluorinated compounds. Despite success in development of fluorinated and silicon-containing CO
2
-philic amphiphiles, the cost (on a mass basis) of these materials (typically, on the order of $1/gram) renders the economics of a process unfavorable unless the amphiphile can be efficiently recycled. Whereas in-process recycling of a “CO
2
-phile” may at times be straightforward, this is not true in all cases where CO
2
has been proposed as a replacement for organic solvents.
It is very desirable to develop CO
2
-philic compounds or CO
2
-philes that are effectively soluble in or miscible in CO
2
while being relatively inexpensive to synthesize and use.
SUMMARY OF THE INVENTION
The present invention provides, generally, a method of synthesizing a CO
2
-philic analog of a CO
2
-phobic compound, comprising the step of: reacting the CO
2
-phobic compound with a CO
2
-philic compound to create the CO
2
-philic analog. Preferably, the CO
2
-philic compound contains no F or Si.
Preferably, the CO
2
-philic compound is a polyether substituted with at least one side group including a group that interacts favorably with or has an affinity for CO
2
(preferably a Lewis base group), a poly(ether-carbonate), a poly(ether-carbonate) substituted with at least one side group including preferably a Lewis base, a vinyl polymer substituted with at least one side group including preferably a Lewis base, a poly(ether-ester) or a poly(ether-ester) substituted with at least one side group including preferably a Lewis base. Preferably, the CO
2
-philic compound contains no F or Si atoms. The CO
2
-philic analog of the CO
2
-phobic compound has increased solubility or miscibility in CO
2
(that is, increased CO
2
-philic nature) compared to the CO
2
-phobic compound.
In one embodiment, the CO
2
-philic compound is a polyether copolymer including the repeat units
wherein R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
, R
8
, R
9
, R
10
, R
11
, and R
12
are, independently,

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