Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2000-02-17
2002-02-26
Geist, Gary (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
Reexamination Certificate
active
06350895
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to processes for making bis(3-hydroxypropyl) dicarboxylate monomer such as bis(3-hydroxypropyl) terephthalate and bis(3-hydroxypropyl) naphthalenedicarboxylate monomers from C
1
-C
4
dialkyl esters of terephthalic acid or naphthalene dicarboxylic acid and 1,3-propanediol in the presence of a yttrium or samarium compound transesterification catalyst.
TECHNICAL BACKGROUND
Preparation of polyester resins by transesterification of a C
1
-C
4
dialkyl ester of terephthalic acid and a diol or of a C
1
-C
4
dialkyl ester of naphthalene dicarboxylic acid acid and a diol, followed by polycondensation is well known in the art.
Generally, the C
1
-C
4
dialkyl ester of terephthalic acid or naphthalene dicarboxylic acid and the diol are reacted in the presence of a transesterification catalyst at elevated temperature and atmospheric pressure to form a monomer and a C
1
-C
4
alkanol corresponding to the C
1
-C
4
alkanol components of the dialkyl ester. The C
1
-C
4
alkanol is removed as it is formed during the reaction. Oligomers having a degree of polymerization of about 4 or less can also be formed. The monomer and any oligomer can then be polymerized at higher temperatures under reduced pressure in the presence of a polycondensation catalyst to form the desired polyester resin. These reactions can be carried out in batch or continuous processes.
Transesterification catalysts known in the art include titanium, manganese, lanthanum and zinc compounds. For example, U.S. Pat. No. 3,671,379 to Evans et al., discloses a process for producing poly(trimethylene terephthalate) using a titanium catalyst compound in both the transesterification and the polycondensation reactions. Cerium and lead acetylacetonate catalysts for the transesterification of dimethyl terephthalate with ethylene glycol are disclosed by Carlson et al. in U.S. Pat. No. 3,532,671. Lanthanum compounds, such as lanthanum acetate, are disclosed by Cavanaugh et al in U.S. Pat. No. 2,820,023 to be effective transestrification catalysts for the preparation of bis(2-hydroxyethyl) terephthalate from dimethyl terephthalate (DMT) and ethylene glycol.
New process improvements which increase transesterification rates resulting in increased throughput and reduced cost of production of bis(3-hydroxypropyl) carboxylate monomer such as bis(3-hydroxypropyl) terephthalate monomer and bis(3-hydroxypropyl) naphthalene dicarboxylate monomer are of significant interest to the chemical industry.
SUMMARY OF THE INVENTION
The present invention is an improved process for making bis(3-hydroxypropyl) dicarboxylate monomer, comprising contacting a C
1
-C
4
dialkyl ester of dicarboxcylic acid with 1,3-propanediol in the presence of a catalytic amount of at least one transesterification catalyst selected from the group consisting of compounds of yttrium and samarium at a temperature from about 150° C. to about 245° C.
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Traub et al, Mechanical Properties of Fibers Made of Polytrimethylene Terephthalate,Chemical Fibers, 45, 110-111, Apr. 1995.
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U.S. Patent Application 09/503,599, Filed Feb. 11, 2000, Griffith et al.
Deemie Robert W.
E. I. Du Pont de Nemours and Company
Geist Gary
Kuller Mark D.
Mayer Nancy S.
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