Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
1999-11-01
2003-04-01
Szekely, Peter (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S120000, C524S150000, C524S151000, C558S071000, C558S078000, C426S547000
Reexamination Certificate
active
06541549
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to stabilizers for polymers and other organic materials. More particularly, the present invention relates to stabilizers for polymers or other organic materials that are phosphorus-containing molecules or oligomers that do not act as xenoestrogens.
2. Description of Related Art
Phosphorus-containing antioxidants, such as, phosphites, have been used as stabilizers in organic materials, such as, rubber, plastics, oils, and the like. The fourth edition of “Plastic Additives” by Gachter and Muller discusses in great detail the stabilization of plastics and polymers by commercialized phosphites, such as, tris(nonylphenyl)phosphite (TNPP) and tris(2,4-di-t-butylphenyl)phosphite. TNPP is the primary low cost liquid phosphite stabilizer used in the plastics and rubber industry. Recently, however, plastic and rubber manufacturers have been reluctant to utilize TNPP in their formulations owing to concerns that TNPP may be a xenoestrogen (foreign estrogen). Many of these concerns were raised recently in Colburn, T. et al.,
Our Stolen Future
, Dutton (1996) and related articles. In this regard, xenoestrogens are suspected of being hormonally active in developing organisms.
Non-polymeric phosphite compounds are disclosed in U.S. Pat. No. 5,290,747 as primary catalysts for the formation of Nylon 6. The generic structures of these disclosed phosphites are represented by generic structure I (where n>5).
With regard to non-polymeric phosphite stabilizers, two general classes of phosphites known in the prior art can be represented by structures II and III.
wherein R is H or CH
3
and X is oxygen, sulfur, nitrogen, and the like. Included in generic structure II is commercially available Irgaphos 38 (where R═CH
3
and X═H) described in European Patent EP-511156A2. The authors describe the phosphites listed in this patent as stabilizers for organic materials. All the stabilizers listed in EP 511156 have structures where R is represented as a methyl group. Much of the variation of the group X includes functionalized heteroatoms, such as, nitrogen, sulfur, oxygen, or functional groups such as cyano, trifluoromethyl, hindered amines, etc. The authors also describe structures wherein R=CH
3
and X is an alkyl or aralkyl group.
Japanese Patent 54163938 describes the improved thermal stability of PVC and ABS polymers containing compounds of structure II where R=H and X is an ethylene glycol.
Japanese Patent 55000747 describes a similar composition wherein R=CH
3
.
German patent DE2709528 describes a stabilizer for plastics, such as, polypropylene, where R=H and X contains a second phosphite in a spiral arrangement.
British patent GB1180398 describes phosphites (where R=H and the entire group attached to X and including X is a tert-butyl group) used as thermal stabilizers for SBR or ABS rubber.
German patent DE4202276 describes a compound related to Irgaphos 38 (where R=H and X=H) that is used as a stabilizer for polyolefins.
Japanese Patent JP03025437 describes a butyl sulfone derivative (where R═H and X═SO
2
-butyl) used in silver halide color photographic materials to prevent fading of color images.
Japanese patent JP59004629 describes a phosphite linked to another phosphite structure through an ether linkage (R═H and X═O). This phosphite is used as a photochemical and thermal stabilizer for polymer compounds.
German patent DE19520337 describes phosphite compounds (R═H, CH
3
and X═O) used to stabilize organic materials, such as, polyolefins, lubricants, etc. against oxidative, thermal or photochemical degradation.
A second general class of non-polymeric phosphites is represented by generic structure III. Phosphites within generic structure III are materials wherein the bis(2,4-di-tert-butylphenol)phosphite groups are joined symmetrically or non-symmetrically to a linkage group Y.
Structure III
Japanese patents 58152029, 01038456, and 02225542 describe a diphosphite derivative of III in which the phosphite moieties are linked together via a spiro ether group. These patents describe the use of this spiro ether linked diphosphite to stabilize polyolefin polymers, such as, polypropylene, used in radiation sterilizable applications.
Japanese patents JP54041948, JP54043952, and JP54030241 describe diphosphite stabilizers for polymers, such as, polypropylene, where the phosphite moieties are linked via either a bis 1,4-methylene substituted cyclohexane group or a 2,2-dimethylpropyl group. The diphosphite containing the 2,2-dimethylpropyl linkage group is also described as a chelating ligand of a hydroformylation catalyst in WO9518089 and in the above-described GB1180398 where this diphosphite is used as a thermal stabilizer for SBR or ABS rubber. Japanese patent JP61113631 describes polyolefin compositions with improved processing stability and heat resistance with the diphosphite containing the 2,2-dimethylpropyl linkage group. In addition, Japanese patent JP61113631 also describes the use of a different diphosphite with an n-hexyl group as the linking agent.
European patent EP-518241 describes a diphosphite with an unsymmetrical ethyl substituted ethylene linkage group useful as a ligand for a hydroformylation catalyst.
Japanese patent JP02097539 describes a substituted diphenol as an antioxidant for polyolefins.
European patent EP33395 describes heat and light stabilizers for polymers also based on a substituted diphenol.
SUMMARY OF THE INVENTION
The present invention is directed to liquid, non-estrogenic phosphites or polymeric phosphites that provide stabilization of organic materials that is similar to or better than that provided by TNPP.
More particularly, the present invention relates to phosphorus-containing molecules or low molecular weight phosphorus-containing polymers that act as stabilizers of organic materials and do not act as xenoestrogens. Generically, the present invention is directed to two types of related alkylated phosphite stabilizers: non-polymeric phosphites and polymeric stabilizers.
The nonestrogenic phosphite stabilizers of the present invention preferably include compounds, such as, bis(2,4-di-t-butylphenyl)octylphosphite (Stabilizer A) and the low molecular weight phosphorus-containing polymer (i.e., phosphorus-containing oligomer) poly(4,4′-{2,2′-dimethyl-5,5′-di-t-butylphenylsulfide}octylphosphite) (Stabilizer B). Stabilizers A and B have the following structures:
In the above formula for Stabilizer B, n is an integer of at least 2, preferably from 2 to about 6, more preferably from 2 to 4. R
9
and R
10
are independently selected from the group consisting of hydrogen and alkyl, preferably alkyl of from 1 to 8 carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isomers of the foregoing, and the like. In a preferred embodiment, R
9
and R
10
are hydrogen.
The oligomeric non-xenoestrogenic phosphorus-containing materials are of the general structure IV:
where Z is a linking group, m is 0 or 1, n is an integer of at least 2, the asterisks are independently selected terminal groups, and Q is selected from the group consisting of
where R
11
is alkyl or aralkyl, preferably having from 1 to 20 carbon atoms inclusive, more preferably 6 through 20, most preferably 6 through 10, in the alkyl moiety and from 6 to 10 carbon atoms in any aryl moiety attached thereto, and
These phosphorus-containing oligomers comprise two main portions: a diphenol portion and a phosphorus portion. The diphenol portion comprises two substituted phenols that are directly linked (when m is 0) or are coupled by common linking groups (Z) for these materials (when m is 1), such as, for example, isopropylidene, hexafluoroisopropylidene, sulfur, sulfone, or oxygen. The phenol portion of the diphenol can also be substituted (R
1
-R
8
) with alkyl groups, aralkyl groups, or halogen groups.
More particularly, the present invention is directed to a non-xenoestrogenic phosphoru
Archibald Scott R.
Coffin-Werner Tracy L.
Crompton Corporation
Dilworth Michael P.
Grandinetti Paul
Szekely Peter
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