Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2000-06-16
2002-02-19
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S220000, C528S227000, C528S486000, C525S415000
Reexamination Certificate
active
06348564
ABSTRACT:
The present invention relates to new cyclic esterketone compounds which are useful as monomers for the production of polymers, to a process for the synthesis thereof and to a process for the preparation of poly(esterketone) polymers and to the poly(esterketone) polymers so obtained therewith.
In recent years there has been a strong preoccupation with the development of biodegradable and nontoxic polymers which may be used for replacing existing polymers. To be useful for such purposes, the polymers must also possess other properties of the polymers which they are intended to replace. Such properties include, inter alia, permeability, biocompatibility, promotion of bioadhesion and reactivity for attachment to drugs.
In this regard, various aliphatic polyesters derived from lactones have drawn interest. Of particular interest in this regard are those aliphatic polyesters derived from lactones and, in particular, those derived from &egr;-caprolactone. Polymers derived from &egr;-caprolactone (such polymers being referred to herein as P&egr;-CL) are one of the very few commercially available biodegradable polymers, being well known for its biocompatibility, permeability and biodegradability. P&egr;-CL also possesses the rare property of being miscible with a variety of other polymers (such as PVC), thereby permitting them to be formed therewith into polymer blends/alloys (e.g., copolymers) in which deficient properties of the other polymer(s), such as poor stress/crack resistance, gloss and adhesion, are ameliorated.
P&egr;-CL has been as particularly desirable for the replacement of certain polymers, vinylic and otherwise in plastic bags and in films and wrappings. Unfortunately, due to a relatively low melting point of about 60° C., the ability for P&egr;-CL to be employed to replace such polymers in such uses is extremely limited, with an increase of at least 20° C. being necessary.
To resolve the above-mentioned problems, a new polymer, (2-oxep ane-1,5-dione(also known, and referred to herein, as PKCL) has been synthesized which possesses a melting point of about 150° C. and a glass transition temperature of about 41° C. This polymer, is formed from the monomer 1,4,8-trioxaspiro[4,6-]-9-undecanone (also known as TOSUO) in a well-controlled “living” ring-opening polymerization reaction using aluminum isopropoxide [A1(OiPr)
3
] as an initiator, whereby polyTOSUO is formed, followed by a reaction for 1 hour at 25° C. using Ph
3
CBF
4
and CH
2
Cl
2
, whereby PKCL is formed.
TOSUO is, in turn, synthesized according to a Baeyer-Villiger reaction by the oxidation of 1,4-cyclohexanedione monoethylene acetal by 3-chloroperoxybenzoic acid (m-CPBA) at 40° C. in CH
2
Cl
2
. Unfortunately, the synthesis of TOSUO follows a pathway that requires separate steps, the first wherein the finctions of the ketone are shielded and the second wherein the acetal functions are deshielded, thereby complicating and increasing the cost and time required for the synthesis.
Accordingly, it can be seen that there remains a need to provide improved compounds which are useful as new monomers that may be polymerized to form poly(esterketone) polymers, which monomer compounds may also be directly synthesized from the starting material in high yield using a one-step process. It can further be seen that there remains a need to provide a process to form poly(esterketone) polymers from the monomer compounds, as well as a need to provide the poly(esterketone) polymers so obtained.
It is a first primary object of the present invention to provide new cyclic esterketone compounds which are useful as new monomers that may be polymerized to form poly(esterketones), in particular poly(oxepane-diones), more particularly poly(unsubstituted oxepane-diones) such as poly(2-oxepane-1,5-dione) (PKCL), so that said compounds may be used to replace TOSUO for use in producing PKCL.
It is a further object of the present invention to provide such a compound which may be easily obtained from the starting material in one-step.
It is a second primary object of the present invention to provide a process whereby the cyclic esterketone compounds of the present invention may be produced from the starting material in one-step.
It is a third primary object of the present invention to provide improved poly(esterketone) polymers.
It is a fourth primary object of the present invention, to provide a process for the preparation of poly(esterketone) polymers.
In accordance with the teachings of the present invention, disclosed herein are novel cyclic esterketone compounds which are useful as monomers for the production of poly(esterketone) polymers, in particular polyoxepane-diones, more particularly poly(unsubstituted oxepane-diones) such as poly(2-oxepane-1,5-dione) (PKCL). These compounds are also simple and easy to synthesize from their starting materials in high yield using a one-step process that involves the oxidation (and, particularly, mono-oxidation) of the starting material (and particularly, cyclic diketones, such as saturated cyclic diketones, more particularly cyclohexanediones, such as unsubstituted cyclohexanediones, for example 1,4-cyclohexanedione).
More precisely, disclosed herein are novel cyclic esterketones that are useful as monomers in the production of, e.g., PKCL. Preferably, these cyclic esterketones are chosen from appropriate oxepane-diones, namely unsubstituted oxepane-diones. Most preferred unsubstituted oxepane-dione is 2-oxepane-1,5-dione (referred to herein as KCL).
Unsubstituted oxepane diones particularly KCL) are particularly attractive compounds for use as monomers due to, inter alia, their long-term stability which translates into a good shelf life. In this regard, unsubstituted oxepane diones (particularly KCL) have a shelf-life, in open air at ambient temperature, of at least three months. Further, they may be conserved without substantial degradation for more than three months at −20° C., in an inert nitrogen atmosphere. Such long-term stability is important in the measure where these compounds may be prepared in large quantities, with all the benefits that are derived from such an economy of scale.
Unsubstituted oxepane diones (particularly KCL) are further particularly useful due to the ease by which they may be synthesized in a one-step reaction by oxidation of the starting material.
In another aspect of the present invention, disclosed herein is a process for the synthesis of the novel cyclic esterketone compounds of the present invention, and in particular of 2-oxepane-1,5-dione (KCL), that permits the compound to be easily and simply prepared directly from the starting material in one, step.
The process of the present invention for the synthesis of unsubstituted oxepane diones (particularly of KCL) permits these (monomer) compounds to be easily and simply prepared in one-step directly from the starting material. In other words, the (monomer) compounds of the present invention (more particularly, 2-oxepane-1,5-dione) are obtainable by this process of the present invention.
In particular, the process of the present invention involves the oxidation (e.g., mono-oxidation) of cyclic diketones (to esters) to produce cyclic esterketone monomers according to the invention. Preferably, these cyclic diketones are saturated cyclic diketones. Cyclohexanediones are specially recommanded such as unsubstituted cyclohexanediones. Most preferred is 1,4-cyclohexanedione (which is used to synthesize KCL).
As will be readily understood (and as is capable of being determined) by one skilled in the art, the precise concentration of the starting material to be employed in the process of the present invention may be varied as needed to obtain the precise quantities of the (monomer) compounds of the present invention desired.
Nonetheless, it is contemplated herein that at least 0.01 M of starting material will be employed in the process of the present invention. Preferably, at least 0.06 M of starting material will be employed in the process of the present invention. Also preferred is the use of at
Dubois Philippe
Jerome Robert
Latere Jean-Pierre
Lecomte Philippe
Wautier Henri
Solvay ( Societe Anonyme)
Truong Duc
LandOfFree
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