Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-02-08
2003-04-01
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S093000, C560S200000
Reexamination Certificate
active
06541656
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for producing &agr;,&bgr;-unsaturated carboxylic acid heterocycle-inserted esters or &agr;,&bgr;-unsaturated carboxylic acid polyheteroalkylene esters. More particularly, it relates to a process for producing &agr;, &bgr;-unsaturated carboxylic acid heterocycle-inserted esters which comprises reacting and &agr;,&bgr;-unsaturated carboxylic acid esters with heterocyclic compounds, a process for producing &agr;, &bgr;-unsaturated carboxylic acid polyheteroalkylene esters which comprises reacting &agr;,&bgr;-unsaturated carboxylic acids with heterocyclic compounds in the presence of polymerization inhibitors and metal oxide catalysts, and a catalyst which can be used with advantage in such processes.
PRIOR ART
&agr;,&bgr;-Unsaturated carboxylic acid heterocycle-inserted esters and &agr;,&bgr;-unsaturated carboxylic acid polyheteroalkylene esters are polymerizable and therefore are useful compounds widely usable on a commercial scale as raw materials for the synthesis of perfumes and of medicinals or agrochemicals, as organic synthetic intermediates, or as polymerizable materials and so forth. For example, polyoxyethylene monomethyl ether (meth)acrylates are known as such &agr;,&bgr;-unsaturated carboxylic acid heterocycle-inserted esters, and 2-hydroxyethyl (meth) acrylate is known as such &agr;,&bgr;-unsaturated carboxylic acid polyheteroalkylene esters.
It is known that polyoxyethylene monomethyl ether (meth) acrylates can be produced by synthesizing polyoxyethylene monoalkyl ethers from methanol and ethylene oxides and subjecting the polyoxyethylene monomethyl ether to esterification or transesterification with (meth)acrylic acids or (meth)acrylate esters. However, such process for producing polyoxyethylene monomethyl ether (meth)acrylates is not satisfactory from the commercial practicing view points since it comprises two reaction steps and allows the formation of an equimolar amount of water or the corresponding alcohol as a reaction byproduct.
For producing 2-hydroxyethyl (meth)acrylates, a process is known which comprises reacting (meth)acrylic acids, which are &agr;,&bgr;-unsaturated carboxylic acids, with an ethylene oxide, which is a heterocyclic compound, in the presence of one of various catalysts, such as various amines, quaternary ammonium salts, trivalent iron compounds, chromium compounds, silver or mercury and metal compounds derived from &agr;,&bgr;-unsaturated carboxylic acids. Such process for producing 2-hydroxyethyl (meth)acrylates, however, has problems: it is difficult to control the number of moles of an ethylene oxide, which is a heterocyclic compound, to be added, therefore the distribution of numbers of moles of ethylene oxides added becomes broad. Furthermore, dimeric diesters resulting from the addition of &agr;,&bgr;-unsaturated carboxylic acids to both termini of the polyoxyalkylene are also formed and, when used for polymerization purposes, in particular, the diesters serve as crosslinking agents, causing a problem of gelation, among others.
Japanese Kokai Publication Hei-11-71328 discloses that a process for producing aliphatic polyoxyalkylene alkyl ethers each having a specific chemical structure which comprises inserting alkylene oxides directly into fatty acid alkyl esters in the presence of composite metal oxide catalysts can produce the desired products in an efficient and economical manner. Further, Japanese Kokai Publication 2000-16958 discloses that a process for producing alkylene oxide adducts which comprises reacting active hydrogen-containing organic compounds with alkylene oxides in the presence of powder-form magnesium oxide catalysts having a specified specific surface area can give the alkylene oxide adducts low in byproduct contents. However, the publications cited above disclose nothing about the production of &agr;,&bgr;-unsaturated carboxylic acid heterocycle-inserted esters or &agr;, &bgr;-unsaturated carboxylic acid polyheteroalkylene esters, which are polymerizable and therefore are compounds of commercial importance for use in a wide range. Thus, there has been room for investigation in search for an appropriate process for producing such &agr;,&bgr;-unsaturated carboxylic acid heterocycle-inserted esters or &agr;,&bgr;-unsaturated carboxylic acid polyheteroalkylene esters.
SUMMARY OF THE INVENTION
In view of the above-mentioned state of the art, it is an object of the present invention to provide a process for producing an &agr;,&bgr;-unsaturated carboxylic acid heterocycle-inserted ester economically and efficiently. Another object is to provide an economical and efficient process for producing an &agr;,&bgr;-unsaturated carboxylic acid polyheteroalkylene ester showing a sharp distribution of numbers of moles of the heterocyclic compounds added and containing almost no &agr;,&bgr;-unsaturated carboxylic acid diesters. A further object is to provide a catalyst suited for use in producing an &agr;,&bgr;-unsaturated carboxylic acid ester in an economical and efficient manner.
The present inventors conducted intensive investigations to provide an economical process for producing an &agr;,&bgr;-unsaturated carboxylic acid heterocycle-inserted ester. As a result, they found in the first place that, by reacting an &agr;,&bgr;-unsaturated carboxylic acid ester with a heterocyclic compound, it is possible to produce an &agr;,&bgr;-unsaturated carboxylic acid heterocycle-inserted ester in an economical and efficient manner since the process is curtailed and the formation of the byproducts water or alcohol is suppressed. Paying attention to the above facts, they thought that such effects might be produced more reliably if the chemical structures of the heterocyclic compounds are restricted to a specific one. They also found that when the reactions are carried out in the presence of a metal oxide catalyst, the desired products can be produced more economically and more efficiently and that when polymerization inhibitors are used and/or the oxygen concentration in the gaseous phase in the reactor employed in carrying out the reaction is specified, the polymerization of &agr;,&bgr;-unsaturated carboxylic acid esters or &agr;,&bgr;-unsaturated carboxylic acid heterocycle-inserted esters can be suppressed and the above effects can fully be expressed.
Thus, the invention provides a process for producing an &agr;,&bgr;-unsaturated carboxylic acid ester
which comprises the step of reacting an &agr;,&bgr;-unsaturated carboxylic acid ester of the general formula (1):
wherein R
1
, R
2
and R
3
are the same or different and each represents a hydrogen atom or an organic residue and R
4
represents an organic residue,
with a heterocyclic compound of the general formula (2):
wherein R
5
represents a hydrogen atom or an organic residue and X
1
represents O, S or NH,
to give an &agr;,&bgr;-unsaturated carboxylic acid ester of the general formula (3):
wherein R
1
, R
2
and R
3
are the same or different and each represents a hydrogen atom or an organic residue, R
4
represents an organic residue, one of R
6
, R
7
, R
8
and R
9
represents R
5
and the remaining three each represents a hydrogen atom, X
1
represents O, S or NH and n1 represents a positive integer one or more.
The present inventors also made intensive studies to provide an economical process for producing an &agr;,&bgr;-unsaturated carboxylic acid polyheteroalkylene ester showing a sharp distribution of numbers of moles of the heterocyclic compounds added and containing almost no &agr;,&bgr;-unsaturated carboxylic acid diesters and, as a result, found that an &agr;,&bgr;-unsaturated carboxylic acid polyheteroalkylene ester can be produced economically by reacting an &agr;,&bgr;-unsaturated carboxylic acid with a heterocyclic compound in the presence of a polymerization inhibitor and a metal oxide catalyst. They thought that such effects might be obtained with greater certainty if the chemical structure of the heterocyclic compound be restricted to a specific one, like the case mentioned above. They also found
Kubo Takafumi
Yurugi Keiji
Connolly Bove & Lodge & Hutz LLP
Killos Paul J.
Nippon Shokubai Company, Ltd.
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