Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-01-11
2001-05-22
Killos, Paul J. (Department: 1623)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S040000, C560S141000, C560S220000, C585S252000, C564S188000
Reexamination Certificate
active
06235851
ABSTRACT:
DESCRIPTION
1. Technical Field
The present invention relates to a process for producing a polymerizable adamantane derivative useful for providing a functional polymer, a catalyst useful for synthesizing polymerizable adamantane derivatives, and the novel polymerizable adamantane derivative.
2. Background Art
Photo-curable polymers or monomers have been utilized in various fields, for example, as photosensitive resins and covering agents for optical fibers, besides paint compositions, paints, coating agents such as printing inks and adhesives. Among such photo-setting polymers or monomers, polycyclic hydrocarbons [e.g., norbornene (meth)acrylate, adamantane (meth)acrylate] are useful for producing coating layers or moldings which are excellent in optical properties, mechanical properties and the like.
Japanese Patent Application Laid-open No. 33350/1988 (JP-A-63-33350) [Japanese Patent Publication No. 61980/1995 (JP-B-7-61980)] proposes to produce adamantane mono(meth)acrylate by bromating an adamantane, hydrolyzing to introduce a hydroxyl group thereto, then esterifying it by using a (meth)acrylic acid or (meth) acrylic acid halide. In the introduction of a hydroxyl group, however, it is required that an adamantane is bromated by using a large amount (e.g., 10 mole or more) of bromine, and that a formed bromide is hydrolyzed with an expensive reagent containing silver (e.g., silver nitrate or silver sulfate) in a stoichiometric excess amount [Chem. Ber., 92 1629(1959), 93 226,1161(1960): J. Org. Chem., 26 2207(1961)]. Moreover, in this method, reacting at a temperature of about 100° C. for hours is required. Specifically, in this method, it is difficult to considerably improve production efficiencies of an adamantane mono(meth)acrylate and yields. Further, in this method, a halogen remains, which is unfavorable in view of safe hygiene and environmental hygiene.
In the above-mentioned esterification, use of (meth)acrylic acid halide (in particular chloride) is advantageous, relative to (meth)acrylic acid, to enhance yields of the objective compounds. In a process using acid halides such as a (meth)acrylic acid chloride, however, separation of amine hydrochloride is required because amines, as a dehydrogen halide agent, are used together with the halides. However, the separation of the amine hydrochloride is considerably difficult, in addition, the separation of excess amines by distillation or recrystallization deteriorates yields of the objective compounds.
As a process for providing an adamantandiol, Japanese Patent Publication No. 16621/1967 (JP-B-42-16621) discloses that adamantanediol is obtained by allowing adamantane to react, in a concentrated acetic acid solution, by using 5-fold mole or more of chromic acid relative to adamantane. In this process, adamantandiol can be formed, however, a treatment of chromium components is required. In addition, oxidation of adamantane does not proceed to the level of polyol bodies such as tri- or more alcohol bodies even under severer reaction conditions.
A preferred oxidation process, from the viewpoints of resources and the environment, is a catalytic oxidation process, which is conducted with the direct use of molecular oxygen or air as an oxidizing agent. In page 762 of the “Lecture Draft II” (1994) of 67th Spring Annual Meeting of Chemical Society of Japan and Japanese Patent Application Laid-open No. 38909/1996 (JP-A-8-38909), it is disclosed that adamantane is oxidized with oxygen by using an oxidation catalyst comprising an imide compound (e.g., N-hydroxyphthalimide) to produce adamantanemonool.
It is conceivable that adamantane mono(meth)acrylate or poly(meth)acrylate is formed by subjecting the adamantanemonool or adamantanepolyol produced in such manner to esterification reaction with (meth)acrylic acid or acid halide. However, since the esterification reaction is an equilibrium reaction, and an esterification efficiency of an alcohol body of adamantane (especially, an adamantanepolyol having plural hydroxyl groups) is low, it is difficult to obtain adamantane (meth)acrylate (in particular, an adamantane poly(meth)acrylate having plural (meth)acryloyl groups) in a high yield.
In the Lecture Draft II (pages 1178 and 1179) of 69th Spring Annual Meeting of Chemical Society of Japan, it is reported that equilibratory advantageous amidation reaction of an ester compound having a simple structure proceeds more efficiently, in the presence of samarium catalyst, than in the presence of a conventional Lewis acid catalyst.
It is, therefore, an object of the present invention to provide a process which can inhibit admixture of an halogen component and produce an adamantane derivative having at least one polymerizable unsaturated group in a high yield.
It is another object of the present invention to provide a process for producing a polymerizable adamantane derivative wherein a highly pure adamantane derivative having at least one polymerizable unsaturated group may effectively be formed with high efficiency, and a catalyst for synthesizing the polymerizable adamantane derivative.
A further object of the present invention is to provide a process for producing a polymerizable adamantane derivative wherein a polymerizable unsaturated group may effectively be introduced to the adamantane derivative by esterification or amidation in a mild or moderate condition, and a catalyst for synthesizing the polymerizable adamantane derivative.
It is still another object of the present invention to provide a novel polymerizable adamantane derivative useful for providing a functional polymer and the like.
A still further object of the present invention is to provide a polymerizable adamantane derivative which does not have a halogen component substantially.
DISCLOSURE OF INVENTION
The inventors of the present invention did intensive research, and finally found that (a) oxidation of adamantane with oxygen, in the presence of an oxidation catalyst comprising an imide compound (e.g., N-hydroxyphthalimide) and a specific transition metal compound, provides not only adamantanemonool but also an adamantanepolyol in high efficiency, and (b) a highly pure adamantane derivative having at least one polymerizable unsaturated bond is formed by conducting an esterification or amidation of the formed adamantanemonool or adamantanepolyol with a polymerizable unsaturated compound, in the presence of a catalyst comprising a rare earth metal compound. The present invention has been accomplished based on the above findings.
Thus, in the present invention, a compound shown by the following formula (1a) (adamantane derivative):
wherein R
1a
, R
2a
, R
3a
and R
4a
independently represent at least one substituent selected from a non-reactive atom, a non-reactive group, a hydroxyl group, a hydroxymethyl group, a carboxyl group, an amino group and a reactive group derived therefrom, and at least one of R
1a
, R
2a
, R
3a
and R
4a
is a hydroxyl group, a hydroxymethyl group a carboxyl group, an amino group or a reactive group derived therefrom, is subjected to esterification reaction or amidation reaction, in the presence of a catalyst comprising a compound containing a Group 3A element of the Periodic Table of Elements, with at least one compound (polymerizable unsaturated compound (1b)) selected from an alcohol having a polymerizable unsaturated bond, a carboxylic acid, an amine and a reactive derivative thereof to provide a polymerizable adamantane derivative shown by the following formula (1):
wherein R
1
, R
2
, R
3
and R
4
independently represent at least one substituent selected from a non-reactive atom, a non-reactive group and a polymerizable unsaturated group, and at least one of R
1
, R
2
, R
3
and R
4
is a polymerizable unsaturated group; X represents a connecting group comprising an ester bond or an amide bond, n denotes 0 or 1, and X may be different from each other according to R
1
, R
2
, R
3
and R
4
, with the proviso that n is 0 when R
1
, R
2
, R
3
or R
4
is a non-reactive atom and a non-reactive group.
In the pol
Hirai Naruhisa
Ishii Yasutaka
Nakano Tatsuya
Daicel Chemical Industries Ltd.
Killos Paul J.
Oh Taylor Victor
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