3-hydroxymethylcycloalkanols and process for producing them

Details 3-hydroxymethylcycloalkanols and process for producing them 3-hydroxymethylcycloalkanols and process for producing them

1998-09-24

2001-04-10

Padmanabhan, Sreeni (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S821000, C568S822000, C568S835000, C568S832000

Reexamination Certificate

active

06215031

ABSTRACT:

This application is the national phase under 35 U.S.C. §371 of prior PCT International Application No. PCT/JP98/00191 which has an International filing date of Jan. 20, 1998 which designated the United States of America, the entire contents of which are hereby incorporated by reference.
TECHNICAL FIELD
The present invention relates to a 3-hydroxymethylcycloalkanol which is useful as, for example, polyhydric alcohol component of thermoplastic and thermosetting polymers and to a process for producing the same.
BACKGROUND TECHNOLOGY
With the expanding application of polyester and polyurethane in recent years, there exists a demand for improvements in various polymer properties including weather resistance, water resistance, heat resistance, resistance to chemicals, electrical characteristics, and mechanical characteristics. In order to improve those polymer properties, there exist many researches for polyhydric alcohols which are component of those polymer. As the polyhydric alcohol, it is known that aliphatic polyols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexanetriol, trimethylolpropane, pentaerythritol and alicyclic diols such as 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol.
However, with those polyhydric alcohols, all the above-mentioned prperties can hardly be implemented in a well-assorted balance.
It is, therefore, an object of the present invention to provide a polyhydric alcohol useful as the starting material in the production of the polymers and a process for producing the polyhydric alcohol.
It is another object to provide a technology for providing the polyhydric alcohol efficiently.
DISCLOSURE OF INVENTION
Having explored into the art for accomplishing the above objects, the inventors of the present invention found that 3-hydroxymethylcycloalkanols are useful as the starting material in the production of the polymers.
Thus, an 3-hydroxymethylcycloalkanol of the present invention is a compound of the following formula (1).
wherein Y
1
represents a saturated aliphatic hydrocarbon group. This 3-hydroxymethylcycloalkanol can be produced by reduction of a 3-formylcycloalkanone or a 3-formylcycloalkenone.
BEST MODE FOR CARRYING OUT THE INVENTION
3-Hydroxymethylcycloalkanol
Referring to any 3-hydroxymethylcycloalkanol of the above formula (1), the bivalent saturated aliphatic hydrocarbon group designated by Y
1
may be straight-chain or branched, and, in the case of a branched-chain hydrocarbon group, the same carbon atom may be substituted by 1 or 2 alkyl groups. The aliphatic hydrocarbon group includes, for example, C
1-10
alkylene groups such as methylene, ethylene, propylene, trimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, tetramethylene, 2-methyltetramethylene, 2,2-dimetyhltetramethylene, pentamethylene, hexamethylene, and so forth. Preferred straight-chain and branched alkylene groups are C
2-8
alkylene groups, with C
2-6
alkylene groups being particularly preferred.
Those aliphatic hydrocarbon groups may each be substituted, in suitable positions, by various substituent groups, for example, hydroxyl, C
1-4
alkoxy, carboxy, alkoxycarbonyl, alicyclic hydrocarbon groups (cycloalkyl, cycloalkenyl, cycloalkinyl groups, etc.), and aromatic hydrocarbon groups (aryl groups such as phenyl group).
The 3-hydroxymethylcycloalkanol of the above formula (1) includes, for example, 3-hydroxymethylcyclopentanol, 3-hydroxymethylcyclohexanol, 3-hydroxymethyl-5-methylcyclohexanol, 3-hydroxymethylcycloheptanol, 3-hydroxymethyl-5,5-dimethylcyclohexanol, 3-hydroxymethylcyclooctanol, 3-hydroxymethyl-5-methylcyclooctanol, 5-phenyl-3-hydroxymethylcyclohexanol, and so forth. The preferred 3-hydroxymethylcycloalkanol is 3-hydroxymethyl-5,5-dimethylcyclohexanol.
When such an 3-hydroxymethylcycloalkanol is used as a starting material in the production of polymers (e.g. diol component of polyesters or polyurethanes, polyhydric alcohol component of epoxy resin), polymers with excellent weather resistance, inhibition the decrease of mechanical strength, and good resistance to chemicals can be obtained due to the existence of substituted hydroxy groups on the alicyclic skeleton and on the methyl group. Moreover, because a cyclic structure is introduced, polymers with high melting points and improved heat resistance can be obtained. In addition, because of its alicyclic structure, polymers of low polarity, good water resistance, and excellent electrical characteristics can be obtained.
Process for Producing a 3-Hydroxymethylcycloalkanol
As illustrated in the following reaction process scheme, the process of the present invention comprises subjecting a 3-formylcycloalkanone or 3-formylcycloalkenone of the following formula (2) (hereinafter may refferd to briefly as the substrate compound) to catalytic reduction in the presence of a catalyst to give a 3-hydroxymethylcycloalkanol of the following formula (1). The substrate 3-formylcycloalkanone or 3-formylcycloalkenone of the formula (2) can be obtained by various methods, for example, by oxidizing a 3-methylcycloalkanone or 3-methylcycloalkenone of the following formula (3). The 3-methylcycloalkenones, as the starting material, are easily produced by condensation of acetones, and 3-methyl-2-cyclopenten-1-on is easily produced by isomerization of 2-cyclohexen-1-on.
wherein Y
1
represents a saturated aliphatic hydrocarbon group; Y
2
represents a saturated or unsaturated hydrocarbon group.
Process for Producing Compound (2)
The 3-formylcycloalkanone or 3-formylcycloalkenone of the above formula (2) may be produced by oxidation of the 3-methylcycloalkanone or 3-methylcycloalkenone of the above formula (3). The 3-formylcycloalkenone or 3-formylcycloalkanone can be produced by an oxidation reaction with oxygen in the presence of a catalyst such as a metal oxide (selenium oxide, chromium oxide, dichromic acid, and oxides of copper, silver, lead, etc.), a naphthenic acid salt (cobalt, chromium, or other salt), or a vanadium oxide catalyst (V
2
O
5
—SnO
2
, V
2
O
5
—SnO
2
—Fe
2
O
3
, V
2
O
5
—Fe
2
O
3
, etc.), an oxidation reaction with oxygen, as described in Japanese Patent Application Laid-open No.154528/1983 (JP-A-58-154528), in the presence of at least one metal salt selected from the group consisting of salts of iron, ruthenium, rhodium, cobalt, etc., or an oxidation process using a heteropolyacid or a salt thereof as the catalyst. Preferred is the process for producing a 3-formylcycloalkenone by using a 3-methylcycloalkenone in combination with, as the oxidation catalyst, a heteropolyacid or a salt thereof.
The heteropolyacid is an oxy-acid condensate containing 2 or more dissimilar center ions and is also known as a heteronuclear condensed acid. The heteropolyacid may for example be composed of the oxy-acid ion (e.g. phosphate, silicate, etc.) of an element such as P, As, Sn, Si, Ti, or Zr and the oxy-acid (e.g. vanadic acid, molybdic acid, tungstic acid, etc.) of an element such as V, Mo, or W. A variety of heteropolyacids for use as catalysts can be obtained according to various combinations of such oxy-acid ion and oxy-acid.
The preferred heteropolyacid anion can be expressed by XM
12
O
40
. “X” represents an element such as Si, P, or the like and “M” represents an element such as Mo, W, V, or the like. The heteropolyacid having such a composition includes phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, phosphovanadomolybdic acid, and so forth. The preferred heteropolyacid are phosphomolybdic acid and phosphovanadomolybdic acid, with phosphovanadomolybdic acid being particularly preferred.
Phosphovanadomolybdic acid or its salt is expressed by the following formula.
A
3+n
[PV
n
Mo
12-n
O
40
]
wherein “A” represents a heteropolyacid cation and n represents an integer of 1 to 10.
The heteropolyacid cation designated by “A” need not only be hydrogen atom but also may be a cation other than H, for example NH
4
, an alkali metal (e.g. Cs, Rb, K, Na, Li) cation or an alkaline earth metal (e.g. Ba, Sr, Ca, Mg) cation.
While the heterop

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