JPH072660B2 - Novel biscyclohexanols - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to novel biscyclohexanols.

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Aliphatic, alicyclic or aromatic diols are used for various polymeric materials such as polyester, saturated polyester resin, unsaturated polyester resin, alkyd resin, polycarbonate resin, epoxy resin and polyurethane. Widely used as a raw material. In these application fields, strength, heat resistance,
There is an increasing demand for improvement in various physical properties such as weather resistance and water resistance.

The present invention relates to novel biscyclohexanols which bring about effective effects for improving various physical properties required for these materials, particularly for improving heat resistance and water resistance.

Further, in the use of many polymer materials such as polyolefin or vinyl chloride, various additives such as lubricants, plasticizers and antistatic agents are used in order to improve moldability and various physical properties. The performance required for additives is also becoming more sophisticated.

The present invention relates to novel biscyclohexanols useful as various additives requiring such high performance or as raw materials for the various additives.

In addition, various oil-based products such as lubricating oil and brake oil also use various additives to enhance their performance, but the performance required for additives in these fields also increases. It is becoming more advanced.

The present invention relates to novel biscyclohexanols useful as additives or raw materials for additives used in such fields.

Further, the present invention relates to novel biscyclohexanols which are also useful as raw materials for various organic compound products such as peroxides.

By the way, biscyclohexanols represented by the following formula are disclosed in JP-A-51-34133.

(In the formula, R _{1 to} R ₄ represent an alkyl group having 1 to 3 carbon atoms, X is a single bond, a divalent aliphatic group having 1 to 20 carbon atoms, and a divalent group having 5 to 15 carbon atoms. A cycloaliphatic group, a divalent aliphatic group having 6 to 15 carbon atoms in total with an aromatic or cycloaliphatic substituent, or Represents This publication teaches that the above-mentioned biscyclohexanols are extremely important in producing a curable polyester composition and can impart chemical resistance to the cured polyester composition. However, this Japanese Patent Laid-Open No.
The compound disclosed in Japanese Patent Publication No. 3 is merely for imparting chemical resistance to the polyester composition, and is not intended to improve the heat resistance or water resistance of the polyester.

OBJECT OF THE INVENTION The present invention has excellent physical properties by being used as a raw material component such as polyester, saturated polyester resin, unsaturated polyester resin, alkyd resin, polycarbonate resin, epoxy resin or polyurethane, or as a part of the raw material component. It is an object of the present invention to provide a novel biscyclohexanol capable of producing the polymer material having excellent heat resistance and water resistance.

The present invention is also useful as various additives such as lubricants, plasticizers and antistatic agents useful for improving the moldability and various physical properties of various polymer materials such as polyolefin or vinyl chloride or as a raw material for various additives. Biscyclohexanols.

Furthermore, the present invention is a novel biscyclohexene compound useful as an additive or a raw material for additives for improving the performance of various oil-based products such as lubricating oils and brake oils, or as a raw material for various organic compound products such as peroxides. The purpose is to provide hexanols.

SUMMARY OF THE INVENTION The novel biscyclohexanols according to the present invention are represented by the following formula [I].

(In the formula, R _{1 to} R ₄ are a hydrogen atom or the same or different alkyl groups having 1 to 4 carbon atoms.) The biscyclohexanols according to the present invention are novel compounds, and their properties, particularly heat resistance, are high. It is also useful as a raw material or a part of raw material components for producing a polymer material having excellent water resistance such as polyester, saturated polyester resin, unsaturated polyester resin, alkyd resin, polycarbonate resin, epoxy resin or polyurethane.

The biscyclohexanols according to the present invention are lubricants useful for improving the moldability or various physical properties of various polymer materials such as polyolefin or vinyl chloride,
It is also useful as various additives such as plasticizers and antistatic agents, or as a raw material for various additives.

Further, the biscyclohexanols according to the present invention are useful as additives or raw materials for additives for improving the performance of various oil-based products such as lubricating oil or brake oil,
It is also useful as a raw material for various organic compound products such as organic peroxides.

DETAILED DESCRIPTION OF THE INVENTION The novel biscyclohexanols according to the present invention will be specifically described below.

Biscyclohexanols The novel biscyclohexanols according to the present invention are represented by the following formula [I].

(In the formula, R _{1 to} R ₄ are hydrogen atoms or the same or different alkyl groups having 1 to 4 carbon atoms.) The structures of the novel biscyclohexanols include melting point measurement, gas chromatography analysis, and mass spectrometry. , ¹ H-NMR
Can be confirmed by. Specifically, performs a gas chromatography analysis by trimethylsilylation of the above compounds, the trimethylsilylated by bis cyclohexanol and mass spectrometry, and using the CDCl ₃ solvent 1H-NMR (60
MHZ) determines the structure by determining the δ value of each proton. ^{By 1} H-NMR, hydrogen of biscyclohexanols is
(B) Proton and -OH proton of cyclohexane ring excluding gem-H of OH group, (b) CH ₃ proton and (c) O
It can be seen that H is attributed to gem-H (axial and equalatorial).

Production Method Biscyclohexanols according to the present invention have the following formula [I
[I] can be produced by a nuclear hydrogenation reaction of the corresponding bisphenols.

(In the formula, R _{1 to} R ₄ are the same as above.) Specifically, for example, 4,4 ′-[1,4-phenylenebis (1
-Methylethylidene)] bisphenol is subjected to nuclear hydrogenation under specific conditions to obtain 4,4 '-[1,4-cyclohexylenebis (1-methylethylidene)] biscyclohexanol. If 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol is subjected to nuclear hydrogenation under specific conditions, 4,4'-[1,3-cyclohexylenebis (1
-Methylethylidene)] biscyclohexanol is obtained.

The nuclear hydrogen reaction of bisphenols can be performed under the following conditions.

When carrying out the nuclear hydrogenation of bisphenols, conventionally known nuclear hydrogenation catalysts are used. Specifically, supported Rh
A catalyst, a supported Ru catalyst, Raney nickel, etc. are used.

In the reaction, bisphenols may be subjected to nuclear hydrogenation as they are, or may be subjected to nuclear hydrogenation in the presence of a solvent such as alcohols such as methanol, ethanol and isopropanol, ethers such as dioxane. The amount of this catalyst used depends on the type of catalyst, the amount of precious metal supported, the concentration of bisphenols, etc.
It is preferably used in an amount of 0.1 to 100 parts by weight with respect to parts by weight.

The reaction temperature is room temperature to 350 ° C, preferably 50 to 250 ° C,
The hydrogen pressure during the reaction is from normal pressure to 300 Kg / cm ² G, preferably 5 to 20
It is 0 Kg / cm ² G.

After completion of the reaction, the catalyst is filtered off from the reaction mixture, and then, if a solvent is used, the solvent is distilled off and, if necessary, purified by distillation under reduced pressure, or a suitable solvent is added to crystallize. The biscyclohexanols of the present invention can be obtained by precipitation and purification.

Utility The novel biscyclohexanols according to the present invention are polymer materials such as polyester, saturated polyester resin, unsaturated polyester resin, alkyd resin, polycarbonate resin, epoxy resin or polyurethane having excellent physical properties, particularly heat resistance and water resistance. It is useful as a raw material or a part of raw material components for producing. For example, when producing polyethylene terephthalate composed of terephthalic acid and ethylene glycol, which is a typical polyester, when the biscyclohexanol according to the present invention is added in an amount of about 10% by weight based on the total weight of terephthalic acid and ethylene glycol. The glass transition temperature of the obtained polyethylene terephthalate is about 85 ° C or higher. On the other hand, the glass transition temperature of polyethylene terephthalate obtained from terephthalic acid and ethylene glycol without adding biscyclohexanol according to the present invention is about 75 ° C. Thus, when the novel biscyclohexanols according to the present invention are added to the reaction system when producing polyethylene terephthalate from terephthalic acid and ethylene glycol, the glass transition temperature of the obtained polyethylene terephthalate rises, and the tensile strength and rigidity are increased. , Practical properties such as elasticity can be maintained at higher temperatures.

The biscyclohexanols according to the present invention are lubricants useful for improving the moldability or various physical properties of various polymer materials such as polyolefin or vinyl chloride,
It is useful as various additives such as plasticizers and antistatic agents, or as a raw material for manufacturing various additives. For example, for soft vinyl chloride, di2-ethylhexyl phthalate,
Although a large amount of a plasticizer such as diheptyl phthalate is blended, when the higher fatty acid ester of biscyclohexanol according to the present invention is used instead of these or a part of them, non-volatility, extraction resistance, and Retention performance such as water resistance and water absorption can be improved.

Further, the biscyclohexanols according to the present invention are also useful as additives or raw materials of additives used for improving the performance of various oil-based products such as lubricating oil and brake oil.

Furthermore, the biscyclohexanols according to the present invention are also useful as a raw material for various organic useful substances such as peroxides.

EFFECTS OF THE INVENTION The biscyclohexanols according to the present invention are novel and useful compounds, as raw materials for various polymeric materials excellent in physical properties, particularly heat resistance and water resistance, and as additives for various polymeric materials. Alternatively, as a raw material for additives of various polymer materials, for example, as an additive for various oily products such as lubricating oil and brake oil, or as a raw material for additives,
Alternatively, it can be used as a raw material for various organic compound products such as peroxides.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Synthesis of 4,4 '-[1,4-cyclohexylene bis (1-methylethylidene)] biscyclohexanol (Formula A) 4,4 '-[1,4-phenylene bis (1-methylethylidene)] bisphenol 50g, isopropyl alcohol 50g
And, 2% of 5% Rh / carbon with 5% by weight of Rh supported on carbon was charged into a 200 ml stainless autoclave equipped with a stirrer, and the absorption of hydrogen under the conditions of 130 ° C and hydrogen pressure of 50 Kg / cm ² G The nuclear hydrogenation reaction of the above-mentioned bisphenol was carried out by stirring until almost disappeared. After the reaction,
After cooling to room temperature, hydrogen remaining in the autoclave was purged outside the system, and the reaction contents were diluted with tetrahydrofuran and taken out. The reaction contents diluted with tetrahydrofuran were filtered off to remove the catalyst, and then tetrahydrofuran and isopropyl alcohol were distilled off under reduced pressure.
Hexane was added to the obtained residue and the mixture was heated and stirred, and then the whole was ice-cooled.

The crystals thus obtained were separated by filtration and dried to give 49 g of white crystals having a melting point (measured using a Metra-FP-61 type automatic melting point measuring device) measured by a light transmission method of 158 ° C to 174 ° C.

This compound was identified as 4,4 '-[1,4-cyclohexylene bis (1-methylethylidene)] biscyclohexanol (cis / cis, cis / trans, trans / trans) having the structure of formula A from the instrumental analysis results described later. It was confirmed that the mixture had a purity of 99.9% by GC analysis.

Gas Chromatographic Analysis The above crystals were subjected to trimethylsilylation with a trimethylsilylating agent “TMSI-H” manufactured by Gaschro Industry Co., Ltd., and then subjected to gas chromatographic analysis. The analysis was performed under the following conditions: retention time 24.5 minutes, 28.6 minutes and 34.2 minutes (retention time: 4.9% for the orthoterphenyl used as standard).
Min), three peaks were observed at areas of 46.0%, 43.2%, and 10.7%, respectively.

(Gas chromatographic analysis conditions): Column; Dexil-300GC, 1m glass column temperature, Col., 200 → 280 ℃ 5 ℃ / min temperature rise Inj., Det., 280 ℃ carrier gas, N ₂ 40ml / min, detector FID Mass spectrometry The molecular weights of the compounds contained in the above three peaks were determined by GC-MS (FI
As a result, it was confirmed that all of the peaks were compounds having a molecular weight of 508.

Molecular weight calculated from the structure of: 508 The attribution of each absorption is as follows.

1) CH ₃ putron 2) Cyclohexane ring proton and -OH proton except gem-H of OH 3) gem-H (axial and equitorial) of OH Example 2 4,4 ′-[1,3-cyclohexylenebis ( 1-Methylethylidene)] biscyclohexanol (Formula B) 4,4 '-[1,3phenylenebis (1-methylethylidene)]
50 g of bisphenol, 50 g of isopropyl alcohol, and 5% Rh / 5 g of carbon supporting 5% by weight of Rh / carbon
Was charged into a 200 ml stainless autoclave equipped with a stirrer, and the mixture was stirred under the conditions of 130 ° C. and hydrogen pressure of 50 kg / cm ² G until the absorption of hydrogen almost disappeared to carry out the nuclear hydrogenation reaction of the bisphenol. After completion of the reaction, the mixture was cooled to room temperature, hydrogen remaining in the autoclave was purged outside the system, and the reaction contents were diluted with tetrahydrofuran and taken out. The reaction contents diluted with tetrahydrofuran were filtered off to remove the catalyst, and then isopropyl alcohol and tetrahydrofuran were distilled off under reduced pressure. Toluene was added to the obtained residue and heated to make the whole uniform, and then ice-cooled to precipitate crystals.

The crystals were separated by filtration and dried, and the melting point was measured by a light transmission method (measured using a Metra-FP-61 type automatic melting point measuring device).
32 g of white crystals having a temperature of 181 ° C to 185 ° C were obtained. This compound has the structure of formula [B] from the following instrumental analysis results 4,
4 '-[1,3-Cyclohexylene bis (1-methylethylidene)] biscyclohexanol (cis / cis, cis / trans, trans / trans mixture, purity by GC analysis, 98.8%) It was

Gas Chromatographic Analysis The above crystals were subjected to trimethylsilylation in the same manner as in Example 1 and then subjected to gas chromatographic analysis. Analysis under the same conditions as in Example 1 revealed that retention times of 20.4 minutes, 22.0 minutes and 25.1 minutes (retention time of the orthoterphenyl used as a standard: 4.9 minutes) were 26.0%, 57.9% and
Three peaks were observed in an area of 14.9%.

Mass spectrometry The molecular weights of the compounds contained in the above three peaks were determined by GC-MS (FI
As a result, it was confirmed that all of the peaks were compounds having a molecular weight of 508.

Molecular weight calculated from the structure of: 508 The attribution of each absorption is as follows.

1) CH ₃ protons 2) Cyclohexane ring protons and -OH protons except OH gem-H 3) OH gem-H (axial and equitorial)

Claims (2)

[Claims] 1. The following formula [I]: (In the formula, R ^{1 to} R ⁴ are hydrogen atoms or the same or different alkyl groups having 1 to 4 carbon atoms) and biscyclohexanols. 2. Biscyclohexanols are 4,4'-
[1,4-Cyclohexylene bis (1-methylethylidene)]
The biscyclohexanols according to claim 1, which are biscyclohexanol or 4,4 '-[1,3-cyclohexylenebis (1-methylethylidene)] biscyclohexanol.