JPH072659B2 - 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 10 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. The polymer material having excellent heat resistance and water resistance can be produced. It is intended to provide new biscyclohexanols.

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].

Represents Here, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group,
Represents a cyclohexyl group or an aryl group, provided that R ₁
And R ₂ may form a ring to form a divalent cyclohexyl group, and when not forming a divalent cyclohexyl group, at least one of R ₁ and R ₂ is a cyclohexyl group or aryl. It is a base. The biscyclohexanols according to the present invention are novel compounds, and have excellent physical properties, particularly heat resistance and water resistance, such as polyester, saturated polyester resin, unsaturated polyester resin, alkyd resin, polycarbonate resin, epoxy resin or polyurethane. It is useful as a raw material or a part of raw material components for producing the polymer material.

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, Represents Here, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group,
Represents a cyclohexyl group or an aryl group, provided that R ₁
And R ₂ may form a ring to form a divalent cyclohexyl group, and when not forming a divalent cyclohexyl group, at least one of R ₁ and R ₂ is a cyclohexyl group or aryl. It is a base. ) The structures of these novel biscyclohexanols are as follows: melting point measurement, gas chromatography analysis, mass spectrometry, ¹ H-NMR
Can be confirmed by.

Specifically, the above compounds as they are, or trimethylsilylated to perform gas chromatographic analysis, at the same time, biscyclohexanols or trimethylsilylated biscyclohexanols are mass analyzed, and CDC |
Δ of each proton by ¹ H-NMR (60MHZ) using ₃ solvents
The structure is determined by determining the value.

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, X is the same as above.) Specifically, for example, 4,4 ′-[1,4-phenylenebis (1
-Methylethylidene)] bisphenol undergoes nuclear hydrogenation under specific conditions to give 4,4 '-[1,4-phenylenebis (1-
Methylethylidene)] biscyclohexanol is obtained, and if 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol is subjected to nuclear hydrogenation under specific conditions, 4,4′- [1,3-Phenylenebis (1-methylethylidene)] biscyclohexanol is obtained. Furthermore, nuclear hydrogenation of 4,4 '-(1-phenylethylidene) bisphenol gives 4,4'-(1-cyclohexylethylidene) biscyclohexanol, which is 4,4 '-(phenylmethylidene) bisphenol. Nuclear hydrogenation of
4,4 '-(Cyclohexylmethylidene) biscyclohexanol is obtained, and nuclear hydrogenation of 4,4'-cyclohexylidenebisphenol gives 4,4'-cyclohexylidenebiscyclohexanol.

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

In carrying out the nuclear hydrogenation of bisphenols, conventionally known nuclear hydrogenation catalysts such as supported Rh catalyst, supported Ru catalyst and Raney nickel are used.

In the reaction, bisphenols may be nuclear hydrogenated as they are, or may be nuclear hydrogenated in the presence of a solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, ethers such as dioxane.

In the present invention, the raw material bisphenols represented by the general formula [II] is subjected to nuclear hydrogenation to produce the biscyclohexanols represented by the general formula [I] according to the present invention. Represented by X in the general formulas [I] and [II] No nuclear hydrogenation of the benzene ring in the group is carried out, and when X is a group of --CR ₁ R _2- , the aryl group in the group is optionally hydrogenated to a cyclohexyl group. , Benzene rings located at both ends of X are subjected to nuclear hydrogenation to obtain biscyclohexanols according to the present invention. The nuclear hydrogenation reaction of such a raw material bisphenol can be controlled by properly selecting the reaction conditions such as the solvent, the type of catalyst and the pressure and temperature during the reaction. As an example, a supported Rh catalyst is used as a catalyst, and the reaction temperature is 130
X in the general formula [II] using ethanol as a solvent under the conditions of ℃ and hydrogen pressure of 40 kg / cm ² G. When the bisphenol compound which is is hydrogen-reduced, X in the general formula [I] becomes A biscyclohexanol compound is obtained. However, when hydrogen reduction is performed using isopropanol as a solvent under the same conditions, X in the general formula [I] is A biscyclohexanol compound reduced to 1 is obtained.

In the present invention, the amount of the catalyst used varies depending on the type of catalyst, the amount of noble metal supported, the bisphenols, the concentration, etc.
It is preferably used in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of bisphenols.

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 an additive or a raw material of an additive used for improving the performance of various oily 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-phenylenebis (1-methylethylidene)] biscyclohexanol (Formula A) 45 ml of 4,4 '-[1,4-phenylene bis (1-methylethylidene)] bisphenol, 45 g of ethanol and 5% Rh / 2 g of carbon supporting 5% by weight of Rh, 200 ml equipped with a stirrer Was charged into a stainless steel autoclave, and stirred at 130 ° C. under a hydrogen pressure of 40 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 temperature was cooled to room temperature, hydrogen remaining in the autoclave was purged out of the system, and then the reaction contents were diluted with ethanol and taken out. The reaction contents diluted with ethanol were filtered to remove the catalyst, and then ethanol was distilled off under reduced pressure. Toluene was added to the obtained residue and heated to homogenize the whole, and then hexane was added 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 METTLER EP-61 type automatic melting point measuring device).
As a result, 35 g of white crystals having a temperature of 130 ° C to 160 ° C were obtained.

This compound was identified as 4,4 '-[1,4-phenylenebis (1-methylethylidene)] biscyclohexanol (cis / cis, cis / trans, and trans / trans) having the structure of formula A from the following instrumental analysis results. It was confirmed that the mixture had a purity of 96.4% by GC analysis.

Gas Chromatographic Analysis The above crystals were subjected to trimethylsilylation with "TMSI-H" manufactured by Gaskro Industrial Co., Ltd., and then subjected to gas chromatographic analysis. An analysis under the following conditions showed that the retention time was 19.4.
Minutes, 21.6 minutes and 24.4 minutes (retention time of the orthoterphenyl used as standard: 4.9 minutes), 40.7 minutes each
%, 44.9% and 13.3% of the area, three peaks were recognized.

(Gas chromatographic analysis conditions): Column: Dexil-300GC, 1m glass column temperature, Col., 200 → 280 ℃ 5 ℃ / min temperature increase Inj., Det., 280 ℃ carrier gas, N ₂ 40ml / min, detector F1D 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 peaks were compounds having a molecular weight of 502.

Molecular weight calculated from the structure of: 502 The attribution of each absorption is as follows.

1) Cyclohexane ring protons and -OH protons except OH gem-H 2) CH ₃ protons 3) OH gem-H (axial and equitorial) 4) Benzene ring proton Example 2 4,4 '-[1,3 -Phenylenebis (1-methylethylidene)] biscyclohexanol (Formula B) 50 g of 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 50 g of ethyl alcohol and 5% Rh in which 5% by weight of Rh is supported on carbon / 2 g of carbon
Was charged into a 200 ml stainless autoclave equipped with a stirrer and stirred under the conditions of 130 ° C. and hydrogen pressure of 40 kg / cm ² G until almost no hydrogen was absorbed, and the nuclear hydrogenation reaction of the bisphenol was carried out. . After completion of the reaction, the mixture was cooled to room temperature, hydrogen remaining in the autoclave was purged out of the system, and then the reaction contents were diluted with ethanol and taken out. The reaction contents diluted with ethanol were filtered off to remove the catalyst, and then ethanol was distilled off under reduced pressure.
Toluene was added to the obtained residue and heated to homogenize the whole, and then hexane was added 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-EP-61 type automatic melting point measuring device).
As a result, 36.5 g of white crystals having a temperature of 122 ° C to 126 ° C were obtained. This compound has the structure of formula [B] from the following instrumental analysis results 4,
4 '-[1,3-phenylenebis (1-methylethylidene)]
It was confirmed to be biscyclohexanol (cis / cis, cis / trans, and trans / trans mixture, purity by GC analysis, 95.6%).

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 16.9 minutes, 18.5 minutes, and 20.6 minutes (retention time of orthoterphenyl used as a standard: 4.9 minutes) were 21.8%, 45.1%, and 45.1%, respectively.
Three peaks were observed in an area of 28.7%.

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 502.

Molecular weight calculated from the structure of: 502 The attribution of each absorption is as follows.

1) Cyclohexane ring protons and -OH protons except OH gem-H 2) CH ₃ protons 3) OH gem-H (axial and equitorial) 4) Benzene ring protons Example 3 4,4 '-(1-cyclohexyl) Synthesis of ethylidene) biscyclohexanol (formula C) 50 g of 4,4 '-(1-phenylethylidene) bisphenol,
50% by weight of isopropyl alcohol and carbon
Rh-supported 5% Rh / carbon 2g, 200 equipped with a stirrer
It was charged in a stainless steel autoclave of ml, and stirred at 130 ° C. under a hydrogen pressure of 50 kg / cm ² G until the absorption of hydrogen was almost eliminated 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 out of the system, and the reaction contents were diluted with tetrahydrofuran and taken out. The reaction contents diluted with tetrahydrofuran were filtered 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 homogenize the whole, 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-EP-61 type automatic melting point measuring device).
29.5 g of white crystals having a temperature of 169 ° C to 171 ° C were obtained.

This compound is 4,4 '-(1-cyclohexylethylidene) biscyclohexanol (cis / cis, cis / trans, and a mixture of trans / trans, GC purity, 87.2%) was confirmed.

Gas chromatographic analysis The above crystals were dissolved in tetrahydrofuran and subjected to gas chromatographic analysis. When analyzed under the same gas chromatography conditions as in Example 1, the retention times of 16.4 minutes, 17.1 minutes and 17.9 minutes (retention time of the orthoterphenyl used as the standard: 4.9 minutes) were 35.1%, 46.2% and 5.9%, respectively. The peak of the book was recognized.

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 the peaks were compounds having a molecular weight of 308.

Molecular weight calculated from the structure of: 308 The attribution of each absorption is as follows.

1) CH ₃ Proton 2) Cyclohexane Ring Proton and -OH Proton Excluding gem-H of OH 3) Gem-H (axial and equitorial) of OH Example 4 4,4′-Cyclohexylidenebiscyclohexanol (Formula D) ) Synthesis 50 g of 4,4'-cyclohexylidene bisphenol, 50 g of isopropyl alcohol and 2 g of 5% Rh / carbon in which 5% by weight of Rh was supported on carbon were charged into a 200 ml stainless steel autoclave equipped with a stirrer, and at 130 ° C. Hydrogen pressure 5
Stirring was carried out under the condition of 0 kg / cm ² G until the absorption of hydrogen was almost eliminated, and the nuclear hydrogenation of the bisphenol was carried out.

After completion of the reaction, the temperature was cooled to room temperature, hydrogen remaining in the autoclave was purged out of the system, and then the reaction contents were diluted with tetrahydrofuran and taken out. After removing the catalyst by filtering the reaction contents diluted with tetrahydrofuran,
Tetrahydrofuran and isopropyl alcohol were distilled off under reduced pressure. Hexane was added to the obtained residue, the mixture was heated and stirred, and then the whole was ice-cooled.

The obtained crystals were separated by filtration and dried to give 24 g of white crystals having a melting point of 160 ° C to 168 ° C measured by a light transmission method.

This compound was identified by the following instrumental analysis results as 4,4'-cyclohexylidenebiscyclohexanol (cis / cis, cis / trans, and trans /
Mixture of trans, purity by GC analysis, 87.5%).

Gas chromatographic analysis The above crystals were dissolved in tetrahydrofuran and subjected to gas chromatographic analysis. Analysis under the same gas chromatography conditions as in Example 1 revealed that retention times of 13.9 minutes, 14.6 minutes, and 15.2 minutes (retention time of the orthoterphenyl used as a standard: 4.9 minutes) were 35.5%, 38.5%, and 13.5%, respectively. Three peaks were recognized.

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 each peak was a compound having a molecular weight of 280.

Molecular weight calculated from the structure of: 280 The attribution of each absorption is as follows.

1) Cyclohexane ring proton and -OH proton except OH gem-H 2) OH gem-H (axial and equitorial) Example 5 Synthesis of 4,4 '-(cyclohexylmethylidene) biscyclohexanol Formula 7 5.0 g of 4,4 '-(phenylmethylidene) bisphenol,
Isopropyl alcohol 5.0g, and 5% Rh / carbon 0.3g
Was charged in a 200 ml stainless autoclave equipped with a stirrer, and stirred under the conditions of 130 ° C. and hydrogen pressure of 50 kg / cm ² G until the absorption of hydrogen almost disappeared. After the reaction,
After cooling to room temperature and purging the hydrogen remaining in the autoclave out of the system, the reaction contents were diluted with tetrahydrofuran and taken out. The reaction contents diluted with tetrahydrofuran were filtered to remove the catalyst, and then tetrahydrofuran and isopropyl alcohol were distilled off under reduced pressure.

Toluene was added to the obtained residue and heated to homogenize the whole, 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-EP-61 type automatic melting point measuring device).
As a result, 3.2 g of white crystals having a temperature of 148 to 153 ° C was obtained. This compound has the structure of formula 7 from the following instrumental analysis results.
(Cyclohexylmethylidene) biscyclohexanol (cis / cis, cis / trans and trans / trans mixture, purity 87.9% by GC analysis).

Gas Chromatographic Analysis The above crystals were subjected to trimethylsilylation with "TMSI-H" manufactured by Gaskro Industrial Co., Ltd., and then subjected to gas chromatographic analysis. When the analysis was performed under the following conditions, the retention time was 12.9.
1.8 min at 14.6 min, 14.6 min and 16.6 min (retention time of the orthoterphenyl used as standard: 5.7 min)
%, 42.3% and 23.8% of the area, three peaks were recognized.

(Gas chromatographic analysis conditions): Column: Dexil-300GC, 1m glass column temperature, Col., 200 → 280 ℃ 5 ℃ / min temperature increase Inj., Det., 280 ℃ carrier gas, N ₂ 40ml / min, detector F1D 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 peaks were compounds having a molecular weight of 438.

Molecular weight calculated from the structure of: 438 The attribution of each absorption is as follows.

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

Claims (2)

[Claims] 1. The following formula [I]: (In the formula, Here, R ¹ and R ² represent a hydrogen atom, a lower alkyl group, a cyclohexyl group or an aryl group (provided that when R ¹ is a hydrogen atom, R ² is a hydrogen atom, a lower alkyl group having 2 or more carbon atoms, a cyclohexyl group). Or an aryl group), and R ¹ and R ² may form a ring to form a divalent cyclohexyl group, and when R ¹ and R ² do not form a divalent cyclohexyl group, At least one of them is a cyclohexyl group or an aryl group. ) Biscyclohexanols represented by. 2. Biscyclohexanols are 4,4'-
[1,4-phenylenebis (1-methylethylidene)] biscyclohexanol, 4,4 '-[1,3-phenylenebis (1-
Methylethylidene)] biscyclohexanol, 4,4 '
Biscyclo according to claim 1, which is-(1-cyclohexylethylidene) biscyclohexanol, 4,4 '-(cyclohexylmethylidene) biscyclohexanol or 4,4'-cyclohexylidenebiscyclohexanol. Hexanols.