JP2000281613A - Alicyclic diol and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound capable of introducing an alicyclic skeleton into the main chain of a polyester, and useful as a raw material for an optical material excellent in heat resistance, transparency and moisture resistance, especially for an alicyclic polyester or the like. SOLUTION: This new compound is the one of formula I (l and m are each 0 or 1; R1 is a 2-6C alkylene; R2 to R4 are each H or a 1-6C alkyl). The compound can be obtained by reacting (A) an olefin part of an alicyclic monoolefin alcohol of formula II with (B) a compound of the formula HO-(R1O)m-H (e.g. water and ethylene glycol) by using an acid catalyst such as sulfuric acid at a reaction temp. of about 50-110 deg.C for 2-10 hr while regulating the amount of the used acid catalyst so as to be >=0.01 pt.mol, especially 0.05-6 pts.mol based on 1 pt.mol of the component A, and the amount of the used component B so that the concentration of the component A may be about 10-30 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel alicyclic diol and a method for producing the same. The alicyclic diol of the present invention can be used as a raw material of an optical material (such as an alicyclic polyester) having excellent heat resistance, transparency, and moisture resistance, and can be modified by modifying a hydroxyl group with, for example, a polymerizable acrylic derivative. It can also be a raw material for structural resin. Further, it is also useful as an additive for imparting physical properties such as heat resistance, transparency and heat resistance of general-purpose resins and various structural material resins.

[0002]

2. Description of the Related Art Alicyclic polyesters obtained from monomers having an alicyclic structure, such as alicyclic dicarboxylic acids and alicyclic diols, have physical properties such as transparency, heat resistance, chemical resistance and dimensional stability. Is known to have excellent chemical and chemical properties. Such alicyclic polyesters are useful polymer materials as various optical materials such as optical disks, optical card substrates, and substrates for liquid crystal display elements by utilizing the inherent properties of the alicyclic skeleton. Further, such polymer materials are required to have mechanical strength, impact resistance, moisture absorption resistance, etc. in addition to optical characteristics.

[0003] However, conventionally known polyesters having an alicyclic structure have good optical properties and heat resistance, but have a monomer in which a hydroxyl group or a carboxyl group is bonded to an adjacent carbon atom or an adjacent carbon atom. Because it is synthesized using, the alicyclic structure of such a monomer is only introduced into the polyester side chain, mechanical strength,
There was a problem in terms of impact resistance.

[0004]

An object of the present invention is to provide a raw material monomer capable of introducing an alicyclic skeleton into a polyester main chain.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the following general formula (1)
The present invention was completed by newly synthesizing an alicyclic diol represented by the formula:

That is, the present invention provides a compound represented by the general formula (1):

[0007]

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(Wherein l and m each independently represent 0 or 1, R ₁ represents an alkylene group having 2 to 6 carbon atoms, and R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom Or an alkyl group having 1 to 6 carbon atoms.) And a general formula (2):

[0009]

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(Wherein l represents 0 or 1, R ₂ ,
R ₃ and R ₄ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms.
6 represents an alkyl group. The alicyclic monoolefin alcohol represented by the general formula (5):

[0011]

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(Wherein, R ₁ represents an alkylene group having 2 to 6 carbon atoms, and m represents 0 or 1). The alicyclic compound represented by the general formula (1) is reacted with the compound represented by the formula (1). The present invention relates to a method for producing a diol.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The general formula (2) used as a starting material of the alicyclic diol represented by the general formula (1) of the present invention:

[0014]

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(Wherein l represents 0 or 1, R ₂ ,
R ₃ and R ₄ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms.
6 represents an alkyl group. The alicyclic monoolefin alcohol represented by the formula (1) can be produced by various methods. For example, a Diels-Alder reaction between cyclopentadiene or dicyclopentadiene, which is a diene compound, and an acrylate ester is performed to obtain a compound represented by the general formula (4):

[0016]

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(Wherein l represents 0 or 1, R ₂ ,
R ₃ and R ₄ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms.
And R ₅ represents an alkyl group having 1 to 6 carbon atoms. The alicyclic carboxylic acid ester represented by the formula (1) is synthesized, and the ester portion of the obtained alicyclic monoolefin carboxylic acid ester represented by the general formula (4) is further reduced.

The alicyclic monoolefin carboxylate represented by the general formula (4) is a mixture of various Diels-Alder adducts (for example, in the case of cyclopentadiene and acrylate, a 1: 1 adduct of both raw materials) of 5-carboxyalkyl bicyclo [2.2.1] hept-2-ene, 2: 1 adduct of 8 carboxyalkyl tetracyclo ^[4.4.0.1 2,5 ^.1 7,10] -3 - dodecene, 3: 1 adduct of 11-carboxyalkyl hexamethylene cyclo ^[6.6.1.1 3,6 ^{.1 10,13.}
0 ^2,7 . 0 ^{9,14] -4-heptadecene} obtained as a mixture), such as, in general formula of interest by appropriately selecting the molar stoichiometry and reaction conditions of the feed of the diene compound and dienophile compound (4) It is generally known that the reaction conversion to the alicyclic monoolefin carboxylate represented by the formula can be improved, and the intended alicyclic monoolefin carboxylate represented by the general formula (4) Can be easily isolated from the reaction product by distillation under reduced pressure.

As the reducing agent used for reducing the ester moiety of the alicyclic monoolefin carboxylic acid ester represented by the general formula (4), the alicyclic monoolefin carboxylic acid ester represented by the general formula (4) may be used. There is no particular limitation as long as the ester site is selectively reduced without reducing the olefin site. As such a reducing agent, for example, lithium aluminum hydride, lithium trimethoxyaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, or the like can be used. The amount of the reducing agent used is based on 1 mol part of the alicyclic monoolefin carboxylic acid ester represented by the general formula (4).
Usually, it is at least 1 part by mole, preferably 1.5 to 5 parts by mole. The reaction solvent is not particularly limited as long as it is inert to the reaction, for example, ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as dichloromethane and chloroform, methanol, ethanol, n- or iso-propanol, Alcohols such as n-, sec- and t-butanol, and aromatic hydrocarbons such as benzene, toluene and xylene can be used. The reaction temperature and the reaction time depend on the reactivity of the alicyclic monoolefin carboxylate represented by the general formula (4), the raw material concentration in the reaction solution, and the amount of the reducing agent.
５０50 ° C., and the reaction time is about 1-10 hours.

The alicyclic diol represented by the general formula (1) of the present invention is obtained by adding the alicyclic monoolefin alcohol represented by the general formula (2) to the olefin moiety of the general formula (3):

[0021]

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(Wherein, R ₁ represents an alkylene group having 2 to 6 carbon atoms, and m represents 0 or 1), and only one of the hydroxyl groups of the compound is converted to a compound represented by the general formula It is produced by adding to the olefin part of the alicyclic monoolefin alcohol represented by (2).

As a reaction method for adding only one of the hydroxyl groups of the compound represented by the general formula (3) to the olefin portion of the alicyclic monoolefin alcohol represented by the general formula (2), for example, sulfuric acid [Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 7, pp. 1617 (1955)], a method using a photochemical reaction [Organic Synthesis (Org. Synth. ) Volume 7 304
Page (1990)], a method using mercury acetate [Chemical
Review (Chem. Rev.), vol. 48, p. 7 (195)
1 year)], a method based on hydroboration [Organic Reaction (Org. React.) Vol. 13, page 1 (1)
963)], etc., and these known methods can be employed as they are. Among these methods, a method using an acid catalyst such as sulfuric acid, in which the reaction and treatment are easy and the reaction reagent is advantageous from an industrial point of view, is preferable.

Hereinafter, a method using an acid catalyst such as sulfuric acid will be described. Specifically, such a method comprises, under an acid catalyst, adding a compound represented by the general formula (3) to an alicyclic monoolefin alcohol represented by the general formula (2) at about 50 to 110 ° C. for 2 to 10 hours. Act on time. Examples of the compound represented by the general formula (3) include water, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-propanediol.
Butanediol, 1,4-butanediol and the like. As the acid catalyst, in addition to sulfuric acid, trifluoroacetic acid,
Formic acid or the like can be used. The amount of the acid catalyst used is determined by the general formula (2)
Is usually 0.01 mol part or more, preferably 0.0 mol part to 1 mol part of the alicyclic monoolefin alcohol represented by
It is 5 to 6 mol parts. In addition, since the compound represented by the general formula (3) usually also serves as a reaction solvent, the amount of the compound used is such that the concentration of the alicyclic monoolefin alcohol represented by the general formula (2) is 10 to 30. It is preferable to adjust so as to be about weight%. In this reaction, only the compound represented by the general formula (3) can be used as a reaction solvent, but if necessary, an organic solvent inert to the reaction may be mixed. Examples of such an organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, halogenated hydrocarbons such as dichloromethane and chloroform, and ethers such as tetrahydrofuran and dioxane. . The reaction is preferably carried out in a homogeneous system by appropriately selecting the solvent from the viewpoints of reaction rate, by-product formation, and the like. The reaction can be carried out in a heterogeneous system. In such a case, the reaction is carried out by vigorously stirring and suspending the inside of the reaction system. After completion of the addition reaction, the obtained alicyclic diol represented by the general formula (1) is extracted with an organic solvent such as ethyl acetate.

[0025]

According to the present invention, a novel alicyclic diol can be provided. Since the alicyclic diol of the present invention has a hydroxyl group via an alicyclic skeleton, an alicyclic polyester having an alicyclic skeleton introduced into the main chain is obtained by using the alicyclic diol as a raw material monomer. Can be

[0026]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the following methods were used for the measurement of the physical property value, spectrum, etc. of the alicyclic diol. NMR: BRUKER ARX300 (manufactured by Bruker) IR: FT-IR FTS-7 (manufactured by Bio-Rad) Elemental analysis: Elemental analyzer 2400CHN
(Perkin Elmer) Hydroxyl value: Measured according to JIS K0070.

Production Example (i) Alicyclic monoolefin carboxylic acid ester (in the general formula (4), 1 = 1, R ₂ , R ₃ and R ₄ are each a hydrogen atom, and R ₅ is a methyl group) Production Methyl acrylate was placed in a 500 ml separable flask equipped with a stirrer, thermometer, cooling tube and dropping funnel.
6.1 g (1 mol) and 0.44 g (2000 ppm) of hydroquinone monomethyl ether were charged, the atmosphere in the flask was replaced with nitrogen, and the mixture was heated and stirred at 190 ° C. Next, 132 g (1 mol) of dicyclopentadiene was added dropwise over 3 hours while maintaining the temperature in the flask at 185 to 190 ° C., and the mixture was further heated and stirred for 30 minutes. After the completion of the reaction, the reaction mixture was distilled under reduced pressure to obtain 118-124 ° C / 2 mm.
60.2 g of a Hg fraction were obtained. This is referred to as ¹ H-NMR,
The compound was identified by IR and elemental analysis, and alicyclic monoolefin carboxylic acid ester (where n is 1, R in general formula (4)
₂ , R ₃ and R ₄ are each a hydrogen atom, R ₅ is a methyl group,
It was confirmed that COOR was endo / exo = 51/49).

(Ii) an alicyclic monoolefin alcohol (in the general formula (2), l = 1, R ₂ , R ₃ , R ₄
Is a hydrogen atom) 250 ml of diethyl ether in a 1-liter three-necked round-bottomed flask equipped with a stirrer, a thermometer, and a condenser under a nitrogen stream.
And 13.1 g of lithium aluminum hydride
(0.344 mol) was suspended and cooled to 0 ° C., and a solution of 50 g (0.229 mol) of the alicyclic monoolefin carboxylic acid ester obtained in the above (i) in 125 ml of diethyl ether was added for 60 minutes. It dripped over. Then
The mixture was stirred at 0 ° C. for 3 hours. After completion of the reaction, 15 ml of water, 15 ml of a 4 mol / l aqueous sodium hydroxide solution and 45 ml of water were added, and liquid separation extraction was performed with 500 ml of diethyl ether, and the obtained organic layer was dried over magnesium sulfate. Thereafter, magnesium sulfate was filtered off, and the obtained organic layer was removed under reduced pressure to obtain 41 g of a colorless and transparent liquid. This was identified by ¹ H-NMR, IR, elemental analysis, and hydroxyl value measurement, and the desired alicyclic monoolefin alcohol (1 in the general formula (2), R
₂ , R ₃ and R ₄ were each hydrogen atoms, and it was confirmed that endo / exo = 67/33).

Example 1 Alicyclic diol (in the general formula (1), l = 1, m =
1. Production of R ₁ having an ethylene group and R ₂ , R ₃ and R ₄ each being a hydrogen atom) Production Example (ii) in a 1-liter three-necked round bottom flask equipped with a stirrer, a thermometer, and a cooling tube After charging 20 g (0.105 mol) of the alicyclic monoolefin alcohol obtained in the above and 200 g (3.22 mol) of ethylene glycol,
While maintaining the temperature in the flask at 30 ° C. or lower, sulfuric acid was added to 0.1 ml.
515 g (5.26 mmol) were added. Then 85
The mixture was heated and stirred up to ℃, and reacted for 5 hours while keeping the temperature in the flask at 80 to 85 ℃. After completion of the reaction, the mixture was neutralized with 10.5 ml of a 1 mol / l sodium hydroxide solution, and then subjected to liquid separation extraction with 900 ml of ethyl acetate, and the obtained organic layer was dried over magnesium sulfate. Thereafter, magnesium sulfate was separated by filtration, and the obtained organic layer was removed under reduced pressure.
9.1 g of a pale yellow transparent viscous liquid was obtained. The yield of the obtained liquid was 71.9%, and the boiling point was 155 to 160.
° C / 0.1 mmHg. In addition, this is ¹ H-NM
Identified by R, IR, elemental analysis and hydroxyl value measurement, alicyclic diol (l = 1, m = 1,
It was confirmed that R ₁ was an ethylene group and R ₂ , R ₃ and R ₄ were each a hydrogen atom). The NMR spectrum data, IR spectrum data, elemental analysis value, and hydroxyl value of the obtained alicyclic diol are shown below.

¹ H-NMR (CDCl ₃ ): 3.77-
3.22 (7H, methylene proton of hydroxymethyl group, methylene proton of hydroxyethoxy group and methine proton of carbon bonded to hydroxyethoxy group), 2.56-0.38 (15H, alicyclic skeleton other than the above) Protons) (ppm)

IR (NaCl): 3388, 2944,
2893, 1462, 1348, 1107, 1049
(Cm ^-1 )

Elemental analysis EA (C ₁₅ H ₂₄ O ₃ ) Calculated: C, 71.39, H, 9.59 Found: C, 70.92, H, 9.75

Hydroxyl value Calculated value: 444.7 mgKOH / g Actual value: 445.3 mgKOH / g

Example 2 Alicyclic diol (l = 1, m =
0, R ₂ , R ₃ , and R ₄ are each a hydrogen atom) Preparation of the fat obtained in the above preparation (ii) in a 1-liter three-necked round bottom flask equipped with a stirrer, a thermometer, and a condenser. 20 g (0.105 mol) of cyclic monoolefin alcohol, water 2
After charging 100 g (11.1 mol) and 312 g (2.32 mol) of diethylene glycol dimethyl ether, sulfuric acid 1 was added while maintaining the temperature in the flask at 30 ° C. or lower.
0.3 g (0.105 mol) was added. Then 10
Heat and stir to 5 ° C, and raise the temperature in the flask to 100 to 10
The reaction was carried out for 8 hours while maintaining the temperature at 5 ° C. After completion of the reaction, the mixture was neutralized with 210 ml of 1 mol / l sodium hydroxide, and then separated and extracted with 900 ml of ethyl acetate. The obtained organic layer was dried over magnesium sulfate. Thereafter, magnesium sulfate was filtered off, and the obtained organic layer was distilled off under reduced pressure.
19.3 g of a pale yellow transparent viscous liquid was obtained. The yield of the obtained liquid is 88.2%. This is ¹ H-NM
Identified by R, IR, elemental analysis and hydroxyl value measurement, alicyclic diol (l = 1, m = 0,
R ₂ , R ₃ , and R ₄ were each a hydrogen atom). The NMR spectrum data, IR spectrum data, elemental analysis value, and hydroxyl value of the obtained alicyclic diol are shown below.

¹ H-NMR (CDCl ₃ ): 4.21-
3.67 (1H, secondary alcohol methine proton),
3.67-3.26 (2H, primary alcohol methylene proton), 2.37-0.36 (15H, proton in the alicyclic skeleton other than the above) (ppm)

IR (NaCl): 3443-3223,
2962-2894, 1740, 1724, 1465,
1451, 1337, 1256, 1070, 985 (c
m ^{- 1} )

Elemental analysis EA (C ₁₃ H ₂₀ O ₂ ) Calculated: C, 74.96, H, 9.68 Found: C, 74.19, H, 9.87

Calculated hydroxyl value: 538.7 mg KOH / g Actual value: 540.4 mg KOH / g

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AA02 AB46 AB48 AB51 AB92 AC11 FC34 FC36 FE11 GN21 GP02

Claims (2)

[Claims] 1. General formula (1): (Wherein, l and m each independently represent 0 or 1,
R ₁ represents an alkylene group having 2 to 6 carbon _{atoms, R} 2,
R ₃ and R ₄ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms.
6 represents an alkyl group. An alicyclic diol represented by the formula: 2. General formula (2): (In the formula, 1 represents 0 or 1, and R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) In the olefin part of the formula (3): (Wherein, R ₁ represents an alkylene group having 2 to 6 carbon atoms;
Represents 0 or 1. Reacting the compound represented by
General formula (1): (Wherein, l and m each independently represent 0 or 1,
R ₁ represents an alkylene group having 2 to 6 carbon _{atoms, R} 2,
R ₃ and R ₄ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms.
6 represents an alkyl group. )).