JPH05214086A - Cyclohexanedimethanol-based polyestercarbonate resin - Google Patents

Abstract

PURPOSE:To provide a polyestercarbonate resin which has cyclohexylene groups as the structural units, is thermoformable, and can impart new characteristics to other well-known resins when blended with these resins. CONSTITUTION:The title resin which structural units of formula I (wherein a group of formula II represents trans-cyclohexylene), structural units of formula III and/or formula IV if necessary, and a reduced viscosity (25 deg.C, 0.5g/dl) of 0.1-1.5.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester carbonate resin having a cyclohexylene group as a structural unit.

[0002]

2. Description of the Related Art Polycarbonate is a polymer having a carbonic acid ester structure in the main chain, and is usually a dihydric phenol such as 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) and phosgene. It is an excellent plastic that is manufactured by the reaction with various carbonic acid derivatives, has excellent impact resistance, has low hygroscopicity, and is stable to heat. In recent years, along with the development of applications of resins, there is a demand for polycarbonates that can improve the properties of resins by mixing with other known resins such as polypropylene,
Polycarbonates having novel structures and functions have been studied. For example, JP-A-1-172424 discloses 1,4
Although a polycarbonate composed of -cyclohexanediol or 4,4'-bicyclohexanediol is disclosed, physical properties and the like are not clear. Further, the applicant of the present invention proposed in Japanese Patent Application No. 2-72689 a polycarbonate consisting of only a trans-form cyclohexane ring, but it was infusible or melted with decomposition, so that thermoforming was impossible.

[0003]

In view of the above problems, an object of the present invention is to provide a novel carbonate resin having a cyclohexylene group in its structural unit. That is, it is to provide a polycarbonate that has thermoformability and can be mixed with other known resins to give new properties, and a method for producing the same.

[0004]

[Means for Solving the Problems]
The polyester carbonate resin of cyclohexanol was presented in -89337, which has a decomposition temperature of 300 ° C.
It is slightly inferior in heat resistance before and after. Therefore, after further study, bis terephthalate [(trans-
4-hydroxymethylcyclohexyl) methyl] polycarbonate was found, and the polyester carbonate resin of the present invention was completed.

The polyester carbonate resin of the present invention has the formula [1]

[Chemical 14] And a structural unit represented by the formula [2]

[Chemical 15] Or a structural unit represented by the formula [3]

[Chemical 16] The reduced viscosity including the structural unit represented by 0.1 to 1.5 (2
5 ° C., 0.5 g / dl).

The first polyester carbonate resin of the present invention is characterized by comprising repeating structural units represented by the above formula [1].

In the second polyester carbonate resin of the present invention, the structural unit represented by the above formula [1], the structural unit represented by the above formula [2], and the structural unit represented by the above formula [3] are irregular. It is characterized by being arranged in.

The third polyester carbonate resin of the present invention is characterized in that the structural unit represented by the above formula [1] and the structural unit represented by the above formula [2] are randomly arranged.

The fourth polyester carbonate resin of the present invention is characterized in that the structural unit represented by the above formula [1] and the structural unit represented by the above formula [3] are randomly arranged.

The method for producing the polyester carbonate resin of the present invention comprises bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate and 2,2-bis (4-hydroxyphenyl) -propane and / or 2,2- Bis (4-hydroxyphenyl) -1,
A diol component composed of 1,1,3,3,3-hexafluoropropane or bis [(trans-terephthalate
4-hydroxymethylcyclohexyl) methyl] diol component is reacted with trichloromethyl chloroformate, phosgene or a carbonic acid diaryl ester in the presence of an acid acceptor.

The method for producing the polyester carbonate resin of the present invention will be described for each of the first to fourth polyester carbonate resins of the present invention. The method for producing the first polyester carbonate of the present invention will be described below.
First, as shown in the following formula, terephthalic acid dichloride represented by the formula [6] and excess trans-formula represented by the formula [7]
Bis [(trans-4-hydroxymethylcyclohexyl) terephthalate represented by the formula [4] by reacting with 1,4-cyclohexanedimethanol in the presence of pyridine
Methyl] is obtained.

[0012]

[Chemical 17]

Subsequently, the obtained diol component represented by the formula [4] is reacted with trichloromethyl chloroformate represented by the formula [8] in the presence of pyridine in 1,2-dichloroethane as a solvent to obtain a compound represented by the formula: A polyester carbonate resin composed of repeating structural units represented by [1] is obtained.

[0014]

[Chemical 18]

Phosgene may be used in place of trichloromethyl chloroformate in the above production method. The reaction temperature is 20 to 100 ° C., and the reaction time is not particularly limited, but 1
~ 5 hours. The amounts of trichloromethyl chloroformate and phosgene used are equimolar or slightly excessive with respect to the total of the diol components.

It can also be produced by a method of reacting the above diol component and a carbonic acid diaryl ester at 200 to 300 ° C. for 4 to 10 hours in the presence of a transesterification catalyst such as a metal oxide.

Another method for producing the first polyester carbonate resin of the present invention will be described below. For example, as shown in the following formula, an excess of trans-1,4-
Cyclohexanedimethanol is reacted with trichloromethyl chloroformate represented by the formula [8] or phosgene to obtain bis [(trans-4-hydroxymethylcyclohexyl) methyl] carbonate represented by the formula [5].

[0018]

[Chemical 19] Then, a polyester carbonate resin composed of repeating structural units represented by the formula [1] is obtained by a polycondensation reaction represented by the following formula between the carbonate and terephthalic acid dichloride represented by the formula [6].

[0019]

[Chemical 20]

The method for producing the second polyester carbonate of the present invention will be described below. As shown by the following formula, bis [(trans-4-hydroxymethylcyclohexyl) methyl] [4] terephthalate, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A).

[9] and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (hereinafter abbreviated as bisphenol AF).
[10] is dissolved in a solvent such as dichloromethane together with an acid acceptor such as pyridine. It can be produced by reacting this solution with trichloromethyl chloroformate [8] or phosgene.

[0021]

[Chemical 21]

The reaction temperature is 20 to 100 ° C., and the reaction time is not particularly limited, but is preferably 1 to 5 hours. The amounts of trichloromethyl chloroformate and phosgene used are calculated according to the formula [4],
formula

It is equimolar to the total of the diol components represented by [9] and the formula [10], or slightly in excess. Further, in the presence of a transesterification catalyst such as a metal oxide, the above-mentioned diol component and carbonic acid diaryl ester are heated at 200 to 300 ° C for 4 to
It can also be produced by a method of reacting for 10 hours.

The third method for producing a polyester carbonate of the present invention will be described below. As shown by the following formula, bis [(trans-4-hydroxymethylcyclohexyl) methyl] [4] terephthalate and bisphenol A

[9] is dissolved in a solvent such as dichloromethane together with an acid acceptor such as pyridine. It can be produced by reacting this solution with trichloromethyl chloroformate [8] or phosgene.

[0024]

[Chemical formula 22]

The reaction temperature is 20 to 100 ° C., and the reaction time is not particularly limited, but is preferably 1 to 5 hours. The amounts of trichloromethyl chloroformate and phosgene used are calculated according to the formula [4] and the formula

It is equimolar to the total amount of the diol components represented by [9] or slightly in excess. It can also be produced by a method of reacting the above-mentioned diol component and carbonic acid diaryl ester at 200 to 300 ° C for 4 to 10 hours in the presence of a transesterification catalyst such as a metal oxide.

The fourth method for producing a polyester carbonate of the present invention will be described below. As shown in the following formula, bis [(trans-4-hydroxymethylcyclohexyl) methyl] [4] terephthalate and bisphenol AF
[10] is dissolved in a solvent such as dichloromethane together with an acid acceptor such as pyridine. It can be produced by reacting this solution with trichloromethyl chloroformate [8] or phosgene.

[0027]

[Chemical formula 23]

The reaction temperature is 20 to 100 ° C., and the reaction time is not particularly limited, but is preferably 1 to 5 hours. The amounts of trichloromethyl chloroformate and phosgene used are equimolar or slightly in excess to the total of the diol components represented by the formulas [4] and [10]. It can also be produced by a method of reacting the above-mentioned diol component and carbonic acid diaryl ester at 200 to 300 ° C for 4 to 10 hours in the presence of a transesterification catalyst such as a metal oxide.

In the production method of the present invention, a molecular weight modifier may be added in an amount of 1 to 10 mol% based on the diol component, if necessary. Monohydric phenol as a molecular weight regulator,
For example, phenol, p-tert-butylphenol, p-cumylphenol and the like can be mentioned.
Examples of the solvent include halogenated hydrocarbons such as dichloromethane and chlorobenzene, aromatic hydrocarbons such as benzene and toluene, and ether-based tetrahydrofuran and dioxane.

As the acid acceptor other than pyridine in the production method of the present invention, specifically, triethylamine, 1,8-
Tertiary amines such as diazabicyclo [5,4,0] -7-undecene, inorganic bases such as sodium hydroxide, phosgene dimer as a carbonic acid derivative such as phosgene, and diphenyl carbonate as a carbonic acid diaryl ester. it can.

When the proportion of bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate in the diol component is 5 mol% or less, the properties of the polycarbonate resin having a cyclohexylene group are difficult to appear. Regarding the molar ratio of the structural units in the molecule, the yield when changing the diol component ratio is 90 to 99%, and since the reaction is considered to proceed quantitatively, it corresponds to the molar ratio of each diol component. It can be considered that the molar ratio of each structural unit is the same.

The polyester carbonate resin of the present invention has a reduced viscosity of 0.1 to 1.50 (25 ° C., 0.5 g / dl).
Chloroform), melting point 200-300 ° C, decomposition temperature 33
It has a physical property value of 0 ° C or higher.

The polyester carbonate of the present invention can be incorporated into other known resins such as polyethylene, polypropylene,
By mixing with polymethylmethacrylate, ABS, polyamides, polyacrylates, polycarbonates, polyesters such as polyethylene terephthalate, or polyphenylene oxides, etc., the mechanical strength and thermoformability of these resins can be improved and new properties can be obtained. Can also be added.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

EXAMPLES The physical properties of the polyester carbonate resins obtained in the examples were measured by the following methods. Reduced viscosity: Chloroform as a solvent at 25 ° C, 0.5 g
It was measured at a concentration of / dl. The reduced viscosity (η _r ) is defined by the following formula 1.

[Equation 1] (Here, η is a Ubbelohde viscometer and the concentration in chloroform is 0.5 g / dl.
Η _o is a value measured using the Ubbelohde viscometer at the same temperature in the same solvent, and C is a concentration of 0.5 g / dl. )

Melting point (Tm): A polarizing microscope equipped with a hot stage (FP-82 manufactured by METTLER CORPORATION) was measured at a temperature rising temperature of 3 ° C. per minute. Decomposition temperature (Td): TG / DTA manufactured by Seiko Instruments Inc.
The temperature was measured at a temperature rise temperature of 10 ° C./min and a weight loss of 5%. Glass transition temperature (Tg): DSC manufactured by Seiko Instruments Inc.
It was measured at a temperature rising temperature of 5 ° C./min using a -200 type. In addition, the yield was calculated by dividing the yield of the polyester carbonate resin by the theoretical yield obtained based on the diol component.

Example 1 Production of First Polyester Carbonate Resin (Polyester Carbonate Consisting of Repeating Structural Units of the Formula [1]): 1) Bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate, Production of (formula [4]). In a 500 ml three-necked flask equipped with a condenser and a stirrer, trans-1,4-cyclohexanedimethanol 41.1 was added.
g (0.29 mol), pyridine (30 ml) and tetrahydrofuran (THF) (200 ml) were added and the mixture was stirred under reflux. 19.5 g (0.10 mol) of terephthalic acid dichloride
) Was dissolved in 100 ml of THF, the solution was added dropwise over 90 minutes, and the reaction was carried out for 4 hours. After the reaction was completed, this reaction solution was filtered. Then, the filtrate was concentrated under reduced pressure, the obtained residue was dissolved in 1 liter of ethyl acetate, and washed with 3N hydrochloric acid three times, 1N sodium hydroxide three times, and further water. The obtained ethyl acetate layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the remaining crystals were recrystallized from methanol to give bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate 13]. 0.1 g (yield 32.6)
%) Was obtained. The melting point was 150.3-152.0 ° C. It was confirmed by IR and NMR that this compound had the structure of formula [4].

2) Polycondensation reaction Bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate was placed in a 100 ml three-necked flask.
1.25 g (3.0 mmol), 1 ml of pyridine and 1,2
-Add 5 ml of dichloroethane (hereinafter referred to as DCE) and stir. Then, this solution is heated to 90 ° C with a mantle heater.
Kept at reflux and under reflux, trichloromethyl chloroformate 0.33
20 g of a solution of g (1.7 mmol) in 2 ml of DCE
The mixture was added dropwise over a period of 3 minutes, and the reaction was performed for 3 hours as it was. The obtained reaction solution was allowed to cool and then poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtrate was washed in methanol and then dried to obtain 0.97 g (yield 72.9%) of polyester carbonate resin. This resin is I
It was confirmed by the R spectrum that it had the structural unit of the formula [1]. This polyester carbonate resin has a reduced viscosity of 0.63, a decomposition temperature of 344.6 ° C., and a melting point of 188.9-1.
It was 99.7 ° C and the glass transition temperature was 124.0 ° C. A chloroform solution of this resin was cast on a glass plate and dried to obtain a transparent polyester carbonate resin film. Further, a good film was obtained even when the resin was placed on a glass plate, heated to 200 ° C., melted and then cooled.

Example 2 Preparation of Second Polyester Carbonate Resin (Polyester Carbonate Consisting of Structural Units Shown by Formula [1], Formula [2] and Formula [3]): Terephthalic Acid in 100 ml Three-necked Flask Bis [(trans-4-hydroxymethylcyclohexyl) methyl] 0.63 g (1.5
mmol), bisphenol-A 0.17 g (0.75 mm
ol), bisphenol-AF 0.25g (0.75mm
ol), 1 ml of pyridine and 5 ml of 1,2-dichloroethane (hereinafter referred to as DCE) were added and stirred. Then,
This solution was kept at 90 ° C. with a mantle heater, and 0.33 g (1.7 mmol) of trichloromethyl chloroformate was added as a solution with 2 ml of DCE. The solution was added dropwise under heating under reflux for 20 minutes and the reaction was continued for 3 hours. .. The obtained reaction solution was allowed to cool and then poured into 300 ml of methanol, and the deposited precipitate was filtered. Washing the filtrate in hot methanol,
Then, it was dried to obtain 1.08 g (yield 95.3%) of a polyester carbonate resin. The structure of this polymer was confirmed by IR spectrum. This polyester carbonate resin has a reduced viscosity of 1.07 and a decomposition temperature of 353.
It had a melting point of 154.1 to 182.6 ° C and a glass transition temperature of 123.4 ° C. Further, a chloroform solution of this polymer was cast on a glass plate and dried to obtain a transparent polyester carbonate film. Also, place the polymer on a glass plate and heat to 200 ° C,
A good film was obtained even after cooling after melting.

Examples 3-4 Preparation of Second Polyester Carbonate Resin: Performed except that the component ratios of bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate, bisphenol-A, and bisphenol-AF were changed. Performed in accordance with Example 2. Table 1 shows the component ratios and the physical properties of the obtained polyester carbonate resin.

Example 5 Production of Third Polyester Carbonate Resin (Polyester Carbonate Comprising Structural Units Shown by Formula [1] and Formula [2]): Bisterephthalate [(trans-4 -Hydroxymethylcyclohexyl) methyl] 0.63 g (1.5 mmol), bisphenol-A 0.34 g (1.5 mmol), pyridine 1
ml and DCE (5 ml) were added and stirred. Then, this solution was kept at 90 ° C. with a mantle heater, and 0.33 g (1.7 mmol) of trichloromethyl chloroformate was heated under reflux.
Was made into a solution with 2 ml of DCE and added dropwise over 20 minutes, and the reaction was continued for 3 hours. The obtained reaction solution was allowed to cool and then poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtered product was washed with hot methanol and then dried to obtain 1.05 g (yield 99.3%) of a polyester carbonate resin. The physical properties of the resin thus obtained are shown in Table 1. The structure of this polymer was confirmed by IR spectrum.

Example 6 Preparation of Third Polyester Carbonate Resin: According to Example 5 except that the component ratios of bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate and bisphenol-A were changed. went. Table 1 shows the component ratios and the physical properties of the obtained polyester carbonate resin.

Example 7 Preparation of Fourth Polyester Carbonate Resin (Polyester Carbonate Consisting of Structural Units Shown in Formulas [1] and [3]): Bisterephthalate [(trans-4 -Hydroxymethylcyclohexyl) methyl] 0.63 g (1.5 mmol), bisphenol-AF 0.50 g (1.5 mmol), pyridine 1 ml, and DCE 5 ml were added and stirred. Then,
This solution was kept at 90 ° C with a mantle heater and heated under reflux to give 0.33 g of trichloromethyl chloroformate (1.7 mmo).
l) was made into a solution with 2 ml of DCE and added dropwise over 20 minutes, and the reaction was continued for 3 hours. The obtained reaction solution was allowed to cool and then poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtered product was washed with hot methanol and then dried to obtain 1.21 g (yield 94.0%) of a polyester carbonate resin. The physical properties of the obtained resin are shown in Table 1.
Shown in. The structure of this polymer was confirmed by IR spectrum.

Example 8 Preparation of Fourth Polyester Carbonate Resin: According to Example 7 except that the component ratios of bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate and bisphenol-AF were changed. went. Table 1 shows the component ratios and the physical properties of the obtained polyester carbonate resin.

[0044]

[Table 1]

[0045]

According to the present invention, a novel polyester carbonate resin having a cyclohexylene group can be provided. The cyclohexanedimethanol polyester carbonate resin of the present invention melts at 200 to 220 ° C. and is excellent in thermoformability. Therefore, a highly transparent film can be formed by thermoforming. Thus, the cyclohexanedimethanol polyester carbonate resin of the present invention is useful by itself but other known resins such as polyethylene, polypropylene, polymethylmethacrylate, ABS polyamides, polyacrylates, polycarbonates, polyethylene. By mixing with polyesters such as terephthalate or polyphenylene oxides, it is possible to improve the mechanical strength and thermoformability of these resins and add new properties.

Claims (10)

[Claims] 1. A formula [1]: And a structural unit represented by the formula [2] And / or a structural unit represented by the formula [3] The reduced viscosity including the structural unit represented by 0.1 to 1.5 (2
Polyester carbonate resin of cyclohexanedimethanol at 5 ° C, 0.5 g / dl). 2. A formula [1]: The reduced viscosity consisting of repeating structural units represented by
-1.5 (25 ° C, 0.5 g / dl) cyclohexanedimethanol polyester carbonate resin. 3. A formula [4]: The polyester carbonate resin of cyclohexanedimethanol according to claim 2, which is obtained by the reaction of bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate represented by ## STR1 ## with phosgene, trichloromethyl chloroformate or diaryl carbonate. 4. A formula [5]: The polyester carbonate resin of cyclohexanedimethanol according to claim 2, which is obtained by the reaction of bis [(trans-4-hydroxymethylcyclohexyl) methyl] carbonate represented by the following formula with terephthalic acid dichloride. 5. A formula [1]: A structural unit represented by the formula [2]: And a structural unit represented by the formula [3] Reduced viscosity in which the structural units shown by are randomly arranged 0.1
Polyester carbonate resin of cyclohexanedimethanol of ~ 1.5 (25 ° C, 0.5 g / dl chloroform). 6. A formula [1]: And a structural unit represented by the formula [2] Reduced viscosity in which the structural units shown by are randomly arranged 0.1
Polyester carbonate resin of cyclohexanedimethanol of ~ 1.5 (25 ° C, 0.5 g / dl chloroform). 7. A formula [1]: And a structural unit represented by the formula [3] Reduced viscosity in which the structural units shown by are randomly arranged 0.1
Polyester carbonate resin of cyclohexanedimethanol of ~ 1.5 (25 ° C, 0.5 g / dl chloroform). 8. The ratio of the structural unit represented by the formula [1] is 5
The polyester carbonate resin of cyclohexanedimethanol according to claim 2, 3, 4, 5, 6, or 7, which is ˜95 mol%. 9. Bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate and 2,2
-Bis (4-hydroxyphenyl) -propane and /
Or 2,2-bis (4-hydroxyphenyl)-
A diol component composed of 1,1,1,3,3,3-hexafluoropropane or a diol component composed of bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate was added to chloroformic acid in the presence of an acid acceptor. A reduced viscosity of 0.1, characterized by reacting with trichloromethyl, phosgene, or carbonic acid diaryl ester.
A method for producing a polyester carbonate of cyclohexanedimethanol which is about 1.5 (25 ° C, 0.5 g / dl chloroform). 10. The polyester carbonate of cyclohexanedimethanol according to claim 9, wherein the proportion of bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate in the diol component is 5 mol% or more. Resin manufacturing method.