JPH05320327A - New polyester carbonate resin - Google Patents

Abstract

PURPOSE:To obtain a polyester carbonate resin which can be molded into a tough film capable of being readily thermal-formed and having excellent transparency, comprising a specific repeating unit containing a cyclohexylene group. CONSTITUTION:A polyester carbonate resin comprises irregular repetitions of a structural unit of formula I (group of formula II is trans-cyclohexylene and a structural unit of formula III and has 0.10-3.0 reduced viscosity (25 deg.C, 0.5g/dl in chloroform). 5-95mol structural unit of formula I is blended with 95-5mol% structural unit of formula III. Bis[(trans-4-hydroxymethylcyclohexyl) methyl] 4,4-biphenyldicarboxylate of formula IV and bis[(trans-4- hydroxymethylcyclohexyl)methyl] terephthalate of formula V are used as diol components and reacted with phosgene, trichloromethyl formate or carbonic acid diaryl ester to give the objective resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyester carbonate resin.

[0002]

2. Description of the Related Art Polycarbonate is a polymer having a carbonic acid ester structure in its main chain and is usually a dihydric phenol such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A). It is an excellent plastic that is produced by the reaction of a carbonic acid derivative such as phosgene with excellent impact resistance, low hygroscopicity, and stable to heat.

In recent years, along with the development of applications of resins, polycarbonates having novel structures and functions have been studied. For example, JP-A-1-172424 discloses a polycarbonate produced by reacting 1,4-cyclohexanediol or 4,4′-bicyclohexanediol with a carbonic acid derivative, but physical properties and the like are not clear. Further, the present applicant has proposed in JP-A-3-273025 a polycarbonate having 1,4-cyclohexanediol and / or 4,4′-bicyclohexanediol and having a cyclohexane ring in an all-trans form.
Thermoforming was impossible because it melted while being infusible or decomposed.

Further, since the conventional polycarbonate resin has an aromatic ring with large anisotropy in its main chain, it is difficult to reduce the birefringence which is an important property of the optical recording substrate. To solve this problem, Applicants have found that 2,2-bis (4-hydroxyphenyl)-
Carbonate derivatives of 1,1,1,3,3,3-hexafluoropropane (hereinafter abbreviated as bisphenol-AF), trans, trans-4,4′-bicyclohexanediol and trans-1,4-cyclohexanediol The fluorine-containing polycarbonate produced by reacting with is disclosed in JP-A-3-259920 or JP-A-3-275717, but all of them have a problem in heat resistance because they decompose at around 280 ° C. Further, this resin has liquid crystallinity, and generally, those exhibiting liquid crystallinity are not suitable as optical resin materials because of large birefringence.

[0005]

In view of the above problems, an object of the present invention is to have a cyclohexylene group in a structural unit,
It is an object of the present invention to provide a novel polyester carbonate resin which is easily thermoformed and has excellent transparency. In addition, other known resins such as polyethylene, polypropylene, polymethylmethacrylate, ABS, polyamides, polyacrylates, polycarbonates, polyesters such as polyethylene terephthalate, or polyphenylene oxides are mixed and mechanically mixed with these resins. It is to improve the strength and thermoformability and add new properties.

[0006]

[Means for Solving the Problems]
-89337 or Japanese Patent Application No. 3-242490 invented a polyestercarbonate resin of cyclohexanol, but the resin required for optical discs has a melting point of 100-
220 ° C, while the melting point is 200-
Since it was as high as 300 ° C, the physical properties were not satisfactory. Therefore, after further study, 4,4′-biphenyldicarboxylic acid bis [(trans-4-hydroxymethylcyclohexyl) methyl] and terephthalic acid bis [(trans-4-hydroxymethylcyclohexyl))
The present inventors have found that a polyester carbonate resin produced by reacting methyl] with a carbonic acid derivative is more excellent in thermoformability and transparency, and completed the present invention.

The polyester carbonate resin of the present invention is as shown in the following 1-2. 1. Formula [1]

[Chemical 8] And a structural unit [2]

[Chemical 9] A polyester carbonate resin comprising an irregular repeating structural unit represented by the formula and having a reduced viscosity of 0.10 to 3.0 (25 ° C., 0.5 g / dl chloroform). 2. The polyester carbonate resin according to 1, wherein the structural unit represented by the formula [1] is 5 to 95 mol%, and the structural unit represented by the formula [2] is 95 to 5 mol%.

The polyester carbonate resin of the present invention has a reduced viscosity of 0.10 to 3.0 (25 ° C., 0.5 g /
dl chloroform), melting point 130-220 ° C., decomposition temperature 340 ° C. or higher.

In the method for producing the polyester carbonate resin of the present invention, first, bis [(trans-4-hydroxymethylcyclohexyl) methyl] 4,4'-biphenyldicarboxylic acid represented by the formula [3] is represented by the following formula. To
It is produced by reacting 4,4'-biphenyldicarboxylic acid dichloride with excess trans-1,4-cyclohexanedimethanol in the presence of pyridine.

[Chemical 10]

Further, bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate represented by the formula [4] is represented by the following formula: terephthalic acid dichloride and excess trans-1,4-cyclohexanedimethanol. Is prepared by reacting in the presence of pyridine.

[Chemical 11]

Subsequently, this was added to the compound of formula [8] in 1,2-dichloroethane as a solvent in the presence of an acid acceptor such as pyridine.

[Chemical formula 12] It can be produced by reacting with trichloromethyl chloroformate represented by.

[Chemical 13] In the above production method, phosgene may be used as the carbonic acid derivative instead of trichloromethyl chloroformate. Reaction temperature is 20 ~
The reaction time at 100 ° C. is not particularly limited, but is 1 to 5 hours. The amounts of trichloromethyl chloroformate and phosgene used are equimolar or slightly excessive with respect to the total of the diol components. Further, in the presence of a transesterification catalyst such as a metal oxide, the above-mentioned diol and carbonic acid diaryl ester are mixed with each other.
It can also be produced by a method of reacting at 0 to 300 ° C. for 4 to 10 hours.

In these methods, the molecular weight modifier may be added in an amount of 1 to 10 mol% based on the diol, if necessary. The molecular weight regulator may be a monohydric phenol such as phenol, p-tert-butylphenol, p
-Cumylphenol etc. can be mentioned. Examples of the solvent include halogenated hydrocarbons such as dichloromethane and chlorobenzene, aromatic hydrocarbons such as benzene and toluene, as well as ether-based tetrahydrofuran and dioxane. Specific examples of acid acceptors other than pyridine include tertiary amines such as triethylamine and 1,8-diazabicyclo [5,4,0] -7-undecene, inorganic bases such as sodium hydroxide, and carbonic acid diaryl esters. Examples thereof include diphenyl carbonate and the like.

The molar ratio of the structural units represented by the formulas [1] and [2] in the polycarbonate molecule is 5 to 9 in the formula [1].
5 mol% and the formula [2] is preferably 95 to 5 mol%, and in other ranges, the thermoformability is slightly inferior. The molar ratio of the structural units [1] and [2] in the polyester carbonate molecule is 89 to 9 when the diol component is changed.
Since it is 8% and the yield does not change greatly, the molar ratio of each diol component [3] [4] and the corresponding structural unit [1]
It can be considered that the molar ratios of [2] are the same.

The polyester carbonate resin of the present invention can also be manufactured by the following method. That is, excess trans-1,4-cyclohexanedimethanol
Then, trichloromethyl chloroformate or phosgene is reacted to produce bis [(trans-4-hydroxymethylcyclohexyl) methyl] carbonate represented by the formula [5]. Next, the obtained bis [(trans-4-
Hydroxymethylcyclohexyl) methyl] carbonate is subjected to polycondensation reaction with 4,4′-biphenyldicarboxylic acid dichloride represented by the formula [6] and terephthalic acid dichloride represented by the formula [7]. If this is shown by the formula,

[Chemical 14] Becomes Here, the amount of bis [(trans-4-hydroxymethylcyclohexyl) methyl] carbonate used is equimolar to the total amount of the dichloride components [6] [7]. Structural unit in polyester carbonate molecule [1]
The molar ratio of [2] is determined by the molar ratio of dichloride components [6] and [7].

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

[0016]

EXAMPLES The physical properties of the polyester carbonate resins obtained in the examples were measured by the following methods. Reduced viscosity: Chloroform as solvent at 25 ° C, 0.5
It was measured at a concentration of g / dl. Melting point (Tm): A hot stage (FP-82, manufactured by METTLER CORPORATION) was attached to a polarizing microscope and measured at a temperature rising temperature of 3 ° C. per minute. Decomposition temperature (Td): TG / DT manufactured by Seiko Instruments Inc.
A-220 type was used and the temperature was raised at 10 ° C./min to measure the temperature at which the weight loss was 5%. Glass transition temperature (Tg): DS manufactured by Seiko Instruments Inc.
It measured using the C-200 type | mold at the temperature rising temperature of 5 degreeC / min. Transparency: The coloring degree and transparency of the obtained polyester carbonate resin in a film form were visually evaluated. 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 Polyester Carbonate Consisting of Structural Units Shown in Formulas [1] and [2]: 1) 4,4′-Biphenyldicarboxylic acid bis [(trans-4-hydroxymethylcyclohexyl) methyl] , Manufacture of formula [3]. In a 300 ml round-bottomed flask equipped with a condenser, 4,4'-biphenyldicarboxylic acid 23.
3 g (0.1 mol), 120 ml of thionyl chloride and 1 ml of pyridine were added and reacted at 80 ° C. for 12 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure, and crude crystals obtained were recrystallized from n-heptane to obtain 4,4′-biphenyldicarboxylic acid dichloride 18.1 g. Subsequently, trans-1,4-cyclohexanedimethanol 7.4 g (0.05 mol), pyridine 6 ml, and tetrahydrofuran (hereinafter abbreviated as THF) 100 ml were placed in a 300 ml three-necked flask equipped with a condenser and a stirrer. The mixture was stirred under heating under reflux. 4,4'-biphenyldicarboxylic acid dichloride 4.8 g (0.017 m)
solution) in THF (50 ml) was added dropwise over 60 minutes, and the reaction was carried out for 5 hours while heating under reflux. After completion of the reaction, this reaction solution was filtered, and then the filtrate was concentrated under reduced pressure. The obtained residue was dissolved in 1 liter of ethyl acetate, washed with 3N hydrochloric acid three times, 1N sodium hydroxide three times, and further washed with water. The obtained ethyl acetate layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, the solvent was distilled off under reduced pressure, and the remaining crude crystals were recrystallized from methanol to give 4,4′-biphenyldicarboxylic acid. Screw [(trans-
4-hydroxymethylcyclohexyl) methyl] 3.1
g (yield 36.9%) was obtained. Melting point 172.6-1
It was 74.3 ° C. The structure of this compound is IR and NM.
Confirmed with R.

2) Bis terephthalate [(trans-4
-Hydroxymethylcyclohexyl) methyl], production of formula [4]. In a 500 ml three-necked flask equipped with a condenser and a stirrer, trans-1,4-cyclohexanedimethanol 41.4 g (0.29 mol) and pyridine 3
0 ml and 200 ml of THF were added, and the mixture was stirred with heating under reflux. To this, 19.5 g of terephthalic acid dichloride (0.
A solution of 10 mol) in 100 ml of THF
It was added dropwise at 0 minutes, and the reaction was carried out as it was under reflux with heating for 4 hours. After completion of the reaction, this reaction solution was filtered, and then the filtrate was concentrated under reduced pressure. The obtained residue was dissolved in 1 liter of ethyl acetate, and 3 times with 3N hydrochloric acid, 3 times with 1N sodium hydroxide,
Further washed with water. The obtained ethyl acetate layer was dried over anhydrous sodium sulfate, the desiccant was filtered off, the solvent was distilled off under reduced pressure, and the remaining crude crystals were recrystallized with methanol to give bis [(trans-4) terephthalate]. -Hydroxymethylcyclohexyl) methyl] (13.1 g, yield 32.6%) was obtained. Melting point is 150.3-152.0 ° C
Met. The structure of this compound was confirmed by IR and NMR.

3) Polycondensation reaction. In a 100 ml three-necked flask equipped with a condenser and a stirrer, 0.15 g (0.3 mmo) of bis [(trans-4-hydroxymethylcyclohexyl) methyl] 4,4'-biphenyldicarboxylate was prepared.
l), 1.13 g (2.7 m) of bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate
mol), 1 ml of pyridine and 5 ml of 1,2-dichloroethane (hereinafter referred to as DCE) were added and stirred. This liquid is heated with a mantle heater and kept at 90 ° C.
0.33 g of trichloromethyl chloroformate with heating under reflux
2 ml of a solution of (1.7 mmol) in 2 ml of DCE
The mixture was added dropwise over 0 minutes, and the reaction was carried out as it was under reflux with heating for 3 hours. After cooling the obtained reaction liquid, 300 ml of methanol
And the deposited precipitate was filtered. The filtered material was washed with hot methanol and then dried to obtain 1.46 g (yield 92.2%) of a polyester carbonate resin. The structure of this polymer was confirmed by IR spectrum. This polyester carbonate resin has a reduced viscosity of 0.60, a decomposition temperature of 355.7 ° C. and a melting point of 174.1-
It was 184.0 ° C and the glass transition temperature was 119.9 ° C.
When a chloroform solution of this polyester carbonate resin was cast on a glass plate and dried,
A polyester carbonate resin film having good transparency was obtained. Also, place the polymer on the glass plate for about 2
A good film was obtained by heating to 00 ° C, melting and then cooling.

Examples 2 to 5 4,4'-biphenyldicarboxylic acid bis [(trans-
4-hydroxymethylcyclohexyl) methyl] and bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate, except that the component ratio is changed.
It carried out according to Example 1. Table 1 shows the component ratios and the physical properties of the obtained polyester carbonate.

[0021]

[Table 1]

[0022]

According to the present invention, a novel polyester carbonate resin having a cyclohexylene group can be provided. The polyester carbonate resin of the present invention melts at about 220 ° C. and has excellent thermoformability. Further, it does not decompose up to 340 ° C or higher and can be used at high temperature. Furthermore, a tough film having excellent transparency can be formed by thermoforming. Thus, the polyester carbonate resins of the present invention are useful by themselves, but other known resins such as polyethylene, polypropylene, polymethylmethacrylate, ABS, polyamides, polyacrylates, polycarbonates, polyethylene terephthalate. It is also possible to add new properties while improving the mechanical strength and thermoformability of these resins by mixing with such polyesters or polyphenylene oxides.

Claims (4)

[Claims] 1. A formula [1]: And a structural unit represented by the formula [2] A polyester carbonate resin comprising an irregular repeating structural unit represented by the formula and having a reduced viscosity of 0.10 to 3.0 (25 ° C., 0.5 g / dl chloroform). 2. The structural unit represented by the formula [1] is 5 to 95.
The polyester carbonate resin according to claim 1, wherein the structural unit represented by the formula [2] is 95 to 5 mol% in mol%. 3. A diol component represented by the formula [3]: 4,4'-biphenyldicarboxylic acid bis [(trans-4-hydroxymethylcyclohexyl) represented by
Methyl] and the formula [4] Bis [(trans-4-hydroxymethylcyclohexyl) methyl] terephthalate represented by phosgene, trichloromethyl chloroformate or diaryl carbonate
3. The method for producing a polyester carbonate resin according to claim 1, wherein the polyester carbonate resin is reacted with a ruester. 4. A formula [5]: And bis [(trans-4-hydroxymethylcyclohexyl) methyl] carbonate represented by the formula [6] 4,4'-biphenyldicarboxylic acid dichloride represented by the formula and a compound of the formula [7] The method for producing a polyester carbonate resin according to claim 1 or 2, characterized in that a polycondensation reaction of terephthalic acid dichloride represented by