JP3139092B2 - Bisphenol fluorene polycarbonate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycarbonate resin containing bisphenolfluorene as a main raw material.

[0002]

2. Description of the Related Art Polycarbonate resin is a synthetic resin widely used industrially, and is usually a divalent resin represented by 2,2-bis (4'-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A). It is produced by reacting a diol component such as phenol with a carbonic acid derivative such as phosgene.

[0003] Polycarbonate resins produced from bisphenol A have excellent properties such as excellent impact resistance, low hygroscopicity, and stability to heat. Accordingly, expectations for the development of a polycarbonate resin having a structure which has not existed in the past and having new characteristics are increasing.

On the other hand, as a polycarbonate resin having a cyclohexane ring, JP-A-1-172424 discloses a polycarbonate resin comprising a mixture of a cis / trans form of the cyclohexane ring, but its physical properties are not clear. The applicant of the present invention has proposed a polycarbonate resin having a cyclohexane ring having an all-trans form, as disclosed in Japanese Patent Application No. 2-726.
However, thermoforming was impossible because it was infused or melted with decomposition.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polycarbonate resin having a structural unit which has not existed conventionally, and a polycarbonate resin having a cyclohexane ring, which has heretofore been a problem in workability. Is to improve the moldability of the resin.

[0006]

The present inventors have made various studies to solve the above-mentioned problems, and as a result, as diol components, bisphenolfluorene, trans, trans-4-4'-bicyclohexanediol and By using trans-1,4-cyclohexanediol, novel polycarbonate resins including those which can be thermoformed having a melting point of 220 to 300 ° C. have been completed. That is,
The polycarbonate resin of bisphenolfluorene of the present invention is as follows.

[0007] 1. A polycarbonate resin of bisphenolfluorene comprising a structural unit represented by the formula [1], a structural unit represented by the formula [2], and a structural unit represented by the formula [3].

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Embedded image (In the formulas [2] and [3], the formula [4] represents transcyclohexylene.)

A polycarbonate resin of bisphenolfluorene comprising the structural unit represented by the formula [1] described in the above item 1 and the structural unit represented by the formula [2] in the above item 1.

A polycarbonate resin of bisphenolfluorene comprising the structural unit represented by the formula [1] described in the above item 1 and the structural unit represented by the formula [3] described in the above item 1.

[0010] 4. Bisphenolfluorene of the formula [5] as a diol component for forming the structural unit of the formula [1], and trans, trans of the formula [6] as a diol component for forming the structural unit of the formula [2] -4,4'-bicyclohexanediol, formula [3]
The polycarbonate resin of bisphenol fluorene according to 1 to 3, which is obtained by using trans-1,4-cyclohexanediol of the formula [7] as a diol component for forming a structural unit represented by the following formula:

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Embedded image (In the formulas [6] and [7], the formula [4] represents transcyclohexylene.)

5. The polycarbonate resin of bisphenol fluorene according to 1 to 4, wherein the proportion of the structural unit represented by the formula [1] is 20 to 95 mol%.

The process for producing the polycarbonate resin of the present invention comprises forming a bisphenol fluorene represented by the formula [5] and a structural unit represented by the formula [2] as a diol component for forming the structural unit represented by the formula [1]. Trans, trans-4,4′-bicyclohexanediol represented by the formula [6],
The trans-1,4-cyclohexanediol represented by the formula [7] is used as a diol component for forming the structural unit represented by the formula [7], and these diol components are appropriately mixed in the presence of an acid acceptor such as pyridine [ 8]

Embedded image Is to react with trichloromethyl chloroformate represented by In the above production method, phosgene may be used instead of trichloromethyl formate. Reaction temperature is 20 ~
The reaction time at 100 ° C. is not particularly limited, but is preferably 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.

The diol and the diaryl carbonate may be reacted at 200 to 300 ° C. for 4 to 10 hours in the presence of a transesterification catalyst such as a metal oxide. In the above production method, the molecular weight modifier can be added as needed at 1 to 10 mol% based on the diol. Monohydric phenols such as phenol, P-tertiary butyl phenol,
P-cumylphenol and the like can be mentioned. Examples of the acid acceptor include pyridine, triethylamine and sodium hydroxide, examples of the carbonic acid derivative include phosgene and trichloromethyl chloroformate, and examples of the diaryl carbonate include diphenyl carbonate.

When the diol component ratio of bisphenol fluorene is less than 20 mol%, the characteristics of bisphenol fluorene do not appear clearly, and when it is more than 95 mol%, the characteristics of the polycarbonate resin having a cyclohexane ring do not appear clearly. Is good.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. First, methods for measuring the physical properties of the polycarbonate resin obtained in the examples will be described. Reduced viscosity: 0.5 ° C., 25 ° C. using chloroform as a solvent
/ Dl. Melting point: Hot stage (Mettler FP)
-82) The temperature was measured at a temperature rise of 3 ° C./minute after mounting. Decomposition temperature: Measured at a temperature rise rate of 10 ° C. per minute using a TG / DA-220 model manufactured by Seiko Denshi Kogyo KK, and measured at a temperature of 5% weight loss. Glass transition temperature: DSC-200 manufactured by Seiko Instruments Inc.
The measurement was performed at a rate of 5 ° C./min using a mold. Further, the yield was calculated by dividing the yield of the polycarbonate resin by the theoretical yield obtained based on the diol component.

Example 1 A method for producing a polycarbonate resin comprising a structural unit represented by the formula [1], a structural unit represented by the formula [2] and a structural unit represented by the formula [3]: bisphenolfluorene in a 100 ml three-necked flask 0.84 g (2.40 mm
ol), trans, trans-4-4'-bicyclohexanediol 0.06 g (0.30 mmol), trans-1,4-cyclohexanediol 0.03 g (0.
30 mmol), 1 ml of pyridine and 5 ml of 1,2-dichloroethane (hereinafter referred to as DCE) were stirred. Next, this liquid was kept at 90 ° C. with a mantle heater, and 0.33 g of trichloromethyl chloroformate was added thereto.
A solution of (1.7 mmol) dissolved in 2 ml of DCE was added dropwise over 20 minutes under reflux, and the reaction was carried out for 3 hours.
The resulting reaction solution was allowed to cool, then poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtrate was washed in hot methanol and then dried to give 0.98 g (yield 9
2.5%) of a polycarbonate resin. This polycarbonate resin has a reduced viscosity of 0.38 and a decomposition temperature of 3
00.3 ° C, melting point 271.9-280.3 ° C.
When a chloroform solution of the polycarbonate resin was cast on a glass plate and dried, a transparent film was obtained.

Examples 2 to 4 Bisphenol fluorene, trans, trans-4-
4'-bicyclohexanediol and trans-1,
Except for changing the component ratio of 4-cyclohexanediol,
Performed according to Example 1. Table 1 shows the physical property values of the obtained polycarbonate resin.

Example 5 Preparation of a polycarbonate resin comprising a structural unit represented by the formula [1] and a structural unit represented by the formula [2]: 0.95 g of bisphenolfluorene (2. 70 mmol), trans, trans-4-4'-bicyclohexanediol 0.06 g (0.30 mmol), pyridine 1 ml and DCE 5 ml were added and stirred. Next, this solution was maintained at 90 ° C. with a mantle heater, and 0.33 g (1.7 mmol) of trichloromethyl chloroformate was added thereto with DCE2.
The solution dissolved in ml was added dropwise over 20 minutes under reflux, and the reaction was allowed to proceed for 3 hours. The resulting reaction solution was allowed to cool, then poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtrate was washed in hot methanol and then dried to obtain 1.05 g (yield 96.5%) of a polycarbonate resin. The physical properties are shown in Table 1.

Examples 6 and 7 The procedure of Example 5 was repeated except that the component ratios of bisphenolfluorene and trans, trans-4-4'bicyclohexanediol were changed. Table 1 shows the physical property values of the obtained polycarbonate resin.

Example 8 A method for producing a polycarbonate resin comprising the structural unit represented by the formula [1] and the structural unit represented by the formula [3]: 100
Bisphenol fluorene 0.1 ml in a 3-ml three-necked flask.
95 g (2.70 mmol), trans-1,4-cyclohexanediol 0.03 g (0.30 mmol),
1 ml of pyridine and 5 ml of DCE were added and stirred.
Next, this solution was maintained at 90 ° C. with a mantle heater, and 0.33 g (1.7 m 3) of trichloromethyl chloroformate was added thereto.
(mol) in 2 ml of DCE was added dropwise over 20 minutes under reflux, and the reaction was carried out for 3 hours. The resulting reaction solution was allowed to cool, then poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtrate was washed in hot methanol and then dried to obtain 0.99 g (yield 94.3%) of a polycarbonate resin. The physical properties are shown in Table 1.

Examples 9 to 10 Bisphenol fluorene and trans-1,4-
The procedure was performed in the same manner as in Example 8 except that the component ratio of cyclohexanediol was changed. Table 1 shows the physical property values of the obtained polycarbonate resin.

Comparative Example 1 Preparation of a polycarbonate resin comprising a structural unit represented by the formula [2] and a structural unit represented by the formula [3]: 100
Trans, Trans-4-4 'in a 3-ml three-necked flask
-Bicyclohexanediol 0.29 g (1.50 mm
ol), 0.17 g (1.50 mmol) of trans-1,4-cyclohexanediol, 2 ml of pyridine and 50 ml of DCE were added and stirred. Then, the solution was maintained at 90 ° C. with a mantle heater, and 0.33 g (1.7 mmol) of trichloromethyl chloroformate was added thereto with DC.
The solution dissolved in E5 ml was added dropwise over 20 minutes under reflux, and the reaction was allowed to proceed for 90 minutes. The resulting reaction solution was allowed to cool, then poured into 300 ml of methanol, and the deposited precipitate was filtered. The filtrate was washed in hot methanol and then dried to obtain 0.47 g (yield: 87.3%) of a polycarbonate resin. This polycarbonate resin has a reduced viscosity of 0.62, a decomposition temperature of 293 ° C., and a melting point of 289 to 29.
It was 8 ° C, and the moldability was not good. The glass transition temperature was 192 ° C.

[0023]

[Table 1]

[0024]

As described above, the present invention has an effect of lowering the melting point by using bisphenolfluorene as a part of the structural unit in a trans-cyclohexane ring-containing polycarbonate resin. Was able to be improved in moldability. The bisphenol fluorene polycarbonate resin of the present invention melts at about 300 ° C. and can be used at higher temperatures than other resins.
Further, a film having excellent transparency can be produced. Thus, the polycarbonate resin of bisphenolfluorene of the present invention is useful by itself, but other known resins such as polyethylene, polypropylene, polymethyl methacrylate, ABS, polyamides, polyacrylates, polycarbonates, By mixing with resins such as polyesters such as polyethylene terephthalate or polyphenylene oxides, it is possible to improve the mechanical strength and thermoformability of these resins and to add new properties.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42 C08L 69/00 CA (STN)

Claims (7)

(57) [Claims] 1. A structural unit represented by the formula [1], a formula [2]
And a polycarbonate resin of bisphenol fluorene comprising the structural unit represented by the formula [3]. Embedded image Embedded image Embedded image Embedded image (In the formulas [2] and [3], the formula [4] represents transcyclohexylene.) 2. A polycarbonate resin of bisphenolfluorene comprising a structural unit represented by the formula [1] according to claim 1 and a structural unit represented by the formula [2] according to claim 1. 3. A polycarbonate resin of bisphenolfluorene comprising a structural unit represented by the formula [1] according to claim 1 and a structural unit represented by the formula [3] according to claim 1. 4. A bisphenolfluorene of the formula [5] as a diol component for forming the structural unit represented by the formula [1] and a formula [6] as a diol component for forming a structural unit represented by the formula [2]. Trans, trans-4,4'-bicyclohexanediol of the formula [7] as a diol component for forming the structural unit of the formula [3]. The polycarbonate resin of bisphenol fluorene according to claim 1 to 3 which is obtained. Embedded image Embedded image Embedded image Embedded image (In the formulas [6] and [7], the formula [4] represents transcyclohexylene.) 5. The method according to claim 1, wherein the proportion of the structural unit represented by the formula [1] is 2
The polycarbonate resin of bisphenol fluorene according to any one of claims 1 to 4, which is 0 to 95 mol%. 6. Use of one or both of trans, trans-4,4′-bicyclohexanediol and trans-1,4-cyclohexanediol as a diol component in combination with bisphenolfluorene, and trichlorochloroformate in the presence of an acid acceptor A method for producing a polycarbonate resin of bisphenolfluorene, characterized by reacting with methyl. 7. The process for producing a bisphenol fluorene polycarbonate resin according to claim 6, wherein the proportion of bisphenol fluorene in the diol component is 20 to 95 mol%.