Polycarbonate resin and method for producing same

Abstract

The purpose of the present invention is to provide: a polycarbonate resin which has a narrow molecular weight distribution and in which the formation of low molecular weight oligomers is suppressed; and a method for producing the polycarbonate resin. According to the present invention, provided are a polycarbonate resin containing a structural unit represented by general formula (1), wherein the molecular weight distribution value (Mw/Mn) is 6.0 or less, and the content of oligomers having a molecular weight of less than 1,000 is suppressed to 0.50 mass % or less; and a method for producing the polycarbonate. (In general formula (1), R.sub.1-26 represent hydrogen, fluorine, chlorine, bromine, iodine, a C1-9 alkyl group, a C6-12 aryl group, a C1-5 alkoxy group, a C2-5 alkenyl group, or a C7-17 aralkyl group). ##STR00001##

Claims

1. A method for producing a polycarbonate resin comprising a structural unit represented by general formula (1) below, wherein a molecular weight distribution value (Mw/Mn) is 6.0 or less and a content of oligomers having a molecular weight of less than 1,000 is 0.50 mass % or less: ##STR00008## where, R.sub.1-26 represent hydrogen, fluorine, chlorine, bromine, iodine, a C1-9 alkyl group, a C6-12 aryl group, a C1-5 alkoxy group, a C2-5 alkenyl group or a C7-17 aralkyl group, wherein the method comprises: a step of mixing a diol compound represented by general formula (2) below and a nitrogen-containing compound represented by general formula (3) below in an amount of less than 0.10 mass % relative to the diol compound, ##STR00009## where, R.sub.1-26 represent the same as in the general formula (1), ##STR00010## where, n represents any one of 2, 3 and 4, Y represents an ethyl group, a propyl group, a butyl group or a benzyl group, and X represents Cl, Br, OH or HSO.sub.4; and adding an organic solvent and a molecular weight control agent to a reaction solution containing the diol compound, the nitrogen-containing compound and phosgene, and emulsifying the resulting solution for a time shorter than 15 minutes.

2. The method according to claim 1, wherein R.sub.1-26 in the general formula (1) are hydrogen.

Description

EXAMPLES

(1) Hereinafter, the present invention will be described in more detail by way of examples, although the present invention should not be limited to the following examples.

(2) <Conditions for measurement by gel permeation chromatography (GPC)>

(3) The weight average molecular weight (Mw), the molecular weight distribution value (Mw/Mn) (in terms of polystyrene) and the content (mass %) of oligomers having a molecular weight of less than 1,000 in each of the polycarbonate resins obtained in the examples and the comparative examples were measured under the following conditions.

(4) Measurement instrument: HLC-8320GPC from Tosoh Corporation

(5) Columns: Shodex K-G+K-805L×2+K-800D

(6) Eluent: Chloroform

(7) Temperature: Thermostatic tank for columns at 40° C.

(8) Flow rate: 1.0 ml/min

(9) Concentration: 0.1 wt/vol %

(10) Injected amount: 100 μl

(11) Pretreatment: Filtration with 0.45 μm filter

(12) Detector: Refractive index detector (RI)

(13) The content (mass %) of oligomers having a molecular weight of less than 1,000 was determined as follows. Specifically, polystyrenes available from AMR Inc. were used to generate the following calibration curve equation, which was used to calculate the log molecular weight.
Log molecular weight=s−1.37T+6.31×10−2×T.sup.2−1.35×10.sup.−3×T.sup.3

(14) where, T represents elution time (min).

(15) From the chromatogram having the molecular weight (log molecular weight) along the horizontal axis and the elution rate (dwt/d (log molecular weight)) along the vertical axis, the ratio of the area of the entire chromatograph and the area of the region of molecular weights of less than 1,000 was calculated to determine the content of oligomers having a molecular weight of less than 1,000.

Example 1

(16) (Step 1)

(17) To 1,050 ml of a 9 w/w % aqueous solution of sodium hydroxide, 100 g of cyclododecane bisphenol (hereinafter, HPCD) from Honshu Chemical Industry Co., Ltd., 0.5 g of hydrosulfite and 0.01 g of benzyltriethylammonium chloride (hereinafter, TEBAC) were added to be dissolved therein. To the resulting solution, 390 ml of dichloromethane was added, and 45 g of phosgene was blown into the resultant by spending 30 minutes while stirring and setting the solution temperature to 20° C.

(18) (Step 2)

(19) After the phosgene blowing, 0.5 g of p-tert-butylphenol (PTBP) dissolved in 50 ml of dichloromethane was added and vigorously stirred for 7 minutes for emulsification (emulsification time was 7 minutes). Thereafter, 0.36 g of triethylamine (TEA) was added as a polymerization catalyst to allow polymerization for 30 minutes.

(20) (Post-Polymerization Process)

(21) The polymerization solution was separated into a water phase and an organic phase, and the organic phase was neutralized with phosphoric acid and repeatedly washed with pure water until pH of the water after washing became pH=7.0. The organic solvent was evaporated and distilled away from the generated polycarbonate resin solution to give polycarbonate resin powder.

(22) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 155,300, the molecular weight distribution value (Mw/Mn) was 4.16, and the content of oligomers having a molecular weight of less than 1,000 was 0.24 mass %.

Example 2

(23) Polycarbonate resin powder was obtained in the same manner as Example 1 except that the emulsification time was changed to 2 minutes in Step 2.

(24) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 157,500, the molecular weight distribution value (Mw/Mn) was 4.16, and the content of oligomers having a molecular weight of less than 1,000 was 0.35 mass %.

Example 3

(25) Polycarbonate resin powder was obtained in the same manner as Example 1 except that TEBAC was changed to benzyltributylammonium chloride (TBBAC) in Step 1.

(26) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 159,300, the molecular weight distribution value (Mw/Mn) was 4.94, and the content of oligomers having a molecular weight of less than 1,000 was 0.27 mass %.

Example 4

(27) Polycarbonate resin powder was obtained in the same manner as Example 1 except that the amount of TEBAC added was changed to 0.05 g in Step 1.

(28) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 155,500, the molecular weight distribution value (Mw/Mn) was 5.82, and the content of oligomers having a molecular weight of less than 1,000 was 0.45 mass %.

Example 5

(29) Polycarbonate resin powder was obtained in the same manner as Example 1 except that emulsification time was changed to 10 minutes in Step 2.

(30) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 157,600, the molecular weight distribution value (Mw/Mn) was 4.81, and the content of oligomers having a molecular weight of less than 1,000 was 0.34 mass %.

Example 6

(31) Polycarbonate resin powder was obtained in the same manner as Example 1 except that 70 g of HPCD and 30 g of bisphenol A (BPA) were used as the diol compound and the amount of PTBP was changed to 1.4 g in Step 1.

(32) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 71,800, the molecular weight distribution value (Mw/Mn) was 2.47, and the content of oligomers having a molecular weight of less than 1,000 was 0.15 mass %.

Example 7

(33) Polycarbonate resin powder was obtained in the same manner as Example 1 except that 50 g of HPCD and 50 g of BPA were used as the diol compound and the amount of PTBP was changed to 1.53 g in Step 1.

(34) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 70,000, the molecular weight distribution value (Mw/Mn) was 2.46, and the content of oligomers having a molecular weight of less than 1,000 was 0.16 mass %.

Example 8

(35) Polycarbonate resin powder was obtained in the same manner as Example 1 except that 30 g of HPCD and 70 g of BPA were used as the diol compound and the amount of PTBP was changed to 1.65 g in Step 1.

(36) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 75,500, the molecular weight distribution value (Mw/Mn) was 2.64, and the content of oligomers having a molecular weight of less than 1,000 was 0.21 mass %.

Comparative Example 1

(37) Polycarbonate resin powder was obtained in the same manner as Example 1 except that the amount of TEBAC added was changed to 0.20 g in Step 1.

(38) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 177,800, the molecular weight distribution value (Mw/Mn) was 7.44, and the content of oligomers having a molecular weight of less than 1,000 was 0.80 mass %.

Comparative Example 2

(39) Polycarbonate resin powder was obtained in the same manner as Example 1 except that the emulsification time was changed to 15 minutes in Step 2.

(40) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 160,500, the molecular weight distribution value (Mw/Mn) was 6.03, and the content of oligomers having a molecular weight of less than 1,000 was 0.68 mass %.

Comparative Example 3

(41) Polycarbonate resin powder was obtained in the same manner as Example 1 except that the amount of TBBAC added was changed to 0.10 g, in other words, 0.10 g of TBBAC was added instead of 0.01 g of TEBAC, in Step 1.

(42) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 153,300, the molecular weight distribution value (Mw/Mn) was 6.12, and the content of oligomers having a molecular weight of 1,000 or less was 0.54 mass %.

Comparative Example 4

(43) (Step 1)

(44) To 1,050 ml of a 9 w/w % aqueous solution of sodium hydroxide, 100 g of HPCD and 0.5 g of hydrosulfite were added to be dissolved therein. To the resulting solution, 390 ml of dichloromethane was added, and 45 g of phosgene was blown into the resultant by spending 30 minutes while stirring and setting the solution temperature to 20° C.

(45) (Step 2)

(46) After the phosgene blowing, the resultant was vigorously stirred for 7 minutes for emulsification (emulsification time was 7 minutes). Thereafter, 0.007 g of pyridine hydrochloride was added as a polymerization catalyst to allow polymerization for 30 minutes.

(47) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 23,400, the molecular weight distribution value (Mw/Mn) was 2.63, and the content of oligomers having a molecular weight of 1,000 or less was 1.30 mass %.

Comparative Example 5

(48) (Step 1)

(49) To 1,050 ml of a 9 w/w % aqueous solution of sodium hydroxide, 100 g of HPCD and 0.5 g of hydrosulfite were added to be dissolved therein. To the resulting solution, 390 ml of dichloromethane was added, and 45 g of phosgene was blown into the resultant by spending 30 minutes while stirring and setting the solution temperature to 20° C.

(50) (Step 2)

(51) After the phosgene blowing, 0.005 g of triethylamine was added as a polymerization catalyst and the resultant was stirred for 15 minutes. Thereafter, 0.5 g of PTBP dissolved in 50 ml of dichloromethane was added.

(52) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 26,900, the molecular weight distribution value (Mw/Mn) was 2.43, and the content of oligomers having a molecular weight of 1,000 or less was 0.63 mass %. However, the chloroformate structure remained and polymerization was incomplete.

Comparative Example 6

(53) Polycarbonate resin powder was obtained in the same manner as Example 1 except that the amount of TEBAC added was changed to 0.10 g in Step 1.

(54) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 165.800, the molecular weight distribution value (Mw/Mn) was 5.74, and the content of oligomers having a molecular weight of less than 1,000 was 0.60 mass %.

Comparative Example 7

(55) Polycarbonate resin powder was obtained in the same manner as Example 1 except that HPCD was changed to BPC, the amount of TEBAC was changed to 0.02 g and the amount of PTBP was changed to 1.4 g in Step 1.

(56) The resulting polycarbonate resin powder was subjected to an analytical measurement by GPC. As a result, Mw was 74,500, the molecular weight distribution value (Mw/Mn) was 3.19, and the content of oligomers having a molecular weight of less than 1,000 was 0.68 mass %.

(57) The results from Examples 1-8 and Comparative examples 1-7 are shown in Table 1.

(58) TABLE-US-00001 TABLE 1 Content of oligomers Nitrogen-containing compound having Percentage molecular relative Emulsi- Molecular weight of Diol compound to diol fication weight less than Mass Mass compound time distribution 1,000 Kind (g) Kind (g) (mass %) (min) Mw (Mw/Mn) (mass %) Notes Example 1 HPCD 100 TEBAC 0.01 0.01 7 155,300 4.16 0.24 — Example 2 HPCD 100 TEBAC 0.01 0.01 2 157,500 4.16 0.35 — Example 3 HPCD 100 TBBAC 0.01 0.01 7 159,300 4.94 0.27 — Example 4 HPCD 100 TEBAC 0.05 0.05 7 155,500 5.82 0.45 — Example 5 HPCD 100 TEBAC 0.01 0.01 10 157,600 4.81 0.34 — Example 6 HPCD 70 TEBAC 0.01 0.01 7 71,800 2.47 0.15 — BPA 30 Example 7 HPCD 50 TEBAC 0.01 0.01 7 70,000 2.46 0.16 — BPA 50 Example 8 HPCD 30 TEBAC 0.01 0.01 7 75,500 2.64 0.21 — BPA 70 Comparative HPCD 100 TEBAC 0.20 0.20 7 177,800 7.44 0.80 — example 1 Comparative HPCD 100 TEBAC 0.01 0.01 15 160,500 6.03 0.68 — example 2 Comparative HPCD 100 TBBAC 0.10 0.10 7 153,300 6.12 0.54 — example 3 Comparative HPCD 100 None 0 — 7 23,400 2.63 1.30 0.007 g pyridine example 4 hydrochloride used instead of TEA Comparative HPCD 100 None 0 — 0 26,900 2.43 0.63 After feeding 0.005 g example 5 TEA, the resultant was stirred for 15 minutes, and PTBP was fed to the resultant. Significant amount of terminal chloroformate structures Comparative HPCD 100 TEBAC 0.10 0.10 7 165,800 5.74 0.60 — example 6 Comparative BPC 100 TEBAC 0.02 0.02 7 74,500 3.19 0.68 — example 7 HPCD: Cyclododecane bisphenol BPA: Bisphenol A BPC: Bisphenol C TEBAC: Benzyltriethylammonium chloride TBBAC: Benzyltributylammonium chloride