METHODS FOR PRODUCING POLYCARBONATE COPOLYMER AND POLYSILOXANE COMPOUND, POLYCARBONATE COPOLYMER, POLYSILOXANE COMPOUND, COMPOSITION, AND MOLDED BODY

Abstract

A polycarbonate copolymer which has siloxane constituent units represented by any of formulae (1-1) to (1-4) and prescribed polycarbonate constituent units.

##STR00001##

Claims

1. A polycarbonate copolymer having a siloxane constituent unit represented by any one of the following formula (1-1) to formula (1-4) and a polycarbonate constituent unit represented by any one of the following formula (3-1) to formula (3-4), and comprising 30% by weight or less of a low molecular weight compound having a weight average molecular weight of 1,000 or less: ##STR00065## wherein, in the above formulae (1-1) to (1-4), R.sup.1 and R.sup.2 each independently represent an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, R.sup.3 to R.sup.10 and R.sup.3 to R.sup.33 each independently represent hydrogen, halogen, alkoxy, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group containing 2 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, Z.sub.1 and Z.sub.2 each independently represent an alkylene group containing 1 to 5 carbon atoms and optionally having a substituent, J.sub.1 each independently represents an integer of 0 or more and 5 or less, K.sub.1 each independently represents an integer of 0 or more and 5 or less, A.sub.1 and A.sub.2 each independently represent either O or CH, L.sub.1 and L.sub.2 each independently represent an integer of 0 or more and 3 or less, and X represents a single bond or any one of structural formulae represented by the following formula (2): ##STR00066## wherein R.sup.11 and R.sup.12 each independently represent hydrogen, halogen, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, or R.sup.11 and R.sup.12 bind to each other to form a carbocyclic or heterocyclic ring containing 1 to 20 carbon atoms and optionally having a substituent, and a and b each independently represent an integer of 0 or 1 or more and 5000 or less, and ##STR00067## wherein, in the above formulae (3-1) to (3-4), R.sup.13 to R.sup.20 and R.sup.40 to R.sup.51 each independently represent hydrogen, halogen, alkoxy, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group containing 2 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, Z.sub.3 and Z.sub.4 each independently represent an alkylene group containing 1 to 5 carbon atoms and optionally having a substituent, J.sub.2 each independently represents an integer of 0 or more and 5 or less, K.sub.2 each independently represents an integer of 0 or more and 5 or less, A.sub.1 and A.sub.2 each independently represent either O or CH, L.sub.1 and L.sub.2 each independently represent an integer of 0 or more and 3 or less, and Y represents a single bond or any one of structural formulae represented by the following formula (4): ##STR00068## wherein R.sup.21 and R.sup.22 each independently represent hydrogen, halogen, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, or R.sup.21 and R.sup.22 bind to each other to form a carbocyclic or heterocyclic ring containing 1 to 20 carbon atoms and optionally having a substituent, and c and d each independently represent an integer of 0 or 1 or more and 5000 or less, wherein the molar ratio between the siloxane constituent unit and the polycarbonate constituent unit is 30:70 to 99.9:0.01.

2. The polycarbonate copolymer according to claim 1, wherein the X has a siloxane constituent unit showing a fluorene ring structure formed by the binding of R.sup.11 and R.sup.12, and/or the Y has a polycarbonate constituent unit showing a fluorene ring structure formed by the binding of R.sup.21 and R.sup.22.

3. The polycarbonate copolymer according to claim 1, wherein the low molecular weight compound has a weight average molecular weight of 1,000 or less, which is calculated from the GPC area ratio.

4. The polycarbonate copolymer according to claim 1, wherein the mole number of the siloxane constituent unit is 1 to 1000, and the mole number of the polycarbonate constituent unit is 1 to 1000.

5. The polycarbonate copolymer according to claim 1, wherein the Q value of the polycarbonate copolymer measured under conditions of 280? C. and 160 kgf is 8 (?10.sup.?2 cm.sup.3s.sup.?1) or more.

6. The polycarbonate copolymer according to claim 1, wherein the total content of ring forms represented by the following formulae (5-1) to (5-3) is 4.0% by weight or less: ##STR00069## wherein, in the above formula (5-1) to (5-3), m represents the total number of consisting units comprising an (OSi(R.sub.1R.sub.2)O) site in each ring form, and the total number of constituent units comprising an (OC(?O)O) site in each ring form, respectively, wherein, in the above formula (5-1), m represents an integer of 2 to 10, in the formula (5-2), n represents an integer of 2 to 10, in the formula (5-3), the total value of m is 1 to 10, and the total value of n is 1 to 10, and in the formula (5-3), the constituent units comprising an (OSi(R.sub.1R.sub.2)O) site and the constituent units comprising an (OC(?O)O) site are arbitrarily disposed, in the formulae (5-1) to (5-3), R.sup.1 and R.sup.2 each independently represent an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, R.sup.3 to R.sup.10 and R.sup.13 to R.sup.20 each independently represent hydrogen, halogen, alkoxy, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group containing 2 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, X.sub.1 and X.sub.2 each independently represent an alkylene group containing 1 to 5 carbon atoms and optionally having a substituent, i and ii each independently represent an integer of 0 or more and 5 or less, and X represents a single bond or any one of structural formulae represented by the following formula (2): ##STR00070## wherein R.sup.11 and R.sup.12 each independently represent hydrogen, halogen, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, or R.sup.11 and R.sup.12 bind to each other to form a carbocyclic or heterocyclic ring containing 1 to 20 carbon atoms and optionally having a substituent, and a and b each independently represent an integer of 0 or 1 or more and 5000 or less.

7. The polycarbonate copolymer according to claim 1, wherein the total content of ring forms represented by the following formulae (6-1) and (6-2) is 2.0% by weight or less: ##STR00071## wherein, in the above formulae (6-1) and (6-2), R.sup.1 and R.sup.2 each independently represent an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, R.sup.3 to R.sup.10 and R.sup.30 to R.sup.33 each independently represent hydrogen, halogen, alkoxy, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group containing 2 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, X.sub.1 and X.sub.2 each independently represent an alkylene group containing 1 to 5 carbon atoms and optionally having a substituent, i and ii each independently represent an integer of 0 or more and 5 or less, n represents an integer of 2 to 10, and X represents a single bond or any one of structural formulae represented by the following formula (2): ##STR00072## wherein R.sup.11 and R.sup.12 each independently represent hydrogen, halogen, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, or R.sup.11 and R.sup.12 bind to each other to form a carbocyclic or heterocyclic ring containing 1 to 20 carbon atoms and optionally having a substituent, and a and b each independently represent an integer of 0 or 1 or more and 5000 or less.

8. The polycarbonate copolymer according to claim 1, wherein the pyrolysis temperature necessary for a loss of 1% mass is 415? C. or lower.

Description

EXAMPLES

Examples of Polycarbonate Resin

[0539] Applying GPC (gel permeation chromatography), and using chloroform as a developing solvent, a calibration curve was produced using standard polystyrene (Shodex STANDARD, SM-105) with a known molecular weight (molecular weight distribution=1). From the measured standard polystyrene, the elution time and the molecular weight value of each peak were plotted, and an approximation was made using an expression of the third order to prepare a calibration curve.

[0540] Thereafter, based on the obtained calibration curve, the weight average molecular weight (Mw) was obtained as a value in terms of polystyrene according to the following equation.

Mw=?(W.sub.i?M.sub.i)/?(W.sub.i)[Equation] [0541] wherein i represents an i.sup.th division point upon division of the molecular weight M; W.sub.i represents an i.sup.th weight; M.sub.i represents an i.sup.th molecular weight; and the molecular weight M represents a molecular weight in terms of polystyrene at the same elution time in the calibration curve.

[Measurement Conditions]

[0542] Apparatus: LabSolutions, manufactured by Shimadzu Corporation [0543] Columns: Guard column (Shodex GPC K-G 4A)?1, Analysis column (Shodex GPC K-805L)?2 [0544] Solvent: chloroform (HPLC grade) [0545] Injected amount: 10 ?L [0546] Sample concentration: 2000 ppm [0547] Flow rate of solvent: 1 mL/min [0548] Measurement temperature: 40? C. [0549] Detector: RI
<Measurement of Content Percentage of Low Molecular Weight Compound with Weight Average Molecular Weight (Mw) of 1,000 or Less>

[0550] The percentage of a low molecular weight compound with Mw of 1,000 or less in the polycarbonate resin was calculated from the ratio between the area of a retention time from 20.5 min to 21.5 min/the area of a retention time from 0 min to 21.5 min (GPC area ratio), based on the data obtained by a GPC analysis performed under the aforementioned conditions.

[0551] Specifically, the GPC analysis was carried out under the conditions described in the section <Measurement of weight average molecular weight (Mw) in terms of polystyrene>. Thereafter, the content percentage (B/A?100(%)) of the low molecular weight compound was measured, based on the ratio between the GPC area (A) of a peak confirmed at a retention time of 21.5 min or less considered to correspond to the amount of all compounds comprised in the sample of the polycarbonate resin, and the GPC area (B) of a peak confirmed at a retention time between 20.5 min and 21.5 min considered to correspond to the amount of the low molecular weight compound with a weight average molecular weight of 1,000 or less.

[0552] As a measurement sample, a test piece with a size of 5 to 12 mg was weighed into a sample container for AI autosampler (an RDC aluminum pan, a cylindrical container having a diameter of 6.8 mm and a height of 2.5 mm), and the upper portion of the sample container was sealed with a cover for AI autosampler.

[0553] The measurement of Tg was carried out using a differential scanning calorimeter (DSC) in a nitrogen atmosphere (nitrogen flow rate: 50 ml/min), and for a reference cell, 10.0 mg of sapphire was used as a standard substance. The measurement sample adjusted to 30? C. was heated to 280? C. at a rate of 20? C./min, and was then cooled to 30? C. at a rate of 20? C./min. Thereafter, the temperature was increased to 280? C. at a rate of 10? C./min, and the Tg of the measurement sample was measured.

[0554] Measurement apparatus: Differential scanning calorimeter (DSC) (product name: DSC-7020, manufactured by Hitachi High-Tech Science Corporation)

[0555] A sample (10 g) was dissolved in 60 g of dichloromethane to prepare a resin solution, and thereafter, 150 g of ethanol was added dropwise into the resin solution during stirring over 30 minutes. The precipitate was filtrated through a NoA5 filter, and the filtrate was then concentrated using an evaporator to obtain an oligomer component a.

[0556] The obtained precipitate was dissolved in 60 g of dichloromethane to prepare a resin solution, and thereafter, 150 g of ethanol was added dropwise to the resin solution, so as to obtain a precipitate and an oligomer component b.

[0557] The obtained oligomer components a and b were each dissolved in dichloromethane to prepare a 1000 ?g/mL solution, which was then analyzed and quantified by GC/FID.

[0558] The quantitative value is a value relative to 2,2-bis(4-hydroxyphenyl)propane, which is obtained from the previously prepared calibration curve of 2,2-bis(4-hydroxyphenyl)propane.

[Measurement Conditions for GC/FID]

[0559] Apparatus: GC2025, manufactured by Shimadzu Corporation [0560] Column: Capillary column DB-35, 30 mm?0.25 mm?0.25 m [0561] Temperature-increasing conditions: 40? C.-300? C. (5 min hold), 10? C./min [0562] Temperature of injection port: 300? C., injected amount: 1.0 ?L (split ratio: 1:20) [0563] Carrier gas: He [0564] Air flow rate: 400 mL/min [0565] H2 flow rate: 40 mL/min [0566] Makeup gas: 30 mL/min [0567] Standard substance: 2,2-bis(4-hydroxyphenyl)propane

[0568] The content of the aforementioned cyclic dimer in the polycarbonate copolymer was measured as follows.

[0569] A sample (20 g) of the polycarbonate copolymer was dissolved in 120 g of dichloromethane to prepare a resin solution, and thereafter, 200 g of ethanol was added dropwise into the resin solution during stirring over 30 minutes. The precipitate was filtrated through a NoA5 filter, and the filtrate was then concentrated using an evaporator to obtain an oligomer component A and a precipitate A.

[0570] Subsequently, the obtained precipitate A was dissolved in 120 g of dichloromethane to prepare a resin solution, and thereafter, 200 g of ethanol was added dropwise into the resin solution during stirring over 30 minutes. The precipitate was filtrated through a NoA5 filter, and the filtrate was then concentrated using an evaporator to obtain an oligomer component B and a precipitate B.

[0571] Subsequently, the obtained precipitate B was dissolved in 120 g of dichloromethane to prepare a resin solution, and thereafter, 200 g of ethanol was added dropwise into the resin solution during stirring over 30 minutes. The precipitate was filtrated through a NoA5 filter, and the filtrate was then concentrated using an evaporator to obtain an oligomer component C and a precipitate C.

[0572] The thus obtained oligomer components A, B and C were each dissolved in dichloromethane to prepare a 1000 ?g/mL solution, and the cyclic dimer was then analyzed by GC/FID. The quantitative value is a value relative to 2,2-bis(4-hydroxyphenyl)propane, which was obtained from the previously prepared calibration curve of 2,2-bis(4-hydroxyphenyl)propane.

[Measurement Conditions for GC-Q-MS/FID]

[0573] Apparatus: Agilent-7890B/Agilent-5975C MSD Inert XL MSD with TAD, manufactured by Agilent Technologies Japan, Ltd. [0574] Column: DB-5MS, 15 mm?0.25 mm?0.1 ?m [0575] Restrictor (MS): 0.18 mm?1.44 mm [0576] Restrictor (FID): 0.18 mm?0.53 mm [0577] Temperature-increasing conditions: 50? C. (2 min hold)-320? C. (15 min hold), 20? C./min [0578] Temperature of injection port: 300? C. [0579] Injected amount: 1.0 ?L (split ratio: 1:10) [0580] Carrier gas: He [0581] FID/MS ratio: 1/1 [0582] Aux temperature: 300? C. [0583] Scan Range: m/z 33 to 700 [0584] Scan rate: 2.22 scan/s [0585] FID temperature: 300? C. [0586] H.sub.2 flow rate: 30 mL/min [0587] Air flow rate: 400 mL/min [0588] Makeup gas: 25 mL/min [0589] Standard substance: 2,2-bis(4-hydroxyphenyl)propane [0590] Quantification of cyclic dimer: Quantified from a peak strength of 16.6 min

[0591] The fluidity (Q value) indicates a melt flow volume (cm.sup.3/sec) per unit time, which was measured at 280? C. and at a load of 160 kg (wherein a melt flow volume was measured using CFT-500D type (1 mm (nozzle diameter)?10 mm (nozzle length)), manufactured by Shimadzu Corporation, and a value per unit time was then calculated at a stroke of 7.0 to 10.0 mm).

[0592] The Charpy impact strength (kJ/m.sup.2) of the molded test piece was measured in accordance with JIS-K7111.

[0593] The refractive index (nd) of a right angle piece with a thickness of 3 mm that consisted of the polycarbonate copolymer produced in the Examples was measured using an Abbe's refractometer in accordance with JIS-K-7142.

[0594] With regard to a right angle piece with a thickness of 3 mm that consisted of the polycarbonate copolymer produced in the Examples, the refractive index at 23? C. and at each of wavelengths of 486 nm, 589 nm and 656 nm was measured using an Abbe's refractometer, and further, an Abbe number was calculated using the following equation.

?d=(nd?1)/(nF?nc) [0595] nd: Refractive index at a wavelength of 589 nm [0596] nC: Refractive index at a wavelength of 656 nm [0597] nF: Refractive index at a wavelength of 486 nm

(Synthesis Example 1) Synthesis of Dimethyldiphenoxy Silane

[0598] Dimethyldiphenoxy silane was synthesized with reference to the method described in US2012/184702.

[0599] Phenol (176.34 g; 1.87 mol) was stirred at 50? C. in an N.sub.2 atmosphere, and dimethyldichlorosilane (113.24 g; 0.88 mol) was added dropwise thereto over 30 min. One hour after completion of the dropwise addition, by-products were distilled away at 170? C. under a reduced pressure of 200 hPa. The reaction solution was cooled to room temperature, and a product was dissolved in 300 mL of dichloromethane. The product dissolved in dichloromethane was washed twice with 300 mL of a 10% NaOH solution, and an organic layer was then extracted. The organic layer was washed twice with 300 mL of water, and after completion of the washing, the organic layer was extracted. The residual water was removed with anhydrous magnesium sulfate, and dichloromethane was then distilled away using an evaporator to obtain an oily component.

[0600] The obtained oily component was analyzed by 1H-NMR, and as a result, the oily component was confirmed to be dimethyldiphenoxy silane (1H-NMR (CDCl3,500 MHz, 6; ppm)=0.378 (s; 6H), 6.942, 6.944 (d; 4H), 6.959, 6.961, 6.995 (t; 2H), 7.230, 7.245, 7.257 (t; 4H)). The molar yield was found to be 66%.

Example A-1

[0601] 2,2-Bis(4-hydroxyphenyl)propane (104.97 g; 0.46 mol), dimethyldiphenoxy silane (4.58 g; 0.02 mol), diphenyl carbonate (101.46 g; 0.47 mol), and 2.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 300-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 190? C., and were stirred for 20 minutes.

[0602] Thereafter, a transesterification reaction was carried out over 1 hour 20 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less.

[0603] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 44,373.

[0604] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 136? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 411? C.

Example A-2

[0605] 2,2-Bis(4-hydroxyphenyl)propane (72.85 g; 0.32 mol), dimethyldiphenoxy silane (7.9 g; 0.032 mol), diphenyl carbonate (65.86 g; 0.31 mol), and 0.6 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 300-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0606] Thereafter, a transesterification reaction was carried out over 1.5 hours, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less.

[0607] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 48,035.

[0608] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 129? C.

[0609] The Q value of the above-described copolymer was measured, and as a result, it was 75 (?10.sup.?2 cm.sup.3/sec).

Example A-3

[0610] 2,2-Bis(4-hydroxyphenyl)propane (21.69 g; 0.10 mol), dimethyldiphenoxy silane (9.52 g; 0.39 mol), diphenyl carbonate (13.5 g; 0.63 mol), and 7.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0611] Thereafter, a transesterification reaction was carried out over 1 hour, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 2 hours, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less.

[0612] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 54,007.

[0613] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 101? C.

[0614] The Q value of the above-described copolymer was measured, and as a result, it was 114 (?10.sup.2 cm.sup.3/sec).

Example A-4

[0615] 2,2-Bis(4-hydroxyphenyl)propane (30.69 g; 0.13 mol), dimethyldiphenoxy silane (25.46 g; 0.10 mol), diphenyl carbonate (9.96 g; 0.046 mol), and 7.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0616] Thereafter, a transesterification reaction was carried out over 1 hour, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 2 hours, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less.

[0617] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 63,068.

[0618] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 75? C.

Example A-5

[0619] 2,2-Bis(4-hydroxyphenyl)propane (30.63 g; 0.13 mol), dimethyldiphenoxy silane (31.05 g; 0.13 mol), diphenyl carbonate (5.04 g; 0.024 mol), and 7.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0620] Thereafter, a transesterification reaction was carried out over 1 hour, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 2 hours, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and 400 Pa or less.

[0621] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 49,161.

[0622] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 62? C.

Examples A-6 to A-14

[0623] Copolymers were produced in the same manner as that of Example A-1, with the exception that the compounds used as raw materials were changed as shown in the following Table 1. The properties of the obtained copolymers are shown in Table 1.

TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Raw Aromatic diol compound g 104.97 72.85 21.69 30.69 30.63 80.14 80.11 materials/ (BPA: 2,2-Bis(4- mol 0.46 0.32 0.10 0.13 0.13 0.35 0.35 catalysts hydroxyphenyl)propane) (molar amount) Diol compound g 0 0 0 0 0 0 0 (BPEF: 9,9-Bis[4-(2- mol 0 0 0 0 0 0 0 hydroxyethoxy)phenyl]fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 0 (BCF: 9,9-Bis(4-hydroxy-3- mol 0 0 0 0 0 0 0 methylphenyl)fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 0 (BPF: 9,9-Bis(4- mol 0 0 0 0 0 0 0 hydroxyphenyl)fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 0 (ISB: Isosorbide) mol 0 0 0 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 0 0 (SPG: Spiroglycol) mol 0 0 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfone) mol 0 0 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfide) mol 0 0 0 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 0 0 (BNEF: 9,9-Bis[6-(2- mol 0 0 0 0 0 0 0 hydroxyethoxy)naphthalen-2- (molar amount) yl]fluorene) Aromatic diol compound g 0 0 0 0 0 0 0 (Biphenol: 4,4-Dihydroxy- mol 0 0 0 0 0 0 0 biphenyl) (molar amount) Aromatic diol compound g 0 0 0 0 0 0 0 (2EO-BINOL: 2,2- mol 0 0 0 0 0 0 0 Bishydroxyethoxy-1,1- (molar amount) binaphthyl) Diaryl carbonate g 101.46 65.86 13.50 9.96 5.04 25.96 25.96 (DPC: Diphenyl carbonate) mol 0.47 0.31 0.06 0.05 0.02 0.12 0.12 (molar amount) Diphenoxysilane compound g 4.58 7.90 9.52 25.46 31.05 0 0 (DMDPS: mol 0.019 0.032 0.039 0.10 0.13 0 0 Dimethyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 0 0 0 96.94 96.94 (DPDPS: mol 0 0 0 0 0 0.26 0.26 Diphenyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 0 0 0 0 0 (DPDMS: mol 0 0 0 0 0 0 0 Diphenyldimethoxysilane) (molar amount) Molar ratio mol/mol 1.07 1.06 1.07 1.12 1.12 1.09 1.09 ((Diphenoxysilane compound + DPC)/BPA) Catalyst ?mol/mol 2 0.6 11 11 11 3 15 (Cs.sub.2Co.sub.3, except for those clearly (Number of described) moles (?mol) per mol of aromatic diol compound) Reaction Final reaction temperature (? C.) 260 260 260 260 260 260 260 conditions Poly- Weight average molecular weight Mw (g/mol) 44373 48035 54,007 49,161 63,068 15,403 18,211 carbonate Percentage of polymer molecules (mass %) 0.03 0.03 0.1 0.6 0.9 2.1 1.4 copolymer with weight average molecular (product) weight of 1,000 or less Siloxane constituent unit (mol %) 2.92 8.17 35.07 66.49 81.47 68.35 48.36 (Si-containing constituent unit) Polycarbonate constituent unit (mol %) 97.08 91.83 64.93 33.51 18.53 31.65 51.64 (PC-containing constituent unit) Si mass % (mass %) 0.32 0.89 3.7 6.8 8.2 5.3 4.1 Q value (280? C./160 kgf) (?10.sup.?2 cm.sup.3/sec) 61 75 114 >121 >121 Glass transition temperature (Tg) (? C.) 136 129 101 75 62 85 91 Temperature for weight loss of (? C.) 411 401 380 365 363 372 334 1% (DSC) Refractive index (nd) 1.583 1.582 1.581 1.579 1.578 1.615 1.612 Abbe number (vd) 30.0 30.0 29.6 29.2 29.0 27.0 27.7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Raw Aromatic diol compound g 80.11 80.12 80.13 80.11 80.13 80.13 80.13 materials/ (BPA: 2,2-Bis(4- mol 0.35 0.35 0.35 0.35 0.35 0.35 0.35 catalysts hydroxyphenyl)propane) (molar amount) Diol compound g 0 0 0 0 0 0 0 (BPEF: 9,9-Bis[4-(2- mol 0 0 0 0 0 0 0 hydroxyethoxy)phenyl]fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 0 (BCF: 9,9-Bis(4-hydroxy-3- mol 0 0 0 0 0 0 0 methylphenyl)fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 0 (BPF: 9,9-Bis(4- mol 0 0 0 0 0 0 0 hydroxyphenyl)fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 0 (ISB: Isosorbide) mol 0 0 0 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 0 0 (SPG: Spiroglycol) mol 0 0 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfone) mol 0 0 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfide) mol 0 0 0 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 0 0 (BNEF: 9,9-Bis[6-(2- mol 0 0 0 0 0 0 0 hydroxyethoxy)naphthalen-2- (molar amount) yl]fluorene) Aromatic diol compound g 0 0 0 0 0 0 0 (Biphenol: 4,4-Dihydroxy- mol 0 0 0 0 0 0 0 biphenyl) (molar amount) Aromatic diol compound g 0 0 0 0 0 0 0 (2EO-BINOL: 2,2- mol 0 0 0 0 0 0 0 Bishydroxyethoxy-1,1- (molar amount) binaphthyl) Diaryl carbonate g 25.96 25.98 25.98 25.99 25.94 25.97 25.98 (DPC: Diphenyl carbonate) mol 0.12 0.12 0.12 0.12 0.12 0.12 0.12 (molar amount) Diphenoxysilane compound g 0 0 64.29 64.30 64.33 64.36 64.30 (DMDPS: mol 0 0 0.26 0.26 0.26 0.26 0.26 Dimethyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 0 0 0 0 0 (DPDPS: mol 0 0 0 0 0 0 0 Diphenyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 64.31 64.31 0 0 0 0 0 (DPDMS: mol 0.26 0.26 0 0 0 0 0 Diphenyldimethoxysilane) (molar amount) Molar ratio mol/mol 1.09 1.09 1.09 1.09 1.09 1.09 1.09 ((Diphenoxysilane compound + DPC)/BPA) Catalyst ?mol/mol 3 15 3 3 3 340 6 (Cs.sub.2Co.sub.3, except for those clearly (Number of (Na.sub.2CO.sub.3) (K.sub.2CO.sub.3) (Bu.sub.2(OAc).sub.2Sn (NaHCO.sub.3) described) moles (?mol) per mol of aromatic diol compound) Reaction Final reaction temperature (? C.) 260 260 260 260 260 260 260 conditions Poly- Weight average molecular weight Mw (g/mol) 2,529 4,467 51,906 33,177 32,810 3,775 29,669 carbonate Percentage of polymer molecules (mass %) 25.9 11.4 0.5 0.5 0.5 22.6 2.7 copolymer with weight average molecular (product) weight of 1,000 or less Siloxane constituent unit (mol %) 14.06 38.14 64.58 61.81 61.36 35.63 64.32 (Si-containing constituent unit) Polycarbonate constituent unit (mol %) 85.94 61.86 35.42 38.19 38.64 64.37 35.68 (PC-containing constituent unit) Si mass % (mass %) 1.4 3.4 6.6 6.4 6.3 3.8 6.6 Q value (280? C./160 kgf) (?10.sup.?2 cm.sup.3/sec) >121 >121 109 118 121 >121 119 Glass transition temperature (Tg) (? C.) 60 74 76 75 75 56 76 Temperature for weight loss of (? C.) 221 256 332 330 330 235 336 1% (DSC) Refractive index (nd) 1.615 1.616 1.578 1.578 1.578 1.579 1.578 Abbe number (vd) 26.8 26.8 30.6 30.6 30.6 30.6 30.6

Example A-15

[0624] 2,2-Bis(4-hydroxyphenyl)propane (2310 g; 10.13 mol), dimethyldiphenoxy silane (1849.26 g; 7.58 mol), diphenyl carbonate (753.04 g; 3.52 mol), and 14.0 ?mol/mol cesium carbonate used a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 10 L reactor equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 40 minutes.

[0625] Thereafter, a transesterification reaction was carried out over 1 hour and 30 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 1 hPa or less, and the reaction mixture was further retained for 1 hour 15 minutes, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 12,000 Pa, 8,000 Pa, 4,000 Pa, and 100 Pa or less.

[0626] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 208,939.

[0627] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 74.2? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 337.1? C.

Example A-16

[0628] 2,2-Bis(4-hydroxyphenyl)propane (2497 g; 10.95 mol), dimethyldiphenoxy silane (1997.20 g; 8.19 mol), diphenyl carbonate (813.00 g; 3.80 mol), and 3.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 10 L reactor equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 45 minutes.

[0629] Thereafter, a transesterification reaction was carried out over 2 hours 30 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 1 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 6,000 Pa, 4,000 Pa, and 100 Pa or less.

[0630] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 81,885.

[0631] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 75.1? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 380.6? C.

[0632] The amount of a low molecular weight contained in the above-described copolymer was quantified using GC. As a result, the copolymer comprised 415 ppm PhOH, 475 ppm BPA, 122 ppm DMDPS, and 44 ppm DPC.

Reference Example

[0633] According to the above-mentioned method for measuring a cyclic dimer, 19.99 g of the copolymer obtained in Example A-16 was dissolved in 121.22 g of dichloromethane, and 196 g of ethanol was then added dropwise to the resin solution during stirring over 30 minutes. Thereafter, a precipitate was filtrated through a NoA5 filter, and a filtrate was then concentrated using an evaporator to obtain 0.652 g of an oligomer component A. The precipitate was dissolved in dichloromethane again, and while ethanol was added dropwise thereto, an operation of separating the precipitate from the oligomer component was repeated twice (by which 0.268 g of an oligomer component B, 0.177 g of an oligomer component C, and 18.99 g of a copolymer reprecipitate, namely, a precipitate were obtained). The obtained oligomer components A, B and C were dissolved in dichloromethane to obtain a 1000 ?g/mL solution. The obtained solution was analyzed by GC-Q-MS/FID, and as a result, the amount of a cyclic dimer in the copolymer as a reprecipitate product was 0.71 wt %.

[0634] Moreover, the Q value of the siloxane-containing polycarbonate copolymer obtained in Example A-16 was 117 (?10.sup.2 cm.sup.3/sec), and the Q value of the reprecipitate product of the siloxane-containing polycarbonate copolymer obtained in the reference example was 74 (?10.sup.2 cm.sup.3/sec). It is found that the O value of the siloxane-containing polycarbonate copolymer is increased by allowing the polycarbonate copolymer to comprise a cyclic dimer, and that the fluidity of the polycarbonate copolymer is high.

TABLE-US-00002 TABLE 2 Reference Ex. Ex. 16 Reprecipitate of Unit Copolymer copolymer Content of GPC % 0.8 0.07 cyclic dimer GC % 0.71 Q value 0.01 ml/sec 117 74 Fluidity Good Slightly poor

Example A-17

[0635] 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene (30.99 g; 0.07 mol), diphenyldimethoxy silane (13.01 g; 0.05 mol), diphenyl carbonate (5.28 g; 0.02 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 190? C., and were stirred for 30 minutes.

[0636] Thereafter, a transesterification reaction was carried out over 1 hour 10 minutes, while phenol and methanol distilled from the reaction system were condensed in a cooling tube and were removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 15 minutes, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less.

[0637] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 115,683.

[0638] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 110.9? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 351.4? C.

Example A-18

[0639] 9,9-Bis(4-hydroxyphenyl)fluorene (24.71 g; 0.071 mol), diphenyldimethoxy silane (18.00 g; 0.074 mol), diphenyl carbonate (0.831 g; 0.004 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 9,9-bis(4-hydroxyphenyl)fluorene) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 190? C., and were stirred for 15 minutes.

[0640] Thereafter, a transesterification reaction was carried out over 1 hour 20 minutes, while phenol and methanol distilled from the reaction system were condensed in a cooling tube and were removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a polycarbonate copolymer having a yellowed transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, and 200 Pa or less.

[0641] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 12,992.

[0642] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 165.5? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 361.1? C.

Example A-19

[0643] 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene (17.07 g; 0.04 mol), 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (12.06 g; 0.03 mol), diphenyldimethoxy silane (12.99 g; 0.05 mol), diphenyl carbonate (5.26 g; 0.02 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the sum of the number of moles of the 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene and the 9,9-bis(4-hydroxy-3-methylphenyl)fluorene) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 200? C., and were stirred for 30 minutes.

[0644] Thereafter, a transesterification reaction was carried out over 1 hour 20 minutes, while phenol and methanol distilled from the reaction system were condensed in a cooling tube and were removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour 20 minutes, so as to obtain a polycarbonate copolymer having a browned transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less.

[0645] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 23,272.

[0646] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 140.4? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 349.4? C.

Example A-20

[0647] 9,9-Bis(4-hydroxyphenyl)fluorene (24.71 g; 0.071 mol), dimethyldiphenoxy silane (1.80 g; 0.007 mol), diphenyldimethoxy silane (16.21 g; 0.066 mol), diphenyl carbonate (0.83 g; 0.004 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 9,9-bis(4-hydroxyphenyl)fluorene) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 210? C., and were stirred for 25 minutes.

[0648] Thereafter, a transesterification reaction was carried out over 1 hour 25 minutes, while phenol and methanol distilled from the reaction system were condensed in a cooling tube and were removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour, so as to obtain a polycarbonate copolymer having a yellowed transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, and 200 Pa or less.

[0649] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 28,050.

[0650] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 171.4? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 339.1? C.

Example A-21

[0651] Isosorbide (10.22 g; 0.07 mol), diphenyldimethoxy silane (17.60 g; 0.07 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the isosorbide) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 100? C., and were stirred for 10 minutes.

[0652] Thereafter, a transesterification reaction was carried out over 1 hour 55 minutes, while methanol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 200? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a yellowed transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 90,000 Pa, 80,000 Pa, 70,000 Pa, 60,000 Pa, 50,000 Pa, 30,000 Pa, 10,000 Pa, 6,000 Pa, 2,000 Pa, and 200 Pa or less.

[0653] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 9,125.

[0654] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 71.1? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 256.2? C.

Example A-22

[0655] Bis(4-hydroxyphenyl)sulfone (17.50 g; 0.07 mol), diphenyldimethoxy silane (17.42 g; 0.07 mol), and 30.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the bis(4-hydroxyphenyl)sulfone) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 220? C., and were stirred for 25 minutes.

[0656] Thereafter, a transesterification reaction was carried out over 1 hour 15 minutes, while methanol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a slightly red-colored transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less.

[0657] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 12,806.

[0658] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 123.6? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 384.7? C.

Example A-23

[0659] 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene (31.00 g; 0.07 mol), diphenyldimethoxy silane (18.98 g; 0.08 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 190? C., and were stirred for 30 minutes.

[0660] Thereafter, a transesterification reaction was carried out over 1 hour 10 minutes, while methanol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a colorless and transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 3,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less.

[0661] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 46,225.

[0662] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 97.4? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 350.6? C.

Example A-24

[0663] 9,9-Bis(4-hydroxyphenyl)fluorene (24.71 g; 0.07 mol), diphenyldimethoxy silane (18.95 g; 0.08 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 9,9-bis(4-hydroxyphenyl)fluorene) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 190? C., and were stirred for 15 minutes.

[0664] Thereafter, a transesterification reaction was carried out over 1 hour and 30 minutes, while methanol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a yellowed transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 80,000 Pa, 60,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 3,000 Pa, 2,000 Pa, and 200 Pa or less.

[0665] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 27,028.

[0666] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 169.7? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 364.8? C.

Example A-25

[0667] Bis(4-hydroxyphenyl)sulfide (15.26 g; 0.07 mol), diphenyldimethoxy silane (17.42 g; 0.07 mol), and 30.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the bis(4-hydroxyphenyl)sulfide) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 190? C., and were stirred for 15 minutes.

[0668] Thereafter, a transesterification reaction was carried out over 2 hours 15 minutes, while methanol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour 20 minutes, so as to obtain a colorless and transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 90,000 Pa, 80,000 Pa, 70,000 Pa, 60,000 Pa, 50,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, and 200 Pa or less.

[0669] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 56,797.

[0670] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 73.2? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 391.6? C.

[0671] The results of the aforementioned Examples A-15 to -25 and the reference example are shown in Table 3.

TABLE-US-00003 TABLE 3 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Raw Aromatic diol compound g 2310.18 2496.50 0 0 0 0 materials/ (BPA: 2,2-Bis(4- mol 10.13 10.95 0 0 0 0 catalysts hydroxyphenyl)propane) (molar amount) Diol compound g 0 0 30.99 0 17.07 0 (BPEF: 9,9-Bis[4-(2- mol 0 0 0.07 0 0.04 0 hydroxyethoxy)phenyl]fluorene) (molar amount) Diol compound g 0 0 0 0 12.06 0 (BCF: 9,9-Bis(4-hydroxy-3- mol 0 0 0 0 0.03 0 methylphenyl)fluorene) (molar amount) Diol compound g 0 0 0 24.71 0 24.71 (BPF: 9,9-Bis(4- mol 0 0 0 0.07 0 0.07 hydroxyphenyl)fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 (ISB: Isosorbide) mol 0 0 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 0 (SPG: Spiroglycol) mol 0 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfone) mol 0 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfide) mol 0 0 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 0 (BNEF: 9,9-Bis[6-(2- mol 0 0 0 0 0 0 hydroxyethoxy)naphthalen-2- (molar amount) yl]fluorene) Aromatic diol compound g 0 0 0 0 0 0 (Biphenol: 4,4-Dihydroxy- mol 0 0 0 0 0 0 biphenyl) (molar amount) Aromatic diol compound g 0 0 0 0 0 0 (2EO-BINOL: 2,2- mol 0 0 0 0 0 0 Bishydroxyethoxy-1,1- (molar amount) binaphthyl) Diaryl carbonate g 753.04 813.00 5.28 0.83 5.26 0.83 (DPC: Diphenyl carbonate) mol 3.52 3.80 0.02 0.004 0.02 0.004 (molar amount) Diphenoxysilane compound g 1849.26 1997.20 0 0 0 1.80 (DMDPS: mol 7.58 8.19 0 0 0 0.01 Dimethyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 0 0 0 0 (DPDPS: mol 0 0 0 0 0 0 Diphenyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 13.01 18.00 12.99 16.21 (DPDMS: mol 0 0 0.05 0.07 0.05 0.07 Diphenyldimethoxysilane) (molar amount) Molar ratio mol/mol 1.10 1.09 1.11 1.10 1.10 1.10 ((Diphenoxysilane compound + DPC)/BPA) Catalyst ?mol/mol 14 3 15 15 15 15 (Cs.sub.2Co.sub.3, except for those clearly (Number of described) moles (?mol) per mol of aromatic diol compound) Reaction Final reaction temperature (? C.) 260 260 260 260 260 260 conditions Poly- Weight average molecular weight Mw (g/mol) 208,939 81,885 115,683 12,992 23,272 28,050 carbonate Percentage of polymer molecules (mass %) 0.8 0.6 0.8 2.2 1.7 1.6 copolymer with weight average molecular (product) weight of 1,000 or less Siloxane constituent unit (mol %) 67.04 65.79 58.18 91.20 58.18 91.20 (Si-containing constituent unit) Polycarbonate constituent unit (mol %) 32.96 34.21 41.82 8.80 41.82 8.80 (PC-containing constituent unit) Si mass % (mass %) 6.9 6.8 2.9 4.9 3.0 5.1 Q value (280? C./160 kgf) (?10.sup.?2 cm.sup.3/sec) 117 110 120 120 118 Glass transition temperature (Tg) (? C.) 74 75 111 166 140 171 Temperature for weight loss of (? C.) 337 381 351 361 349 339 1% (DSC) Refractive index (nd) 1.578 1.578 1.643 1.658 1.646 1.654 Abbe number (vd) 30.6 30.6 23.7 22.1 23.1 22.4 Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 Raw Aromatic diol compound g 0 0 0 0 0 materials/ (BPA: 2,2-Bis(4- mol 0 0 0 0 0 catalysts hydroxyphenyl)propane) (molar amount) Diol compound g 0 0 31.00 0 0 (BPEF: 9,9-Bis[4-(2- mol 0 0 0.07 0 0 hydroxyethoxy)phenyl]fluorene) (molar amount) Diol compound g 0 0 0 0 0 (BCF: 9,9-Bis(4-hydroxy-3- mol 0 0 0 0 0 methylphenyl)fluorene) (molar amount) Diol compound g 0 0 0 24.71 0 (BPF: 9,9-Bis(4- mol 0 0 0 0.07 0 hydroxyphenyl)fluorene) (molar amount) Diol compound g 10.22 0 0 0 0 (ISB: Isosorbide) mol 0.07 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 (SPG: Spiroglycol) mol 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 17.50 0 0 0 (Bis(4-hydroxyphenyl)sulfone) mol 0 0.07 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 15.26 (Bis(4-hydroxyphenyl)sulfide) mol 0 0 0 0 0.07 (molar amount) Diol compound g 0 0 0 0 0 (BNEF: 9,9-Bis[6-(2- mol 0 0 0 0 0 hydroxyethoxy)naphthalen-2- (molar amount) yl]fluorene) Aromatic diol compound g 0 0 0 0 0 (Biphenol: 4,4-Dihydroxy- mol 0 0 0 0 0 biphenyl) (molar amount) Aromatic diol compound g 0 0 0 0 0 (2EO-BINOL: 2,2- mol 0 0 0 0 0 Bishydroxyethoxy-1,1- (molar amount) binaphthyl) Diaryl carbonate g 0 0 0 0 0 (DPC: Diphenyl carbonate) mol 0 0 0 0 0 (molar amount) Diphenoxysilane compound g 0 0 0 0 0 (DMDPS: mol 0 0 0 0 0 Dimethyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 0 0 0 (DPDPS: mol 0 0 0 0 0 Diphenyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 17.60 17.42 18.98 18.95 17.42 (DPDMS: mol 0.07 0.07 0.08 0.08 0.07 Diphenyldimethoxysilane) (molar amount) Molar ratio mol/mol 1.03 1.02 1.10 1.10 1.02 ((Diphenoxysilane compound + DPC)/BPA) Catalyst ?mol/mol 15 30 15 15 30 (Cs.sub.2Co.sub.3, except for those clearly (Number of described) moles (?mol) per mol of aromatic diol compound) Reaction Final reaction temperature (? C.) 200 260 260 260 260 conditions Poly- Weight average molecular weight Mw (g/mol) 9,125 12,806 46,225 27,028 56,797 carbonate Percentage of polymer molecules (mass %) 1.0 5.3 1.1 1.9 3.2 copolymer with weight average molecular (product) weight of 1,000 or less Siloxane constituent unit (mol %) 100.00 100.00 100.00 100.00 100.00 (Si-containing constituent unit) Polycarbonate constituent unit (mol %) 0.00 0.00 0.00 0.00 0.00 (PC-containing constituent unit) Si mass % (mass %) 8.6 6.5 4.5 5.3 7.1 Q value (280? C./160 kgf) (?10.sup.?2 cm.sup.3/sec) >121 >121 118 119 120 Glass transition temperature (Tg) (? C.) 71 124 97 170 73 Temperature for weight loss of (? C.) 256 385 351 365 392 1% (DSC) Refractive index (nd) 1.631 1.643 1.656 1.659 Abbe number (vd) 24.5 23.9 22.3 22.9

Example A-26

[0672] 9,9-Bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (37.73 g; 0.07 mol), dimethyldiphenoxy silane (19.47 g; 0.07 mol), and 30.0 ?mol/mol sodium hydrogen carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 9,9-bis(6-hydroxynaphthyl)fluorene) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 210? C., and were stirred for 30 minutes.

[0673] Thereafter, a transesterification reaction was carried out over 1 hour and 30 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 280? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour 50 minutes, so as to obtain a yellowed transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 30,000 Pa, 27,500 Pa, 25,000 Pa, 22,500 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000, 1,000, and 200 Pa or less.

[0674] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 39,353.

[0675] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 138? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 369.3? C.

Example A-27

[0676] 4,4-Dihydroxy-biphenyl (61.04 g; 0.33 mol), dimethyldiphenoxy silane (89.64 g; 0.37 mol), and 3.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 4,4-dihydroxy-biphenyl) were added into a 200-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 220? C., and were stirred for 60 minutes.

[0677] Thereafter, a transesterification reaction was carried out over 1 hour, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 1 hPa or less, and the reaction mixture was further retained for 2 hours, so as to obtain a colorless and transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 6,000 Pa, 4,000 Pa, and 100 Pa or less.

[0678] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 46,000.

[0679] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 70.4? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 378? C.

Example A-28

[0680] 4,4-Dihydroxy-biphenyl (79.71 g; 0.43 mol), diphenyldimethoxy silane (107.42 g; 0.44 mol), and 3.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 4,4-dihydroxy-biphenyl) were added into a 200-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 220? C., and were stirred for 30 minutes.

[0681] Thereafter, a transesterification reaction was carried out over 2 hours, while methanol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 1 hPa or less, and the reaction mixture was further retained for 2 hours, so as to obtain a colorless and transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 90,000 Pa, 80,000 Pa, 70,000 Pa, 60,000 Pa, 50,000 Pa, 40,000 Pa, 20,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, and 200 Pa or less.

[0682] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 17,000.

[0683] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 110? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 345? C.

Example A-29

[0684] 4,4-Dihydroxy-biphenyl (39.06 g; 0.21 mol), dimethyldiphenoxy silane (38.58 g; 0.16 mol), diphenyl carbonate (15.60 g; 0.07 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 4,4-dihydroxy-biphenyl) were added into a 300-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 220? C., and were stirred for 20 minutes.

[0685] Thereafter, a transesterification reaction was carried out over 1 hour and 30 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 1 hPa or less, and the reaction mixture was further retained for 10 minutes, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 30,000 Pa, 25,000 Pa, 20,000 Pa, 15,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa or less.

[0686] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 33,710.

[0687] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 78.8? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 357? C.

Example A-30

[0688] 4,4-Dihydroxy-biphenyl (39.06 g; 0.21 mol), diphenyldimethoxy silane (35.00 g; 0.14 mol), diphenyl carbonate (15.60 g; 0.07 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 4,4-dihydroxy-biphenyl) were added into a 300-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 220? C., and were stirred for 20 minutes.

[0689] Thereafter, a transesterification reaction was carried out over 1 hour and 30 minutes, while methanol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 1 hPa or less, and the reaction mixture was further retained for 10 minutes, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 30,000 Pa, 25,000 Pa, 20,000 Pa, 15,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa or less.

[0690] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 11,845.

[0691] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 120? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 363? C.

Example A-31

[0692] 2,2-Bishydroxyethoxy-1,1-binaphthyl (26.18 g; 0.07 mol), dimethyldiphenoxy silane (19.82 g; 0.08 mol), and 30 ?mol/mol sodium hydrogen carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bishydroxyethoxy-1,1-binaphthyl) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 210? C., and were stirred for 35 minutes.

[0693] Thereafter, a transesterification reaction was carried out over 1 hour and 30 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 1 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a colorless and transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,500 Pa, 25,000 Pa, 22,500 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa or less.

[0694] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 19,975.

[0695] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 54? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 296? C.

Example A-32

[0696] 2,2-Bishydroxyethoxy-1,1-binaphthyl (26.18 g; 0.07 mol), diphenyl carbonate (5.40 g; 0.03 mol), dimethyldiphenoxy silane (12.65 g; 0.05 mol), and 30 ?mol/mol sodium hydrogen carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bishydroxyethoxy-1,1-binaphthyl) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 220? C., and were stirred for 1 hour.

[0697] Thereafter, a transesterification reaction was carried out over 1 hour 10 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 1 hPa or less, and the reaction mixture was further retained for 1 hour 20 minutes, so as to obtain a polycarbonate copolymer having a colorless and transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 27,500 Pa, 25,000 Pa, 22,500 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 100 Pa or less.

[0698] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 32,178.

[0699] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 74? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 317? C.

Example A-33

[0700] Isosorbide (10.22 g; 0.07 mol), diphenyl carbonate (5.20 g; 0.02 mol), dimethyldiphenoxy silane (12.86 g; 0.05 mol), and 15.0 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the isosorbide) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 200? C., and were stirred for 30 minutes.

[0701] Thereafter, a transesterification reaction was carried out over 1 hour 20 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour and 30 minutes, so as to obtain a polycarbonate copolymer having a yellowed transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 30,000 Pa, 25,000 Pa, 20,000 Pa, 15,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less.

[0702] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 39,378.

[0703] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 55? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 242? C.

Example A-34

[0704] 3,9-Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (21.28 g; 0.07 mol), dimethyldiphenoxy silane (19.82 g; 0.08 mol), and 30.0 ?mol/mol sodium hydrogen carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 210? C., and were stirred for 30 minutes.

[0705] Thereafter, a transesterification reaction was carried out over 1 hour 50 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour, so as to obtain a colorless and transparent arylene siloxane. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 30,000 Pa, 25,000 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less.

[0706] The Mw of the arylene siloxane was measured using GPC, and as a result, it was 15,708.

[0707] The Tg of the above-described arylene siloxane was measured using DSC, and as a result, it was 51? C. The weight loss of the above-described arylene siloxane was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 236? C.

Example A-35

[0708] 3,9-Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (21.28 g; 0.07 mol), diphenyl carbonate (5.20 g; 0.02 mol), dimethyldiphenoxy silane (12.86 g; 0.05 mol), and 30.0 ?mol/mol sodium hydrogen carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 210? C., and were stirred for 30 minutes.

[0709] Thereafter, a transesterification reaction was carried out over 1 hour and 30 minutes, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 2 hPa or less, and the reaction mixture was further retained for 1 hour, so as to obtain a polycarbonate copolymer having a transparent arylene siloxane structure. Besides, upon the pressure reduction, the pressure was adjusted such that the atmospheric pressure was gradually changed to 30,000 Pa, 25,000 Pa, 20,000 Pa, 17,500 Pa, 15,000 Pa, 12,500 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa or less.

[0710] The Mw of the siloxane-containing polycarbonate copolymer was measured using GPC, and as a result, it was 68,693.

[0711] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 63? C. The weight loss of the above-described copolymer was measured using TG-DTA, and as a result, the temperature necessary for a weight loss of 1% was 252? C.

Comparative Example A-1

[0712] 2,2-Bis(4-hydroxyphenyl)propane (17.51 g; 0.08 mmol), dimethyldiphenoxy silane (20.93 g; 0.09 mol), and 7 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0713] Thereafter, a transesterification reaction was carried out over 1 hour, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 2 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0714] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 63,257.

[0715] The Tg of the above-described copolymer was measured using DSC, and as a result, it was 54? C.

Comparative Example A-2

[0716] The Mw of a polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.; Iupilon S-3000) was measured using GPC, and as a result, it was 51,252.

[0717] The Tg of the above-described polycarbonate was measured using DSC, and as a result, it was 149? C.

Comparative Example A-3

[0718] Iupizeta EP6000 manufactured by Mitsubishi Gas Chemical Company, Inc., namely, a polycarbonate resin comprising BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene) as a diol compound, was used in Comparative Example A-3. The Mw of the polycarbonate resin of Comparative Example A-3 was 30000, the Q value thereof was 97?10.sup.?2 cm.sup.3/sec, and the Tg thereof was 142? C., the refractive index (nd) thereof was 1.638, and the Abbe number (?d) thereof was 23.5.

[0719] It was confirmed that, in Examples A-17, -19, and -23, in which a similar diol compound was used, fluidity could be improved (i.e., the Q value could be increased) without largely changing the optical properties, compared with Comparative Example A-3.

[0720] The results of the aforementioned Examples A-26 to A-35 and Comparative Example A-1 and -2 are shown in Table 4.

TABLE-US-00004 TABLE 4 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Ex. 31 Raw Aromatic diol compound g 0 0 0 0 0 0 materials/ (BPA: 2,2-Bis(4- mol 0 0 0 0 0 0 catalysts hydroxyphenyl)propane) (molar amount) Diol compound g 0 0 0 0 0 0 (BPEF: 9,9-Bis[4-(2- mol 0 0 0 0 0 0 hydroxyethoxy)phenyl]fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 (BCF: 9,9-Bis(4-hydroxy-3- mol 0 0 0 0 0 0 methylphenyl)fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 (BPF: 9,9-Bis(4- mol 0 0 0 0 0 0 hydroxyphenyl)fluorene) (molar amount) Diol compound g 0 0 0 0 0 0 (ISB: Isosorbide) mol 0 0 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 0 (SPG: Spiroglycol) mol 0 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfone) mol 0 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfide) mol 0 0 0 0 0 0 (molar amount) Diol compound g 37.73 0 0 0 0 0 (BNEF: 9,9-Bis[6-(2- mol 0.07 0 0 0 0 0 hydroxyethoxy)naphthalen-2- (molar amount) yl]fluorene) Aromatic diol compound g 0 61.04 79.71 39.06 39.06 0 (Biphenol: 4,4-Dihydroxy- mol 0 0.33 0.43 0.21 0.21 0 biphenyl) (molar amount) Aromatic diol compound g 0 0 0 0 0 26.18 (2EO-BINOL: 2,2- mol 0 0 0 0 0 0.07 Bishydroxyethoxy-1,1- (molar amount) binaphthyl) Diaryl carbonate g 0 0 0 15.60 15.60 0 (DPC: Diphenyl carbonate) mol 0 0 0 0.07 0.07 0 (molar amount) Diphenoxysilane compound g 19.47 89.64 0 38.58 0 19.82 (DMDPS: mol 0.08 0.37 0 0.16 0 0.08 Dimethyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 0 0 0 0 (DPDPS: mol 0 0 0 0 0 0 Diphenyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 107.42 0 35.00 0 (DPDMS: mol 0 0 0.44 0 0.14 0 Diphenyldimethoxysilane) (molar amount) Molar ratio mol/mol 1.14 1.12 1.03 1.10 1.03 1.16 ((Diphenoxysilane compound + DPC)/BPA) Catalyst ?mol/mol 30 3 3 15 15 30 (Cs.sub.2Co.sub.3, except for those clearly (Number of (NaHCO.sub.3) (NaHCO.sub.3) described) moles (?mol) per mol of aromatic diol Reaction Final reaction temperature (? C.) 280 260 260 260 260 260 conditions Poly- Weight average molecular weight Mw (g/mol) 39,353 46,000 17,000 33,710 11,845 19,975 carbonate Percentage of polymer molecules (mass %) 1.5 0.03 0.01 0.81 9.0 copolymer with weight average molecular (product) weight of 1,000 or less Siloxane constituent unit (mol %) 100.00 100 100 67.86 67.23 100 (Si-containing constituent unit) Polycarbonate constituent unit (mol %) 0.00 0 0 32.14 32.77 0 (PC-containing constituent unit) Si mass % (mass %) 4.7 11.6 7.6 8.2 6.0 6.5 Q value (280? C./160 kgf) (?10.sup.?2 cm.sup.3/sec) 35 115 117 96 91 >121 Glass transition temperature (Tg) (? C.) 138 70 110 79 120 54 Temperature for weight loss of (? C.) 369 378 345 357 363 296 1% (DSC) Refractive index (nd) 1.667 1.633 1.653 1.636 1.650 1.644 Abbe number (vd) 19.2 22.8 22.5 21.9 21.6 20.0 Comp. Comp. Ex. 32 Ex. 33 Ex. 34 Ex. 35 Ex. 1 Ex. 2 Raw Aromatic diol compound g 0 0 0 0 17.51 BPA-type materials/ (BPA: 2,2-Bis(4- mol 0 0 0 0 0.08 poly- catalysts hydroxyphenyl)propane) (molar amount) carbonate Diol compound g 0 0 0 0 0 resin (BPEF: 9,9-Bis[4-(2- mol 0 0 0 0 0 (Iupilon hydroxyethoxy)phenyl]fluorene) (molar amount) S-3000) Diol compound g 0 0 0 0 0 (BCF: 9,9-Bis(4-hydroxy-3- mol 0 0 0 0 0 methylphenyl)fluorene) (molar amount) Diol compound g 0 0 0 0 0 (BPF: 9,9-Bis(4- mol 0 0 0 0 0 hydroxyphenyl)fluorene) (molar amount) Diol compound g 0 10.22 0 0 0 (ISB: Isosorbide) mol 0 0.07 0 0 0 (molar amount) Diol compound g 0 0 21.28 21.28 0 (SPG: Spiroglycol) mol 0 0 0.07 0.07 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfone) mol 0 0 0 0 0 (molar amount) Aromatic diol compound g 0 0 0 0 0 (Bis(4-hydroxyphenyl)sulfide) mol 0 0 0 0 0 (molar amount) Diol compound g 0 0 0 0 0 (BNEF: 9,9-Bis[6-(2- mol 0 0 0 0 0 hydroxyethoxy)naphthalen-2- (molar amount) yl]fluorene) Aromatic diol compound g 0 0 0 0 0 (Biphenol: 4,4-Dihydroxy- mol 0 0 0 0 0 biphenyl) (molar amount) Aromatic diol compound g 26.18 0 0 0 (2EO-BINOL: 2,2- mol 0.07 0 0 0 Bishydroxyethoxy-1,1- (molar amount) binaphthyl) Diaryl carbonate g 5.40 5.20 0 5.20 0 (DPC: Diphenyl carbonate) mol 0.03 0.02 0 0.02 0 (molar amount) Diphenoxysilane compound g 12.65 12.86 19.82 12.86 20.93 (DMDPS: mol 0.05 0.05 0.08 0.05 0.09 Dimethyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 0 0 0 (DPDPS: mol 0 0 0 0 0 Diphenyldiphenoxysilane) (molar amount) Diphenoxysilane compound g 0 0 0 0 0 (DPDMS: mol 0 0 0 0 0 Diphenyldimethoxysilane) (molar amount) Molar ratio mol/mol 1.10 1.10 1.16 1.10 1.12 ((Diphenoxysilane compound + DPC)/BPA) Catalyst ?mol/mol 30 15 30 30 7 (Cs.sub.2Co.sub.3, except for those clearly (Number of (NaHCO.sub.3) (NaHCO.sub.3) (NaHCO.sub.3) described) moles (?mol) per mol of aromatic diol Reaction Final reaction temperature (? C.) 260 260 260 260 260 conditions Poly- Weight average molecular weight Mw (g/mol) 32,178 39,378 15,708 68,693 63,257 51,252 carbonate Percentage of polymer molecules (mass %) 7.4 0.50 1.4 1.0 1.6 0.15 copolymer with weight average molecular (product) weight of 1,000 or less Siloxane constituent unit (mol %) 64.37 61.98 100 61.40 100 0 (Si-containing constituent unit) Polycarbonate constituent unit (mol %) 35.63 38.02 0 38.60 0 100 (PC-containing constituent unit) Si mass % (mass %) 4.3 9.1 7.8 4.9 9.8 0 Q value (280? C./160 kgf) (?10.sup.?2 cm.sup.3/sec) >121 >121 >121 116 8 Glass transition temperature (Tg) (? C.) 74 55 51 63 54 149 Temperature for weight loss of (? C.) 317 242 236 252 335 420 1% (DSC) Refractive index (nd) 1.653 1.511 1.482 1.490 1.577 1.583 Abbe number (vd) 19.4 54.8 54.3 49.0 28.8 30.2

Example A-36

[0721] The polycarbonate copolymer obtained in Example A-3 (10 g) and 190 g of a polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.; Iupilon S-3000) were kneaded and extruded at 280? C. using a kneading extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.; LABO PLASTOMILL 4C150). The Q value of the obtained composition was 11.9 (?10.sup.?2 cm.sup.3/sec). In addition, the composition was dried using a dryer at 110? C. for 12 hours, and it was then molded into a test piece for use in a Charpy impact test, using an injection molding machine (manufactured by Shinko Sellbic Co., Ltd.; C-Mobile) at a resin temperature of 300? C. and at a mold temperature of 90? C. Thereafter, a notched Charpy impact test was carried out in accordance with JIS-K7111. As a result, the Charpy impact strength was 60.9 kJ/m.sup.2.

Example A-37

[0722] The polycarbonate copolymer obtained in Example A-4 (10 g) and 190 g of a polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.; Iupilon S-3000) were kneaded and extruded at 280? C. using a kneading extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.; LABO PLASTOMILL 4C150). The Q value of the obtained composition was 14.1 (?10.sup.?2 cm.sup.3/sec). In addition, the composition was dried using a dryer at 110? C. for 12 hours, and it was then molded into a test piece for use in a Charpy impact test, using an injection molding machine (manufactured by Shinko Sellbic Co., Ltd.; C-Mobile) at a resin temperature of 300? C. and at a mold temperature of 90? C. Thereafter, a notched Charpy impact test was carried out in accordance with JIS-K7111. As a result, the Charpy impact strength was 65.8 kJ/m.sup.2.

Example A-38

[0723] The polycarbonate copolymer obtained in Example A-16 (150 g) and 1850 g of a polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.; Iupilon E-2000) were kneaded at a resin temperature of 280? C. using a kneading extrusion injection molding machine (high-speed injection molding machine, SODICK TR100EH), and were then subjected to injection molding under conditions of a mold temperature of 80? C. and a retained pressure of 90 MPa, so as to mold the mixture into a test piece for use in a Charpy impact test. A notched Charpy impact test was carried out in accordance with JIS-K7111. As a result, the Charpy impact strength was 70.1 kJ/m.sup.2. Moreover, the Q value of the obtained composition was 5.5 (?10.sup.?2 cm.sup.3/sec).

Example A-39

[0724] The polycarbonate copolymer obtained in Example A-16 (300 g) and 1700 g of a polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.; Iupilon E-2000) were kneaded at a resin temperature of 280? C. using a kneading extrusion injection molding machine (high-speed injection molding machine, SODICK TR100EH), and were then subjected to injection molding under conditions of a mold temperature of 80? C. and a retained pressure of 90 MPa, so as to mold the mixture into a test piece for use in a Charpy impact test. A notched Charpy impact test was carried out in accordance with JIS-K7111. As a result, the Charpy impact strength was 76.7 kJ/m.sup.2. Moreover, the Q value of the obtained composition was 8.1 (?10.sup.?2 cm.sup.3/sec).

Example A-40

[0725] The polycarbonate copolymer obtained in Example A-16 (600 g) and 1400 g of a polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.; Iupilon E-2000) were kneaded at a resin temperature of 280? C. using a kneading extrusion injection molding machine (high-speed injection molding machine, SODICK TR100EH), and were then subjected to injection molding under conditions of a mold temperature of 80? C. and a retained pressure of 90 MPa, so as to mold the mixture into a test piece for use in a Charpy impact test. A notched Charpy impact test was carried out in accordance with JIS-K7111. As a result, the Charpy impact strength was 6.9 kJ/m.sup.2. Moreover, the Q value of the obtained composition was 17.2 (?10.sup.?2 cm.sup.3/sec).

Comparative Example A-4

[0726] The Q value of a polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.; Iupilon S-3000) was 8.0 (?10.sup.?2 cm.sup.3/sec). In addition, the polycarbonate was dried at 110? C. for 12 hours, using a dryer, and was then molded into a test piece for use in a Charpy impact test, using an injection molding machine (manufactured by Shinko Sellbic Co., Ltd.; C-Mobile) at a resin temperature of 300? C. and at a mold temperature of 90? C. Thereafter, a notched Charpy impact test was carried out in accordance with JIS-K7111. As a result, the Charpy impact strength was 62.9 kJ/m.sup.2.

Comparative Example A-5

[0727] 2000 g of a polycarbonate (manufactured by Mitsubishi Gas Chemical Company, Inc.; Iupilon E-2000) was kneaded at a resin temperature of 300? C. using a kneading extrusion injection molding machine (high-speed injection molding machine, SODICK TR100EH), and was then subjected to injection molding under conditions of a mold temperature of 80? C. and a retained pressure of 90 MPa, so as to mold the mixture into a test piece for use in a Charpy impact test. A notched Charpy impact test was carried out in accordance with JIS-K7111. As a result, the Charpy impact strength was 72.7 kJ/m.sup.2. Moreover, the Q value of the obtained composition was 2.8 (?10.sup.2 cm.sup.3/sec).

[0728] The results of Examples A-36 to -40 and Comparative Examples A-4 and -5 are shown in the following Table 5.

TABLE-US-00005 TABLE 5 Comp. Comp. Ex. A-36 Ex. A-37 Ex. A-38 Ex. A-39 Ex. A-40 Ex. A-4 Ex. A-5 Raw BPA-type polycarbonate resin g 190 190 200 materials (Iupilon S-3000) Siloxane-containing polycarbonate g 10 copolymer (Ex. A-3) Siloxane-containing polycarbonate g 10 copolymer (Ex. A-4) Siloxane-containing polycarbonate g 150 300 600 copolymer (Ex. A-16) BPA-type polycarbonate resin g 1850 1700 1400 2000 (Iupilon E-2000) Total g 200 200 2000 2000 2000 200 2000 Evaluation Charpy impact test (notched) (kJ/m.sup.2) 60.9 65.8 70.1 76.7 6.9 62.9 72.7 of physical Relative value 97 105 96 106 9 100 100 properties of (value (%) composition based on value of Comp. Ex. 3 (or 4) Q value (280? C., 160 kgf) (?10.sup.?2 cm.sup.3/sec) 11.9 14.1 5.5 8.1 17.2 8.0 2.8 Relative value 149 176 196 289 614 100 100 (value (%) based on value of Comp. Ex. 3 (or 4)

[Examples of Polysiloxane Compound]

[0729] Hereafter, examples of the polysiloxane compound will be described.

[0730] Applying GPC (gel permeation chromatography), and using chloroform as a developing solvent, a calibration curve was produced using standard polystyrene with a known molecular weight (molecular weight distribution=1). Based on this calibration curve, the weight average molecular weight (Mw) in terms of polystyrene was calculated from the retention time of GPC.

[0731] The glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC). In the obtained DSC curve, the glass transition temperature (Tg) was obtained from an intersection of the baseline on the low temperature side extended to the high temperature side, with a tangent drawn with a point that made maximum the gradient of the curve of the stepwise change part of the glass transition.

(Synthesis Example 2) Synthesis of Dimethyldiphenoxy Silane

[0732] Decamethylcyclopentasiloxane (7.5 g; 20.2 mmol; Si molar amount: 101.0 mmol), diphenyl carbonate (21.6 g; 101.0 mmol), and cesium carbonate used as a catalyst (33 mg; 0.1 mmol) were substituted in a nitrogen atmosphere, and were stirred at 200? C. for 60 minutes.

[0733] Subsequently, the reaction mixture was cooled to 40? C., and was then distilled under reduced pressure at a degree of pressure reduction of 4hPa and at 150? C., so as to obtain 23.7 g of a colorless oily component.

[0734] The obtained oily component was analyzed by 1H-NMR, and it was confirmed that the oily component was dimethyldiphenoxy silane. (.sup.1H-NMR (CDCl.sub.3, 500 MHz, 6; ppm)=0.378 (s; 6H), 6.942, 6.944 (d; 4H), 6.959, 6.961, 6.995 (t; 2H), 7.230, 7.245, 7.257 (t; 4H)). The molar yield was found to be 96.0%.

Example B-1

[0735] 2,2-Bis(4-hydroxyphenyl)propane (30.03 g; 0.13 mol), dimethyldiphenoxy silane (33.50 g; 0.14 mol), and 11 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0736] Thereafter, a transesterification reaction was carried out over 1.5 hours, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 240? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0737] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 26,699.

Example B-2

[0738] 2,2-Bis(4-hydroxyphenyl)propane (30.03 g; 0.13 mol), dimethyldiphenoxy silane (34.40 g; 0.14 mol), and 11 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0739] Thereafter, a transesterification reaction was carried out over 1.5 hours, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 240? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0740] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 33,521.

Example B-3

[0741] 2,2-Bis(4-hydroxyphenyl)propane (30.05 g; 0.13 mol), dimethyldiphenoxy silane (34.69 g; 0.14 mol), and 11 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0742] Thereafter, a transesterification reaction was carried out over 1.5 hours, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 240? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0743] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 30,603.

Example B-4

[0744] 2,2-Bis(4-hydroxyphenyl)propane (30.03 g; 0.13 mol), dimethyldiphenoxy silane (35.10 g; 0.14 mol), and 11 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0745] Thereafter, a transesterification reaction was carried out over 1.5 hours, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 240? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0746] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 36,940.

Example B-5

[0747] 2,2-Bis(4-hydroxyphenyl)propane (30.08 g; 0.13 mol), dimethyldiphenoxy silane (36.00 g; 0.15 mol), and 11 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0748] Thereafter, a transesterification reaction was carried out over 1.5 hours, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 240? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0749] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 39,994.

[0750] The Tg of the polyarylene siloxane was measured using DSC, and as a result it was 49? C.

Example B-6

[0751] 2,2-Bis(4-hydroxyphenyl)propane (30.03 g; 0.13 mol), dimethyldiphenoxy silane (37.38 g; 0.15 mol), and 11 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0752] Thereafter, a transesterification reaction was carried out over 1.5 hours, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 240? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0753] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 34,196.

Example B-7

[0754] 2,2-Bis(4-hydroxyphenyl)propane (17.51 g; 0.077 mol), dimethyldiphenoxy silane (20.93 g; 0.086 mol), and 7 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0755] Thereafter, a transesterification reaction was carried out over 1 hour, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0756] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 63,257.

[0757] The Tg of the polyarylene siloxane was measured using DSC, and as a result it was 54? C.

Synthesis Example 3

[0758] Octaphenylcyclotetrasiloxane represented by the following formula (3) (14.9 g; 0.19 mol), diphenyl carbonate (16.1 g; 0.08 mol), and cesium carbonate used as a catalyst (33 mg; 0.1 mmol) were substituted in a nitrogen atmosphere, and were stirred at 200? C. for 10 minutes. After cooling to room temperature, 20 g of heptane was added to the solidified reaction mixture, and the temperature of the mixture was heated to 90? C., and was then subjected to hot filtration. The obtained filtrate was left at room temperature for 3 days, so that a white crystal was precipitated. Furthermore, a crystal obtained by filtration of the mixture, to which 10 g of heptane cooled to 5? C. had been added, was removed from the filter, and was then dried at 40? C. at a degree of pressure reduction of 1 hPa for 45 hours. As a result, 24.1 g of white powders were obtained. As a result of an analysis by .sup.1H-NMR, the obtained powders were confirmed to be diphenyldiphenoxy silane. Diphenyldiphenoxy silane (.sup.1H-NMR (CDCl3, 500 MHz, ?; ppm)=6.915, 6.927, 6.939, 6.952, 6.965 (p; 6H), 7.142, 7.155, 7.169 (t; 4H), 7.354, 7.366, 7.379 (t; 4H), 7.425, 7.437, 7.449 (t; 2H)), 7.750, 7.762 (d; 4H). The molar yield was found to be 81.1%.

##STR00064##

Example B-8

[0759] 2,2-Bis(4-hydroxyphenyl)propane (11.75 g; 0.052 mol), diphenyldiphenoxy silane (20.25 g; 0.055 mol), and 20 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0760] Thereafter, a transesterification reaction was carried out over 1 hour, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 260? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0761] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 24,482.

[0762] The Tg of the polyarylene siloxane was measured using DSC, and as a result it was 89? C.

Comparative Example B-1

[0763] 2,2-Bis(4-hydroxyphenyl)propane (20.00 g; 0.088 mol) and dimethyldiphenoxy silane (23.62 g; 0.097 mol) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0764] Thereafter, the inside of the system was set to be 240? C. and a degree of pressure reduction was set to be 4 hPa (400 Pa) or less, and a transesterification reaction was attempted. However, the raw materials were distilled away, and the reaction did not progress.

Comparative Example B-2

[0765] 2,2-Bis(4-hydroxyphenyl)propane (21.28 g; 0.093 mol), dimethyldiphenoxy silane (25.12 g; 0.10 mol), and 11 ?mol/mol cesium carbonate used as a catalyst (wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0766] Thereafter, the temperature in the system was increased to 240? C. under normal pressure over 1.5 hours, and was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0767] The Mw of the polyarylene siloxane was measured using GPC, and as a result, it was 1,547.

Comparative Example B-3

[0768] 2,2-Bis(4-hydroxyphenyl)propane (29.96 g; 0.13 mol), dimethyldiphenoxy silane (36.10 g; 0.15 mol), and 16600 ?mol/mol cesium carbonate used as a catalyst (or 16.6 mmol/mol: wherein the amount of the catalyst indicates a relative number of moles to the 2,2-bis(4-hydroxyphenyl)propane) were added into a 100-ml four-neck flask equipped with a stirrer, and the inside of the reaction system was then substituted in a nitrogen atmosphere. The raw materials were melted by heating at 180? C., and were stirred for 30 minutes.

[0769] Thereafter, a transesterification reaction was carried out over 1 hour, while phenol distilled from the reaction system was condensed in a cooling tube and was removed. The inside of the system was set at 240? C. and a degree of pressure reduction was set at 4 hPa or less, and the reaction mixture was further retained for 1.5 hours, so as to obtain a colorless and transparent polyarylene siloxane.

[0770] The Mw of the colorless and transparent polyarylene siloxane was measured using GPC, and as a result, it was 886.

Comparative Example B-4

[0771] 2,2-Bis(4-hydroxyphenyl)propane (30.75 g; 0.14 mol) and dimethyldiphenoxy silane (36.90 g; 0.15 mol) were added into a 100-ml four-neck flask equipped with a stirrer.

[0772] Thereafter, the inside of the reaction system was immediately set to be 240? C. and a degree of pressure reduction was set to be 4 hPa (400 Pa) or less, and a transesterification reaction was attempted. However, the raw materials were distilled away, and the reaction did not progress.

[0773] The results of individual examples and comparative examples are shown in Table 6.

TABLE-US-00006 TABLE 6 Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42 Ex. 43 Raw Aromatic diol compound: g 30.03 30.03 30.05 30.03 30.08 30.03 materials/ (BPA: 2,2- mol 0.13 0.13 0.13 0.13 0.13 0.13 catalysts bis(4-hydroxyphenyl)propane) (molar amount) Diphenoxysilane compound: g 33.50 34.40 34.69 35.10 36.00 37.38 DMDPS mol 0.14 0.14 0.14 0.14 0.15 0.15 (dimethyldiphenoxysilane) (molar amount) (only in Ex. 8, DPDPS (diphenyldiphenoxysilane)) Diphenoxysilane compound/ (molar ratio) 1.04 1.07 1.08 1.09 1.12 1.16 BPA Catalyst (Cs.sub.2CO.sub.3) ?mol/mol 11 11 11 11 11 11 (Number of moles (?mol) per mol of aromatic diol compound) Reaction Reaction temperature (? C.) 240 240 240 240 240 240 conditions Polyarylene Weight average molecular Mw (g/mol) 26,699 33,521 30,603 36,940 39,994 34,196 siloxane weight compound Glass transition temperature (? C.) 49 (product) Remarks Comp. Comp. Comp. Comp. Ex. 44 Ex. 45 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Raw Aromatic diol compound: g 17.51 11.75 20.00 21.28 29.96 30.75 materials/ (BPA: 2,2- mol 0.077 0.052 0.088 0.093 0.13 0.14 catalysts bis(4-hydroxyphenyl)propane) (molar amount) Diphenoxysilane compound: g 20.93 20.25 23.62 25.12 36.10 36.90 DMDPS mol 0.086 0.055 0.097 0.10 0.15 0.15 (dimethyldiphenoxysilane) (molar amount) (only in Ex. 8, DPDPS (diphenyldiphenoxysilane)) Diphenoxysilane compound/ (molar ratio) 1.12 1.07 1.10 1.10 1.13 1.12 BPA Catalyst (Cs.sub.2CO.sub.3) ?mol/mol 7 20 0 11 16,600 11 (Number of moles (?mol) per mol of aromatic diol compound) Reaction Reaction temperature (? C.) 260 260 240 240 240 240 conditions Polyarylene Weight average molecular Mw (g/mol) 63,257 24,482 1,547 886 siloxane weight compound Glass transition temperature (? C.) 54 89 (product) Remarks Raw Reacted Pressure materials under reduction at were distilled normal initiation of away, and the pressure reaction: raw reaction did (without materials were not progress vacuum distilled away, (without distillation) and were not catalysts). polymerized.

METHODS FOR PRODUCING POLYCARBONATE COPOLYMER AND POLYSILOXANE COMPOUND, POLYCARBONATE COPOLYMER, POLYSILOXANE COMPOUND, COMPOSITION, AND MOLDED BODY

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