Process for producing high impact resistant polycarbonate

Abstract: High impact resistant polycarbonate, a process for producing said polycarbonate, and a polycarbonate resin composition are disclosed. This polycarbonate consists of a main chain with a cumylphenoxy group, as a terminal group, bonded to at least one end thereof, said main chain comprising a repeating unit represented by the formula (I): and has a viscosity average molecular weight of at least 10,000 and an acetone soluble content of not more than 3.5 wt%. The polycarbonate can be efficiently produced by the process of the invention. The composition comprises a polycarbonate resin and a specific amount of a phosphorus-based antioxidant.

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing high impact resistant polycarbonate More particularly, it relates to a process for producing high impact resistant polycarbonate resin having cumylphenoxy group as terminal group(s), a viscosity average molecular weight of at least 10,000 and an acetone soluble content of not more than 3.5% by weight. 2. Description of Related Art A process for producing polycarbonate using cumylphenol as a terminator or polymerization modifier has heretofore been known, as described in Japanese Patent Application Laid-Open No. 20993/1976. The polycarbonate produced by this process, however, suffers from a disadvantage in that impact resistance is not sufficiently high, because it is produced by the conventional process with no special modifications except that cumylphenol is used as a terminator. As a result of extensive investigations, it has been found that the polycarbonate produced by the process described in Japanese Patent Application Laid-Open No. 20993/1976, has the acetone soluble content of 3.5% by weight or more, which is mainly responsible for a reduction in impact resistance. Based on the above findings, further investigations have been made to develop a process for producing polycarbonate which is excellent in impact resistance. As a result, it has been found that if a polycarbonate oligomer and bisphenol A as polymerization starting materials and cumylphenol as a terminator are first reacted under the turbulent flow condition and, thereafter, an aqueous solution of alkali hydroxide is added thereto and the resulting mixture is further reacted under the laminar flow condition, there can be obtained novel polycarbonate which has a decreased acetone soluble content and is of improved impact resistance. Polycarbonate is generally excellent in heat resistance, mechanical characteristics (particularly impact resistance), optical characteristics and electrical characteristics, and further is low in shrinkage during molding because it is an amorphous polymer. Thus it has been widely used in production of electric parts, illumination devices, OA (office automation) devices, construction materials, automobile parts, and so forth, particularly as a typical engineering plastic material. SUMMARY OF THE INVENTION An object of the present invention is to provide a process for efficiently producing a polycarbonate resin having improved impact resistance. Other objects and the advantages of the present invention will become apparent from the following explanation. The present invention relates to a process for producing high impact resistant polycarbonate consisting of a main chain and terminal groups bonded thereto, said main chain consisting essentially of a repeating unit represented by the formula (I): and at least one of said terminal groups being a cumylphenoxy group represented by the formula (II): and having a viscosity average molecular weight of at least 10,000 and an acetone soluble content of not more than 3.5% by weight, which comprises the following steps: i) preparing a polycarbonate oligomer solution having (a) moles of chloroformate groups, by reacting bisphenol A and phosgene in a solvent, ii) mixing the polycarbonate oligomer solution with an aqueous solution containing (c) moles of bisphenol A and (d) moles of alkali hydroxide, iii) adding thereto (b) moles of cumylphenol and (f) moles of a tertiary amine, iv) stirring the resulting mixture under turbulent flow conditions at at least 400 rpm, v) adding an aqueous solution of (e) moles of alkali hydroxide at the point in time when the viscosity of the reaction mixture increases, and vi) subsequently continuing the reaction in a laminar flow condition at not more than 300 rpm, wherein the proportion of each component is chosen within the following ranges: 0.04/1 < b/a < 0.17/1, 0.40/1 < c/a < 0.55/1, 2.02/1 < d/c < 2.50/1, 1.40/1 < (d + e)/a < 1.60/1, 1.0x10 -3 < f/a < 5.0x10 -3 wherein a = mole number of the chloroformate group of the polycarbonate oligomer, b = mole number of cumylphenol, c = mole number of bisphenol A to be used in the polymerization d = mole number of alkali hydroxide contained in an aqueous alkali hydroxide solution in which bisphenol A is dissolved, e = mole number of alkali hydroxide contained in an aqueous alkali hydroxide solution to be added at the point of time that the flow of the reaction mixture is changed from a turbulent flow to a laminar flow, and f = mole number of tertiary amine. DESCRIPTION OF PREFERRED EMBODIMENTS The polycarbonate obtained is a polymer comprising the repeating unit represented by the formula (I), with a cumylphenoxy group (p-cumylphenoxy group) bonded at at least one terminal thereof, preferably with cumylphenoxy groups bonded at both terminals thereof. If the terminal group is a p-tert-butylphenoxy group which has been well known as a terminal group for the conventional polycarbonate resins, the resulting polycarbonate resin is not satisfactory in impact resistance. The viscosity average molecular weight of the polycarbonate obtained is at least 10,000, preferably 10,000 to 50,000 and particularly preferably 15,000 to 30,000. If the viscosity average molecular weight is less than 10,000, impact resistance is not sufficiently high. The acetone soluble content of the polycarbonate obtained is not more than 3.5% by weight. If the acetone soluble content is more than 3.5% by weight, impact resistance is not sufficiently high. The acetone soluble content was measured as follows: A polycarbonate sample was ground and filtered with a 100 mesh metal screen. Then, 15 g of the sample having passed through the metal screen was placed in a cylindrical filter paper No. 84 (28 mm x 100 mm) and extracted with 300 milliliters (ml) of acetone in a Soxhlet extractor by refluxing it for 8 hours in such a manner that 20 ml of the acetone was refluxed once per 3-4 minutes. Then, the acetone was evaporated, and the residue was weighed. Based on the weight of the residue, the acetone soluble content was determined, and it was indicated in percent by weight. The polycarbonate obtained comprises, as described above, a main chain comprising the repeating unit represented by the formula (I) and a cumylphenoxy group or cumylphenoxy groups bonded thereto as a terminal group or terminal groups, as represented by the formula (II). The polycarbonate obtained can be produced by various methods. It is, however, quite difficult to produce polycarbonate having an acetone soluble content of not more than 3.5% by weight by the conventional methods. In accordance with the process of the invention, the polycarbonate can be produced with high efficiency and high quality. In accordance with the process of the invention, a polycarbonate oligomer previously derived from bisphenol A and phosgene, and bisphenol A are used as polymerization starting materials, and as a terminator, cumylphenol is added to the reaction system. In addition, if necessary, an organic solvent such as methylene chloride, chloroform, chlorobenzene, carbon tetrachloride and the like, and a catalyst such as tertiary amines (e.g., triethylamine) are added to prepare a reaction mixture. In this case, bisphenol A is added after dissolving in an aqueous solution of alkali hydroxide such as sodium hydroxide and potassium hydroxide. In the process of the invention, the above components are first reacted with each other while stirring so that the reaction mixture is in a turbulent flow condition. In connection with this stirring is carried out at 400 rpm or more. In connection with the reaction time, it varies with various conditions and cannot be determined unconditionally. In general, it suffices that at a stirring speed of 400 rpm or more, the reaction is carried out for at least one minute. The above reaction in a turbulent flow condition is continued until the viscosity of the reaction mixture increases. At this point of time that the viscosity of the reaction mixture increases, an aqueous alkali hydroxide (e.g., sodium hydroxide, potassium hydroxide and the like) solution is added and at the same time, stirring conditions are changed so that the flow of the reaction mixture is converted from a turbulent flow to a laminar flow. In this state, the reaction is continued. Stirring conditions under which the reaction mixture is in a laminar flow condition are influenced by the viscosity of the reaction mixture and so forth and cannot be determined unconditionally. Stirring is carried out at a speed of not more than 300 rpm. In connection with the reaction time, it varied with various conditions and cannot be determined unconditionally. In general, it suffices that at a stirring speed of not more than 300 rpm, the reaction is carried out for 0.5 to 2 hours. In the process of the invention, the flow of the reaction mixture is changed from a turbulent flow to a laminar flow at the point of time that the viscosity of the reaction mixture increases. This increase in viscosity, however, cannot be specified numerically. Thus it suffices that the point of time that the flow of the reaction mixture is changed is determined by observing with the eye a change in viscosity of the reaction mixture. This determination can be made relatively easily in practice. In the process of the invention, the polymerization reaction is carried out according to the steps as described above. It is preferred that the proportion of each component at each reaction step be chosen within the range as described below. 0.04 < b/a < 0.17 0.40 < c/a < 0.55 2.02 < d/c < 2.50 1.40 < (d + e)/a < 1.60 1.0x10 -3 < f/a < 5.0x10 -3 wherein a: mole number of the chloroformate group of the polycarbonate oligomer; b: mole number of cumylphenol; c: mole number of bisphenol A to be used in the polymerisation; d: mole number of alkali hydroxide contained in an aqueous alkali hydroxide solution in which bisphenol A is dissolved; e: mole number of alkali hydroxide contained in an aqueous alkali hydroxide solution to be added at the point of time that the flow of the reaction mixture is changed from a turbulent flow to a laminar flow; and f: mole number of a tertiary amine. If b/a is 0.04 or less, the viscosity undesirably increases. On the other hand, if it is 0.17 or more, the strength of the resulting polycarbonate is low. If c/a is 0.40 or less, the molecular weight is not sufficiently high. On the other hand, if it is 0.55 or more, unreacted bisphenol A remains excessively. If d/c is 2.02 or less, bisphenol A is not dissolved. On the other hand, if it is 2.50 or more, the chloroformate group is decomposed. If (d + e)/a is 1.40 or less, the molecular. weight is not sufficiently high. On the other hand, if it is 1.60 or more, the decomposition of the chloroformate group vigorously occurs. If f/a is 1.0x10⁻³ or less, the rate of reaction is low. On the other hand, if it is 5.0x10⁻³ or more, the decomposition of the chloroformate group vigorously occurs. As described above, the polycarbonate obtained is excellent in impact resistance, particularly at low temperatures. The polycarbonate resin of the invention can be efficiently produced by the process of the invention. The polycarbonate of the invention can be used widely and effectively in production of various industrial materials such as home electric appliances, Office Automation devices, construction materials and the like. The present invention is described in greater detail with reference to the following examples. EXAMPLE 1 (1) Preparation of Polycarbonate Oligomer 60 kg of bisphenol A was dissolved in 400 liters of a 5% aqueous sodium hydroxide solution to prepare a bisphenol A solution. Then the bisphenol A solution as prepared above and methylene chloride each maintained at room temperature were introduced into a tubular reactor (inner diameter: 10 mm; length: 10 m) through an orifice at flow rates of 138 liters/hr. and 69 liters/hr., respectively, and phosgene was blown into the reactor as a parallel flow at a flow rate of 10.7 kg/hr. and reacted continuously for 3 hours. The above tubular reactor was jacketed, and the discharge temperature of the reaction mixture was maintained at 25°C by passing cooling water in the jacket portion. The pH of the reaction mixture discharged was maintained at 10-11. The reaction mixture thus obtained was allowed to stand, and an aqueous layer was separated to obtain 220 liters of a methylene chloride layer. To this methylene chloride layer was added 170 liters of methylene chloride, and the resulting mixture was thoroughly stirred to obtain a polycarbonate oligomer (concentration: 314.7 g/liter; degree of polymerization: 3-4; chloroformate concentration: 0.74 N). (2) Preparation of Polycarbonate To 5.72 liters of the polycarbonate oligomer obtained in (1) above was added 3.28 liters of methylene chloride to prepare Solution (I) (concentration: 200 g/liter; chloroformate concentration: 0.47 N). 173.4 g of sodium hydroxide and 482.9 g of bisphenol A were dissolved in 2.9 liters of water to prepare Solution (II). Solutions (I) and (II) were mixed, and 0.856 g of triethylamine as a catalyst and 72.3 g of cumylphenol as a terminator were added. The resulting mixture was stirred in a turbular flow condition for 10 minutes at 600 rpm. Then, 167 milliliters of an aqueous solution of sodium hydroxide (concentration: 48% by weight) was added, and the resulting mixture was reacted in a laminar flow condition for 60 minutes by stirring at 200 rpm. After the reaction was completed, 5 liters of water and 5 liters of methylene chloride were added, and the resulting mixture was separated into a methylene chloride layer and an aqueous layer. This methylene chloride layer was subjected to alkali washing using a 0.01 N aqueous sodium hydroxide solution and further to acid washing using 0.1 N hydrochloric acid. Then the layer was washed with water to remove the methylene chloride, and polycarbonate in a flake form was obtained. The viscosity average molecular weight (Mv) of the polymer thus obtained was 19,000. Furthermore the flake-shaped polycarbonate was subjected to Soxhlet extraction for 8 hours to determine the acetone soluble content. The flake-shaped polymer was pelletized by the use of an extruder at a temperature of 220-270°C. The pellets thus obtained were injection molded to produce a test piece. This test piece was used to measure Izod impact resistance. The results are shown in Table 1. EXAMPLE 2 The procedure of (2) of Example 1 was repeated with the exception that 67.2 g of cumylphenol was used in place of 72.3 g of cumylphenol. The results are shown in Table 1. EXAMPLE 3 The procedure of (2) of Example 1 was repeated with the exception that 176.0 g of sodium hydroxide was used in place of 173.4 g of sodium hydroxide. The results are shown in Table 1. EXAMPLE 4 The procedure of (2) of Example 1 was repeated with the exception that 178.5 g of sodium hydroxide was used in place of 173.4 g of sodium hydroxide. The results are shown in Table 1. COMPARATIVE EXAMPLE 1 253.8 g of sodium hydroxide and 482.9 g of bisphenol A were dissolved in 3.0 liters of water to prepare Solution (III). Solution (I) prepared in Example 1 and Solution (III) as prepared above were mixed, and 0.856 g of triethylamine as a catalyst and 72.3 g of cumylphenol as a terminator were added. The resulting mixture was reacted for 1.5 hours while stirring at 500 rpm. After the reaction was completed, the reaction mixture was processed in the same manner as in Example 1. The results are shown in Table 1. COMPARATIVE EXAMPLE 2 432 g of sodium hydroxide was dissolved in 5.3 liters of water. In the resulting solution were dissolved 912 g of bisphenol A, 20 g of cumylphenol and 1.0 g of hydrosulfite while maintaining the temperature at 20°C, and 3,250 g of methylene chloride was added. Then, 436 g of phosgene was blown into the resulting mixture over 60 minutes while stirring. After the completion of introduction of phosgene, the reaction mixture was emulsified by vigorously stirring at 600 rpm. After emulsification, 1.0 g of triethylamine was added, and the resulting mixture was stirred for about one hour to achieve polymerization. An aqueous layer and a methylene chloride layer were separated from the polymerization mixture, and the methylene chloride layer was neutralized with phosphoric acid. Washing with water was repeated until the washing water became neutral. Then, 4,000 g of isopropanol was added to precipitate a polymer. The precipitate was filtered off and dried in vacuum at 50°C to obtain polycarbonate in a white powder form. Thereafter the polycarbonate was processed in the same manner as in Example 1. The results are shown in Table 1.

Claims: A process for producing high impact resistant polycarbonate: consisting of a main chain and terminal groups bonded thereto, said main chain consisting essentially of a repeating unit represented by the formula (I): and at least one of the terminal groups being a cumylphenoxy group represented by the formula (II): and having a viscosity average molecular weight of at least 10,000 and an acetone soluble content of not more than 3.5% by weight, which comprises the following steps: i) preparing a polycarbonate oligomer solution having (a) moles of chloroformate groups, by reacting bisphenol A and phosgene in a solvent, ii) mixing the polycarbonate oligomer solution with an aqueous solution containing (c) moles of bisphenol A and (d) moles of alkali hydroxide, iii) adding thereto (b) moles of cumylphenol and (f) moles of a tertiary amine, iv) stirring the resulting mixture under turbulent flow conditions at at least 400 rpm, v) adding an aqueous solution of (e) moles of alkali hydroxide at the point in time when the viscosity of the reaction mixture increases, and vi) subsequently continuing the reaction in a laminar flow condition at not more than 300 rpm, wherein the proportion of each component is chosen within the following ranges: 0.04/1 < b/a < 0.17/1, 0.40/1 < c/a < 0.55/1, 2.02/1 < d/c < 2.50/1, 1.40/1 < (d + e)/a < 1.60/1, 1.0x10 -3 < f/a < 5.0x10 -3 wherein a = mole number of the chloroformate group of the polycarbonate oligomer, b = mole number of cumylphenol, c = mole number of bisphenol A to be used in the polymerization d = mole number of alkali hydroxide contained in an aqueous alkali hydroxide solution in which bisphenol A is dissolved, e = mole number of alkali hydroxide contained in an aqueous alkali hydroxide solution to be added at the point of time that the flow of the reaction mixture is changed from a turbulent flow to a laminar flow, and f = mole number of tertiary amine. The process for producing a polycarbonate as claimed in Claim 1 wherein both the terminal groups of the polycarbonate are cumylphenoxy groups. The process for producing a polycarbonate as claimed in claim 2 wherein the viscosity average molecular weight of the polycarbonate is 10,000 to 50,000.

Inventors: EIICHI TERADA, MASAYA OKAMOTO, EIICHI, TERADA, MASAYA, OKAMOTO, EIICHI, TERADA IDEMITSU PETROCHEMICAL CO., LTD., MASAYA, OKAMOTO IDEMITSU PETROCHEMICAL CO., LTD.
Applicants: IDEMITSU PETROCHEMICAL CO, IDEMITSU PETROCHEMICAL CO., LTD.
Application year: 1988
Main classification: C08G64
IPC codes: C08G64