USRE38050E1 - Polycarbonate comprising different kinds of bonding units and process for the preparation thereof - Google Patents

Polycarbonate comprising different kinds of bonding units and process for the preparation thereof Download PDF

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USRE38050E1
USRE38050E1 US09/920,724 US92072401A USRE38050E US RE38050 E1 USRE38050 E1 US RE38050E1 US 92072401 A US92072401 A US 92072401A US RE38050 E USRE38050 E US RE38050E
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polycarbonate
group
formula
heterounit
represented
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Hiroshi Hachiya
Kyosuke Komiya
Miyuki Kazunori
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Asahi Kasei Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates

Definitions

  • the present invention relates to a polycarbonate having heterounits and a method for producing the same. More particularly, the present invention is concerned with a polycarbonate comprising a plurality of aromatic polycarbonate main chains, wherein the aromatic polycarbonate main chains collectively contain specific heterounits in a specific amount in the polycarbonate main chains, and a method for producing the same.
  • the polycarbonate of the present invention is advantageous in that not only does it have high transparency and colorlessness as well as high mechanical strength, but also it can exhibit high non-Newtonian flow properties, so that it exhibits high molding melt fluidity. Therefore, the polycarbonate of the present invention is extremely advantageous from a commercial point of view.
  • Polycarbonates have been widely used in various fields as engineering plastics having excellent heat resistance, impact resistance and transparency. Production of polycarbonates has conventionally been conducted by using the phosgene process. However, polycarbonates produced by using the phosgene process have problems in that the production thereof needs the use of phosgene, which is poisonous, and that they contain residual methylene chloride (solvent), which not only adversely affects the thermal stability of the polycarbonates, but also causes corrosion of a mold used for the molding of the polycarbonates. Therefore, recently, polycarbonates produced by using the transesterification process have been drawing attention.
  • methylene chloride solvent
  • transesterification polycarbonates With respect to transesterification polycarbonates, it is known: that almost colorless, transparent transesterification can be obtained on a laboratory scale; however, when the production of transesterification polycarbonates is conducted on a commercial scale, only those having slightly yellowish color can be obtained [see “Purasuchikku Zairyo Koza (5), Porikaboneto Jushi (Lecture on Plastic Materials (5), Polycarbonate Resins)”, page 66, published in 1981 by The Nikkan Kogyo Shimbun Ltd., Japan], and that transesterification polycarbonates have disadvantages in that they have many branched structures, so that they have poor strength (danger of brittle fracture is high), as compared to phosgene process polycarbonates [see “Kobunshi (Polymer)”, vol. 27, p. 521, July 1978)].
  • a branched chain grows and extends through ester bonds.
  • such a branched chain forms a crosslinked structure in the final polycarbonate [see “Purasuchikku Zairyo Koza (5), Porikaboneto Jushi (Lecture on Plastic Materials (5), Polycarbonate Resins)”, page 64, published in 1981 by The Nikkan Kogyo Shimbun Ltd., Japan; and “Porikaboneto Jushi Hando Bukku (Polycarbonate Resin Hand Book)”, page 49, published in 1992 by The Nikkan Kogyo Shimbun Ltd., Japan].
  • Unexamined Japanese Patent Application Laid-Open Specification No. 7-18069 proposes a method for producing a polycarbonate, in which, by the use of a specific catalyst, the amount of the above-mentioned branched structure formed by the side reaction similar to the Kolbe-Schmitt reaction is suppressed to a level as low as 300 ppm or less.
  • the polycarbonates disclosed in these prior art documents have high transparency and colorlessness; however, these polycarbonates have problems in that they exhibit poor non-Newtonian flow properties, so that they disadvantageously exhibit low molding melt fluidity.
  • Unexamined Japanese Patent Application Laid-Open Specification Nos. 5-271400 and 5-295101 disclose a transesterification technique in which the formation of the above-mentioned disadvantageous branched structure resulting from the side reaction of the above reaction formula is reduced by the use of a specific catalyst to thereby achieve an improvement in transparency and colorlessness of the formed polycarbonate, whereas the non-Newtonian flow properties of the polycarbonate are improved by intentionally introducing another specific branched structure to the polycarbonate by the use of a multifunctional compound, to thereby improve the properties of the polycarbonate so that it can be advantageously used for blow molding.
  • a special type of polymerizer as a final stage polymerizer, such as a special type of horizontal agitation type polymerizer (see Unexamined Japanese Patent Application Laid-Open Specification No. 2-153923) or a twin screw vented extruder (see Examined Japanese Patent Application Publication No. 52-36159 and Unexamined Japanese Patent Application Laid-Open Specification No. 63-23926.
  • the task of the present invention is to provide a polycarbonate which is advantageous in that not only does it have high transparency and colorlessness as well as high mechanical strength, but also it exhibits high non-Newtonian flow properties, so that it can exhibit high molding melt fluidity.
  • a polycarbonate comprising a plurality of aromatic polycarbonate main chains, wherein the aromatic polycarbonate main chains collectively contain specific heterounits in a specific amount in the polycarbonate chains, is free from the above-mentioned problems accompanying the conventional polycarbonates, and is advantageous in that not only does it have high transparency and colorlessness as well as high mechanical strength, but also it exhibits high non-Newtonian flow properties, so that it can exhibit high molding melt fluidity.
  • FIG. 1 is a diagram showing the system employed for producing a polycarbonate in Example 1.
  • 6 A, 6 B, 6 C, 6 D Agitator
  • 101 A, 101 B Inlet for a prepolymer
  • a polycarbonate comprising a plurality of aromatic polycarbonate main chains, each comprising recurring units each independently represented by the following formula (1):
  • Ar represents a divalent C 5 -C 200 aromatic group
  • the plurality of aromatic polycarbonate main chains collectively contain at least one heterounit (A) and at least one heterounit (B) in the polycarbonate main chains,
  • heterounit (A) being represented by a formula selected from the following group (2) of formulae:
  • Ar′ represents a trivalent C 5 -C 200 aromatic group
  • Ar′′ represents a tetravalent C 5 -C 200 aromatic group
  • X represents a polycarbonate chain having recurring units each represented by the formula
  • Ar is as defined above and having a weight average molecular weight of from 214 to 100,000, and
  • heterounits (A) when the polycarbonate main chains contain a plurality of heterounits (A), the heterounits (A) are the same or different,
  • heterounit (B) being represented by a formula selected from the following group (3) of formulae:
  • Ar, Ar′ and X are as defined above and Y represents a polycarbonate chain having recurring units each represented by the formula
  • Ar is as defined above and having a weight average molecular weight of from 214 to 100,000, and
  • heterounits (B) when the polycarbonate main chains contain a plurality of heterounits (B), the heterounits (B) are the same or different,
  • the sum of the amounts of the heterounit (A) and the heterounit (B) being from 0.01 to 0.3 mole %, based on the molar amount of the recurring units (1),
  • each of X and Y optionally contains at least one heterounit selected from the group consisting of heterounits (A) and (B),
  • the polycarbonate having a weight average molecular weight of from 5,000 to 300,000.
  • a polycarbonate comprising a plurality of aromatic polycarbonate main chains, each comprising recurring units each independently represented by the following formula (1):
  • Ar represents a divalent C 5 -C 200 aromatic group, wherein the plurality of aromatic polycarbonate main chains collectively contain at least one heterounit (A) and at least one heterounit (B) in the polycarbonate main chains,
  • heterounit (A) being represented by a formula selected from the following group (2) of formulae:
  • Ar′ represents a trivalent C 5 -C 200 aromatic group
  • Ar′′ represents a tetravalent C 5 -C 200 aromatic group
  • X represents a polycarbonate chain having recurring units each represented by the formula
  • Ar is as defined above and having a weight average molecular weight of from 214 to 100,000, and
  • heterounits (A) when the polycarbonate main chains contain a plurality of heterounits (A), the heterounits (A) are the same or different,
  • heterounit (B) being represented by a formula selected from the following group (3) of formulae:
  • Ar, Ar′ and X are as defined above and Y represents a polycarbonate chain having recurring units each represented by the formula
  • heterounits (B) when the polycarbonate main chains contain a plurality of heterounits (B), the heterounits (B) are the same or different,
  • the sum of the amounts of the heterounit (A) and the heterounit (B) being from 0.01 to 0.3 mole %, based on the molar amount of the recurring units (1),
  • each of X and Y optionally contains at least one heterounit selected from the group consisting of heterounits (A) and (B),
  • the polycarbonate having a weight average molecular weight of from 5,000 to 300,000.
  • heterounit (A) is represented by a formula selected from the following group (2′) of formulae:
  • heterounit (B) is represented by a formula selected from the following group (3′) of formulae:
  • molten prepolymer obtained by a process comprising reacting an aromatic dihydroxy compound with a carbonic diester
  • Ar represents a divalent C 5 -C 200 aromatic group
  • Ar 3 and Ar 4 are the same or different and each represent a monovalent C 5 -C 200 aromatic group
  • i the zone number assigned in an arbitrary order among n reaction zones of the reaction system
  • Ti represents the average temperature (°C.) of the polymerizable material in the i-th reaction zone
  • Hi represents the average residence time (hr) of the polymerizable material in the i-th reaction zone
  • ki represents a coefficient represented by the following formula (5):
  • Ti is as defined above, and a and b depend on Ti, and wherein:
  • a 1.60046 ⁇ 10 5 and b is 0.472
  • a is 4 ⁇ 10 49 and b is 19.107, and
  • a is 1 ⁇ 10 122 and b is 49.082.
  • the polycarbonate of the present invention comprises a plurality of aromatic polycarbonate chains, each comprising recurring units each independently represented by the formula (1) above, wherein the aromatic polycarbonate chains collectively contain at least one heterounit (A) and at least one heterounit (B).
  • the heterounit (A) is represented by a formula selected from the above-mentioned formulae of group (2).
  • the heterounits (A) may be the same or different.
  • the heterounit (B) is represented by a formula selected from the above-mentioned formulae of group (3).
  • the aromatic polycarbonate chains contain a plurality of the heterounits (B) may be the same or different.
  • each Ar independently represents a divalent C 5 -C 200 aromatic group
  • each Ar′ independently represents a trivalent C 5 -C 200 aromatic group which has a structure equivalent to a mono-substituted Ar
  • each Ar′′ independently represents a tetravalent C 5 -C 200 aromatic group which has a structure equivalent to a di-substituted Ar.
  • divalent aromatic groups Ar include phenylene, naphthylene, biphenylene, pyridylene and a divalent aromatic group represented by the formula: —Ar 1 —Q—Ar 2 —, wherein each of Ar 1 and Ar 2 independently represents a divalent C 5 -C 70 carbocyclic or heterocyclic aromatic group, and Q represents a divalent C 1 -C 30 alkane group.
  • At least one hydrogen atom may be replaced by a substituent which does not adversely affect the reaction, such as a halogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or a nitro group.
  • a substituent which does not adversely affect the reaction, such as a halogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or a nitro group.
  • heterocyclic aromatic groups include an aromatic group having in a skeleton thereof at least one hetero atom, such as a nitrogen atom, an oxygen atom or a sulfur atom.
  • Examples of divalent aromatic groups Ar 1 and Ar 2 include an unsubstituted or substituted phenylene group, an unsubstituted or substituted biphenylene group and an unsubstituted or substituted pyridylene group. Substituents for Ar 1 and Ar 2 are as described above.
  • divalent alkane groups Q include organic groups respectively represented by the following formulae:
  • each of R 1 , R 2 , R 3 and R 4 independently represents a hydrogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 5 to 10 ring-forming carbon atoms, a carbocyclic aromatic group having from 5 to 10 ring-forming carbon atoms or a carbocyclic aralkyl group having from 6 to 10 ring-forming carbon atoms; k represents an integer of from 3 to 11; each Z represents a carbon atom and has R 5 and R 6 bonded thereto; each R 5 independently represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, and each R 6 independently represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; and
  • each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be independently replaced by a substituent which does not adversely affect the reaction, such as a halogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or a nitro group.
  • a substituent which does not adversely affect the reaction such as a halogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or a nitro group.
  • divalent aromatic groups Ar include groups respectively represented by the following formulae:
  • each of R 7 and R 8 independently represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 5 to 10 ring-forming carbon atoms, or an phenyl group; each of m and n independently represents an integer of from 1 to 4, with the proviso that when m is an integer of from 2 to 4, the R 7 s are the same or different, and when n is an integer of from 2 to 4, the R 8 's are the same or different.
  • divalent aromatic groups Ar include those which are represented by the following formula:
  • Z′ represents a single bond or a divalent group, such as —O—, —CO—, —S—, —SO 2 , —SO—, —COO—, or —CON(R 1 )—, wherein R 1 is as defined above.
  • divalent aromatic groups Ar examples include groups respectively represented by the following formulae:
  • R 7 , R 8 , m and n are as defined above.
  • these aromatic groups Ar may be used individually or in combination.
  • recurring units of the formula (1) in the polycarbonate of the present invention there can be mentioned a unit represented by the above-mentioned formula (1′), which is derived from bisphenol A. It is preferred that 85 mole % or more of the recurring units (1) are the units of the formula (1′).
  • heterounit (A) is one which is represented by a formula selected from the formulae of the following group (2′) of formulae:
  • the aromatic polycarbonate chains collectively contain at least one heterounit (A).
  • heterounit (B) is one which is represented by a formula selected from the following group (3′) of formulae:
  • Y is as defined for formula (3).
  • the aromatic polycarbonate chains collectively contain at least one heterounit (B).
  • the sum of the amounts of the heterounit (A) and the heterounit (B) be in the range of from 0.01 to 0.3 mole %, based on the molar amount of the recurring units (1).
  • the non-Newtonian flow properties of the polycarbonate lowers, so that the molding melt fluidity, (i.e., the fluidity of the polycarbonate at a high shear rate) is caused to lower.
  • the mechanical properties such as tensile elongation and Izod impact strength
  • the sum of the heterounit (A) and the heterounit (B) is preferably in the range of from 0.02 to 0.25 mole %, more preferably from 0.03 to 0.2 mole %, based on the molar amount of the recurring units (1).
  • the polycarbonate contains the heterounit (B) in an amount of from 0.1 to 30 mole %, more preferably from 0.1 to 10 mole %, based on the molar amount of the heterounit (A).
  • each of the recurring units (1), and the heterounits (A) and (B) can be conducted, for example, by a method in which the polycarbonate is completely hydrolyzed, and the resultant hydrolysis mixture is analyzed by reversed phase liquid chromatography (the analysis by reversed phase liquid chromatography can be conducted under the conditions as described below in the Examples).
  • the hydrolysis of the polycarbonate it is preferred that the hydrolysis be conducted at room temperature by the method described in Polymer Degradation and Stability 45 (1994), 127-137.
  • the hydrolysis by this method is advantageous in that the complete hydrolysis of a polycarbonate can be achieved by simple operation, wherein it is free from the danger of occurrence of side reactions during the hydrolysis.
  • the polycarbonate of the present invention has a weight average molecular weight of from 5,000 to 300,000. When the weight average molecular weight is lower than 5,000, the mechanical strength of the polycarbonate lowers. When the weight average molecular weight is higher than 300,000, the molding melt fluidity of the polycarbonate lowers. In the present invention, the weight average molecular weight of the polycarbonate is preferably from 7,000 to 100,000, more preferably from 10,000 to 80,000.
  • the terminal structure of the polycarbonate is not particularity limited.
  • the terminal group of the polycarbonate may be at least one group selected from a hydroxyl group, an aryl carbonate group and an alkyl carbonate group.
  • the above-mentioned terminal hydroxyl group is derived from the aromatic dihydroxy compound used in the polymerizable material.
  • the terminal aryl carbonate group is represented by the following formula:
  • Ar 3 represents an unsubstituted or
  • terminal aryl carbonate groups include groups respectively represented by the following formulae:
  • the terminal alkyl carbonate group is represented by the following formula:
  • R 7 represents a straight chain or branched alkyl group having 1 to 20 carbon atoms.
  • terminal alkyl carbonate groups include groups respectively represented by the following formulae:
  • a phenyl carbonate group, a p-t-butylphenyl carbonate group and a p-cumylphenyl carbonate group are preferred.
  • the molar ratio of the terminal hydroxyl group to other terminal groups there is no particular limitation. However, the molar ratio is generally selected in the range of from 0:100 to 100:0 depending on the use. From the viewpoint of improving heat resistance and hot water resistance, it is preferred that the amount of the terminal hydroxy group be as small as possible.
  • the method of the present invention comprises subjecting to a stepwise transesterification reaction, in a plurality of reaction zones, at least one polymerizable material selected from the group consisting of:
  • molten prepolymer obtained by a process comprising reacting an aromatic dihydroxy compound with a carbonic diester
  • Ar represents a divalent C 5 -C 200 aromatic group
  • Ar 3 and Ar 4 are the same or different and each represent a monovalent C 5 -C 200 aromatic group
  • i the zone number assigned in an arbitrary order among n reaction zones of the reaction system
  • Ti represents the average temperature (° C.) of the polymerizable material in the i-th reaction zone
  • Hi represents the average residence time (hr) of the polymerizable material in the i-th reaction zone
  • ki represents a coefficient represented by the following formula (5):
  • a 1.60046 ⁇ 10 5 and b is 0.472
  • a is 4 ⁇ 10 49 and b is 19.107, and
  • a is 1 ⁇ 10 122 and b is 49.082.
  • aromatic dihydroxy compound means a compound represented by the formula: HO—Ar—OH wherein Ar is as defined above.
  • the aromatic dihydroxy compound may be a single type of aromatic dihydroxy compound or a combination of 2 or more types of aromatic dihydroxy compounds. It is preferred to use an aromatic dihydroxy compound in which the contents of a chlorine atom, an alkali metal and an alkaline earth metal are low. It is more preferred to use an aromatic dihydroxy compound substantially free from a chlorine atom, an alkali metal and an alkaline earth metal.
  • the carbonic diester used in the present invention is represented by the following formula:
  • Ar 3 and Ar 4 are the same or different and each represent a monovalent C 5 -C 200 aromatic group.
  • At least one hydrogen atom may be replaced by a substituent which does not adversely affect the reaction, such as a halogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or a nitro group.
  • a substituent which does not adversely affect the reaction, such as a halogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group or a nitro group.
  • Ar 3 and Ar 4 may be the same or different.
  • monovalent aromatic groups Ar 3 and Ar 4 include a phenyl group, a naphthyl group, a biphenyl group and a pyridyl group. These groups may or may not be substituted with the above-mentioned substitutent or substituents.
  • Preferred examples of monovalent aromatic groups as Ar 3 and Ar 4 include those which are respectively represented by the following formulae:
  • carbonic diesters include di(unsubstituted or substituted)phenyl carbonate compounds represented by the following formula:
  • each of R 9 and R 10 independently represents a hydrogen atom, an alkyl group having from 1 to 10 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 5 to 10 ring-forming carbon atoms or a phenyl group; each of p and q independently represents an integer of from 1 to 5, with the proviso that when p is an integer of 2 or more, the R 9 's are the same or different, and when q is an integer of from 2 or more, the R 10 's are the same or different.
  • diphenyl carbonate compounds preferred are those having a symmetrical configuration, for example di(unsubstituted)phenyl carbonate and di(lower alkyl-substituted)phenyl carbonates, e.g., ditolyl carbonate and di-t-butylphenyl carbonate. Particularly preferred is diphenyl carbonate which has the simplest structure.
  • These carbonic diesters may be used individually or in combination. It is preferred that these carbonic diesters have a low content of a chlorine atom, an alkali metal or an alkaline earth metal. It is most preferred that these carbonic diesters are substantially free from a chlorine atom, an alkali metal and an alkaline earth metal.
  • the ratio in which the aromatic dihydroxy compound and the carbonic diester are used may be varied depending on the types of the aromatic dihydroxy compound and carbonic diester employed, the polymerization temperature and other polymerization conditions, and the desired molecular weight of a polycarbonate to be obtained and the desired proportions of the terminal groups in the polycarbonate.
  • the carbonic diester is generally used in an amount of from 0.9 to 2.5 moles, preferably from 0.95 to 2.0 moles, more preferably from 0.98 to 1.5 moles, per mole of the aromatic dihydroxy compound.
  • the heterounit (A) and the heterounit (B) are formed during the polymerization reaction, so that the final polycarbonate contains the heterounit (A) and the heterounit (B).
  • an aromatic poly(tri or more)hydroxy compound may be used in a small amount in the production of the polycarbonate, as long as the polycarbonate satisfying the above-mentioned requirements of the present invention can be obtained.
  • an aromatic monohydroxy compound or an aliphatic alcohol may be used for changing the terminal groups, or adjusting the molecular weight of the polycarbonate.
  • the production of a polycarbonate is conducted by a transesterification process which is a process wherein a condensation polymerization of the polymerizable material is performed by transesterification in the molten state or solid state while heating in the presence or absence of a catalyst under reduced pressure, under an inert gas flow or under both reduced pressure and an inert gas flow.
  • a transesterification process which is a process wherein a condensation polymerization of the polymerizable material is performed by transesterification in the molten state or solid state while heating in the presence or absence of a catalyst under reduced pressure, under an inert gas flow or under both reduced pressure and an inert gas flow.
  • the mode of the transesterification process, the polymerization equipment and the like are not specifically limited.
  • examples of reactors employable for performing the transesterification reaction include an agitation type reactor vessel, a wiped film type reactor, a centrifugal wiped film evaporation type reactor, a surface renewal type twin-screw kneading reactor, a twin-screw horizontal agitation type reactor, a wall-wetting fall reactor, a free-fall polymerizer having a perforated plate, and a wire-wetting fall polymerizer having a perforated plate and at least one wire provided in association with the perforated plate.
  • reactors can be used individually or in combination.
  • the transesterification reaction can also be performed by a method in which a molten-state transesterification is first conducted to obtain a prepolymer, and the obtained prepolymer is then subjected to a solid-state polymerization under reduced pressure, under an inert gas flow or under both reduced pressure and an inert gas flow, using a solid-state polymerizer.
  • stainless steel, nickel or glass is generally used as a material for at least inner wall portions of polymerizers.
  • any of the above-mentioned transesterification reaction modes can be used as long as the transesterification is performed under the reaction conditions defined above.
  • the reaction temperature of the transesterification for producing a polycarbonate is generally in the range of from 50 to 350° C., preferably from 100 to 300° C. It is well known that when the reaction temperature is higher than the above-mentioned range, the produced polycarbonate is likely to suffer serious discoloration and tends to have poor thermal stability, and that when the reaction temperature is lower than the above-mentioned range, the polymerization proceeds so slowly that such a low temperature cannot be practically employed.
  • i the zone number assigned in an arbitrary order among n reaction zones of the reaction system
  • Ti represents the average temperature (° C.) of the polymerizable material in the i-th reaction zone
  • Hi represents the average residence time (hr) of the polymerizable material in the i-th reaction zone
  • ki represents a coefficient represented by the following formula (5):
  • a 1.60046 ⁇ 10 5 and b is 0.472
  • a is 4 ⁇ 10 49 and b is 19.107, and
  • a is 1 ⁇ 10 122 and b is 49.082.
  • the transesterification reaction of the polymerizable material is stepwise conducted in a plurality of reaction zones, wherein the reaction temperature, residence time and reaction pressure are stepwise changed over the plurality of reaction zones involved in the process.
  • the value of ⁇ i 1 n ⁇
  • (ki ⁇ Ti ⁇ Hi) in the formula (4) represents the sum of the values of (k ⁇ T ⁇ H) for all of the reaction zones.
  • (ki ⁇ Ti ⁇ Hi) is the sum of (k ⁇ T ⁇ H in the melting and mixing vessel), (k ⁇ T ⁇ H in the conduit connecting the melting and mixing vessel to the agitation type reactor vessel), (k ⁇ T ⁇ H in the agitation type reaction vessel), (k ⁇ T ⁇ H in the conduit connecting the agitation type reactor vessel to the centrifugal wiped film evaporation type reactor), (k ⁇ T ⁇ H in the centrifugal wiped film evaporation type reactor), (k ⁇ T ⁇ H in the conduit connecting the centrifugal wiped film evaporation type reactor to the surface renewal type twin screw kneading reactor), (k ⁇ T ⁇ H in the surface renewal type twin screw kneading reactor) and (k ⁇ T ⁇ H in the conduit connecting the surface renewal type twin screw kneading reactor to a nozzle for withdrawal of the produced polymer), that is, the sum of values of (k ⁇ T ⁇ H) for all of the reaction zones including the conduits.
  • i-th reaction zone means a reaction zone falling on the number i which is determined by the numbering system in which all reaction zones including conduits, such as a mixing vessel, a reactor or a conduit which connect these apparatuses, are assigned their respective numbers in the arbitrary order.
  • conduits such as a mixing vessel, a reactor or a conduit which connect these apparatuses
  • the average temperature of the polymerizable material means the average temperature of the polymerizable material in the i-th reaction zone.
  • the average temperature can be obtained by averaging one or more temperatures measured by one or more thermometers disposed at a reactor or a conduit. When no thermometers are disposed at a reactor or a conduit, the temperature of a heating medium in a jacket may be used as the average temperature.
  • the average temperature of the inlet and outlet of a jacket for circulating a heating medium may be employed as the average temperature of the polymerizable material in the i-th reaction zone.
  • the average residence time is calculated by dividing the volume of the polymerizable material held in the i-th reaction zone by the volume of the polymerizable material passing through or withdrawn from the i-th reaction zone per unit time.
  • a suitable reaction pressure is selected depending on the molecular weight of the polycarbonate in the reaction system.
  • a reaction pressure in the range of from 50 mmHg to atmospheric pressure is generally employed.
  • a reaction pressure in the range of from 3 mmHg to 80 mmHg is generally employed.
  • a reaction pressure of 10 mmHg or less, preferably 5 mmHg or less is generally employed.
  • a transesterification reaction can be carried out in the absence of a catalyst. However, if it is desired to accelerate the polymerization, the polymerization can be effected in the presence of a catalyst.
  • the polymerization catalysts which are customarily used in the art can be used without particular limitation.
  • Such catalysts include hydroxides of an alkali metal and of an alkaline earth metal, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal salts of, alkaline earth metal salts of and quaternary ammonium salts of boron hydride and of aluminum hydride, such as lithium aluminum hydride, sodium boron hydride and tetramethyl ammonium boron hydride; hydrides of an alkali metal and of an alkaline earth metal, such as lithium hydride, sodium hydride and calcium hydride; alkoxides of an alkali metal and of an alkaline earth metal, such as lithium methoxide, sodium ethoxide and calcium methoxide; aryloxides of an alkali metal and of an alkaline earth metal, such as lithium phenoxide, sodium phenoxide, magnesium phenoxide, LiO—Ar—OLi wherein Ar represents an arylene group, and NaO—Ar
  • the catalysts can be used individually or in combination.
  • the amount of the catalysts used is generally in the range of from 10 ⁇ 8 to 1% by weight, preferably from 10 ⁇ 7 to 10 ⁇ 1 % by weight, based on the weight of the aromatic dihydroxy compound.
  • the polycarbonate of the present invention is advantageous in that not only does it have high transparency and colorlessness as well as high mechanical strength, but also it exhibits high non-Newtonian flow properties, so that it exhibits high molding melt fluidity. Therefore, the polycarbonate of the present invention can be advantageously used in various application fields.
  • the polycarbonate of the present invention may contain additives depending on the use of the polycarbonate.
  • additives include a thermal stabilizer, an antioxidant, a weathering stabilizer, a UV light absorber, a mold release agent, a lubricant, an antistatic agent, a plasticizer, a resin other than a polycarbonate or a polymer such as a rubber, a pigment, a dye, a filler, a reinforcing agent, and a flame retardant.
  • additives may be mixed with the polycarbonate obtained in the molten state.
  • the mixing of additives may be performed by a method in which the polycarbonate is first pelletized, the additives are mixed with the pelletized polycarbonate and the resultant mixture is again subjected to melt-kneading.
  • the weight average molecular weight of a polycarbonate was measured by gel permeation chromatography (GPC).
  • the elongation at break of a polycarbonate was measured, using a test specimen having a 3.2 mm thickness which was obtained by injection molding at 280° C., in accordance with ASTM D638.
  • the Izod impact strength (notched) of a polycarbonate was measured, using a test specimen having a 3.2 mm thickness which was obtained by injection molding at 280° C., in accordance with ASTM D256.
  • the HMI which is a melt flow rate under a load of 21.6 kg
  • ASTM D1238 As a yardstick of the fluidity at a high shear rate, the HMI (which is a melt flow rate under a load of 21.6 kg) at 280° C. was measured in accordance with ASTM D1238.
  • the reversed phase liquid chromatography was performed, using a 991L UV detector (manufactured and sold by Waters Corporation, U.S.A) and Inertsil ODS-3 column (registered trade mark, manufactured and sold by GL Science Inc., Japan) at 25° C.
  • a mixture of methanol and 0.1 weight % aqueous solution of phosphoric acid was used as an eluent, and measurement was carried out by gradient elution technique at a gradient such that the volume ratio [methanol/0.1 weight % aqueous solution of phosphoric acid] is changed from 20/80 at the start to 100/0.
  • the absorbance at 300 nm was measured using the UV detector.
  • Absorbance coefficients for determining recurring unit (1), heterounit (A) and heterounit (B) were obtained by using standard compounds [as standard compounds, hydroxy compounds having structures formed by hydrolysis of recurring unit (1′), heterounit (2′) and heterounit (3′) were used].
  • a polycarbonate was produced by melt transesterification in accordance with a system as shown in FIG. 1 .
  • the system of FIG. 1 comprises first stage, second stage and third stage agitation polymerizations, and first stage, and second stage wire-wetting fall polymerizations.
  • first stage agitation polymerization in first agitation type polymerizer vessels 3 A and 3 B (each having a capacity of 100 liters and equipped with an agitator having agitating blades of anchor type) was batchwise conducted, whereas the second stage and third stage agitation polymerizations in second and third agitation type polymerizer vessels 3 C and 3 D (each having a capacity of 50 liters and equipped with an agitator having agitating blades of anchor type) were continuously conducted.
  • first and second wire-wetting fall polymerizations in first and second wire-wetting fall polymerizers 108 A and 108 B were continuously conducted.
  • Each of the first and second wire-wetting fall polymerizers is equipped with a perforated plate which has 50 holes having a diameter of 7.5 mm and arranged in a zigzag configuration.
  • 50 strands of 1 mm ⁇ SUS 316 L wires are hung vertically from the respective holes of the perforated plate to a reservoir portion at the bottom of wire-wetting fall polymerizer 108 so that a polymerizable material will not fall freely (not free-fall) but fall along and in contact with the wires (wire-wetting fall).
  • each wire 103 is secured at the upper end thereof to a support rod (not shown) provided above the perforated plate 102 and extends downwardly through a hole (not shown) of the perforated plate 102 .
  • the wire-wetting fall distance is 8 m.
  • the polymerization reaction conditions in both of first agitation type polymerizer vessels 3 A and 3 B were as follows: the reaction temperature was 180° C., the reaction pressure was atmospheric pressure, and the flow rate of nitrogen gas was 1 liter/hr.
  • first agitation type polymerizer vessel 3 A 80 kg of polymerizable materials [i.e., bisphenol A as an aromatic dihydroxy compound and diphenyl carbonate as a carbonic diester (the molar ratio of diphenyl carbonate to bisphenol A:1.04)] were charged together with a disodium salt of bisphenol A as a catalyst (the amount of the disodium salt of bisphenol A in terms of the amount of sodium atom: 25 ppb by weight, based on the weight of the bisphenol A as a polymerizable material) into first agitation type polymerizer vessel 3 A.
  • the monomer mixture in polymerizer 3 A was polymerized in a molten state for 4 hours while agitating, to obtain prepolymer 4 A.
  • Outlet 5 A was opened, and prepolymer 4 A was fed to second agitation type polymerizer vessel 3 C, having a capacity of 50 liters, at a flow rate of 5 kg/hr.
  • first agitation type polymerizer vessel 3 B While feeding prepolymer 4 A obtained in first agitation type polymerizer vessel 3 A to second agitation type polymerizer vessel 3 C, first agitation type polymerizer vessel 3 B was operated to polymerize the monomer mixture of bisphenol A and diphenyl carbonate in the same manner as in the agitation polymerization in first agitation type polymerizer vessel 3 A, to obtain prepolymer 4 B.
  • first agitation type polymerizer vessel 3 A When first agitation type polymerizer vessel 3 A became empty, outlet 5 A of polymerizer 3 A was closed and, instead, outlet 5 B of polymerizer 3 B was opened, so that prepolymer 4 B was fed from first agitation type polymerizer vessel 3 B to second agitation type polymerizer vessel 3 C at a flow rate of 5 kg/hr. In this instance, the same polymerizable materials and catalyst as mentioned above were charged into polymerizer 3 A. While feeding prepolymer 4 B obtained in first agitation type polymerizer vessel 3 B to second agitation type polymerizer vessel 3 C, polymerizer vessel 3 A was operated, so that the monomer mixture charged therein was polymerized in the same manner as mentioned above.
  • second agitation type polymerizer vessel 3 C a further agitation polymerization of prepolymers 4 A and 4 B, alternately fed from first agitation type polymerizer vessels 3 A and 3 B, was continuously carried out under polymerization reaction conditions wherein the reaction temperature was 230° C., the reaction pressure was 100 mmHg and the flow rate of nitrogen gas was 2 liters/hr, thereby obtaining prepolymer 4 C.
  • third agitation type polymerizer vessel 3 D a further agitation polymerization of prepolymer 4 C fed from second agitation type polymerizer vessel 3 C was continuously carried out under polymerization reaction conditions wherein the reaction temperature was 240° C., the reaction pressure was 10 mmHg and the flow rate of nitrogen gas was 2 liters/hr, thereby obtaining prepolymer 4 D.
  • first wire-wetting fall polymerizer 108 A a wire-wetting fall polymerization of prepolymer 4 C was continuously carried out under polymerization reaction conditions wherein the reaction temperature was 245° C., and the reaction pressure was 1.5 mmHg and the flow rate of nitrogen gas was 4 liter/hr, thereby obtaining prepolymer 109 A.
  • first wire-wetting fall polymerizer 108 A When the volume of prepolymer 109 A at the bottom of first wire-wetting fall polymerizer 108 A reached 10 liters, a part of prepolymer 109 A was continuously fed to second wire-wetting fall polymerizer 108 B so that the volume of prepolymer 109 A in first wire-wetting fall polymerizer 108 A was constantly maintained at 10 liters.
  • second wire-wetting fall polymerizer 108 B a wire-wetting fall polymerization reaction was continuously carried out under polymerization reaction conditions wherein the reaction temperature was 245° C., and the reaction pressure was 0.3 mmHg and the flow rate of nitrogen gas was 2 liter/hr, thereby obtaining polycarbonate 109 B.
  • polycarbonate 109 B was continuously withdrawn in the form of a strand from second wire-wetting fall polymerizer 108 B through outlet 107 B by means of discharge pump 106 B so that the volume of polycarbonate 109 B in second wire-wetting fall polymerizer 108 B was constantly maintained at 10 liters.
  • the obtained strand was cut into pellets by means of a strand cutter.
  • the obtained polycarbonate contained units of formula (2′)-(a) as heterounit (A) and units of formula (3′)-(d) as heterounit (B), wherein the units of formula (3′)-(d) were present in an amount of 0.50 mole %, based on the molar amount of the units of formula (2′)-(a), and wherein the sum of the amounts of the units of formula (2′)-(a) and the units of formula (3′)-(d) was 0.09 mole %, based on the molar amount of recurring units (1).
  • a polycarbonate was produced in substantially the same manner as in Example 1, except that the temperatures in some of the reaction zones were changed as shown in Table 3.
  • a polycarbonate was produced in substantially the same manner as in Example 1, except that a centrifugal wiped film evaporation type reactor and a horizontal twin-screw agitation type polymerizer were used instead of first wire-wetting fall polymerizer 108 A and second wire-wetting fall polymerizer 108 B, respectively, and that the reaction conditions were changed as shown in Table 4.
  • a polycarbonate was produced in substantially the same manner as in Example 1, except that the reaction conditions were changed as shown in Table 5.
  • Example 1 Example 2
  • Example 3 Example 2 Molar ratio 0.09 0.46 0.69 0.00 0.16 (%) of the total of heterounits (A) and (B) to the total of recurring units (1) Molar ratio 0.30 33.00 42.00 — 2.30 (%) of hete- rounits (B) to heterounits (A) Weight 26,800 26,900 27,000 26,800 26,900 average molecular weight Molding 145 166 179 118 153 melt fluidity, HMI (g/10 min) Color (b* 3.2 4.3 5.0 3.2 3.4 value) Tensile 107 78 69 107 102 elongation (%) Izod impact 98 83 81 98 96 strength (kg ⁇ cm/ cm)
  • the polycarbonate of the present invention is advantageous in that not only does it have high transparency and colorlessness as well as high mechanical strength, but also it can exhibit extremely high molding melt fluidity. Therefore, the polycarbonate of the present invention can be used in a wide variety of application fields.

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JP5804387B2 (ja) 2011-02-11 2015-11-04 三菱瓦斯化学株式会社 所望の分岐化度を有する分岐化芳香族ポリカーボネート樹脂の製造方法
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KR102159519B1 (ko) 2012-11-17 2020-09-24 미츠비시 가스 가가쿠 가부시키가이샤 방향족 폴리카보네이트 수지 조성물
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