JPH06220182A - Aromatic polycarbonate - Google Patents

Abstract

PURPOSE:To obtain the subject polymer containing an end group of a specific structure, having hydrolytic stability. CONSTITUTION:The objective polymer contains a group of the formula -A-ORf [A is phenylene, naphthylene or biphenylene; Rf is (CHR1)R2 (R1 is H or F; R2 is alkyl which may contain fluorine atom with the proviso that R2 is fluorine atom-containing alkyl when R1 is H] at the end. The polymer is preferably obtained from an aromatic hydroxy compound such as bisphenol A and a carbonate precursor such as phosgene by interfacial polymerization method. For example, 4-(1'-hydroperfluoroethyloxy) benzoic acid, 4-(1',1',7'- trihydroperfluoroheptyloxy)phenol may be cited as the compound of the formula Y-A-ORf.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to aromatic polycarbonates. More specifically, it relates to an aromatic polycarbonate having a group having a specific structure as an end group.

[0002]

2. Description of the Related Art Conventionally, aromatic polycarbonate has been
It is known as an engineering plastic excellent in transparency, heat resistance, mechanical strength, dimensional stability, etc., and is widely used as parts for automobiles, electric products and the like. Usually, when producing an aromatic polycarbonate, for the purpose of controlling the molecular weight of the aromatic polycarbonate produced, it is also referred to as a terminal blocking agent (a molecular weight regulator, a polymerization terminator, a chain terminator, an end terminator, etc.). Are added and polymerization is carried out (for example, US Pat. No. 3,028,365).
issue). Among them, phenol or phenols such as p-tert-butylphenol is most commonly and widely used as the end capping agent.

Further, it has been reported that compounds having various structures are useful as an end-capping agent. For example, alkanolamines (US Pat. No. 3,085,992).
), Imides (US Pat. No. 3,399,172), aniline, methylaniline (US Pat. No. 3,275,601).
No.), ammonium compounds, primary or secondary amines (US Pat. No. 4,111,910) have been proposed for use as endcapping agents. But on the other hand,
It has been reported that a small amount of amines such as monoethanolamine or morpholine has an action of decomposing a high-molecular weight polycarbonate into a low-molecular weight polycarbonate (US Pat. No. 3,232,678). Thus, although various reports have been made regarding the end-capping agent of polycarbonate, what kind of compound or compound group effectively functions as the end-capping agent is
It is still not fully understood. Furthermore, even if a compound having a specific structure is useful as an end-capping agent, it is not possible to predict what kind of physical property or function a polycarbonate having such a compound as an end group has. Further approaches through experimental methodologies are needed to further elucidate chemistry.

[0004]

The object of the present invention is to provide an aromatic polycarbonate having excellent hydrolysis stability.

[0005]

The present inventors have arrived at the present invention as a result of extensive studies on aromatic polycarbonates. That is, the present invention is an aromatic polycarbonate in which at least one of the terminal groups has a group represented by the general formula (1). -A-OR _f (1) [In the formula, A represents a phenylene group, a naphthylene group, or a biphenylene group, and R _f represents a-(CHR ₁ ) R ₂ group (R ₁ represents a hydrogen atom or a fluorine atom, R ₂ represents an alkyl group which may contain a fluorine atom, and when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having at least one fluorine atom)] General formula (1) according to the present invention In the compound represented by, R _f is a — (CHR ₁ ) R ₂ group (R ₁ and R ₂ have the same meanings as described above), and more preferably R _f is a group represented by the following formula. Is. -(CHR ₁ ) [C _p (R ₃ R ₄ ) _p ] (C _q F _2q ) R ₅ (wherein R ₁ , R ₃ , R ₄ , and R ₅ each represent a hydrogen atom or a fluorine atom, and p And q represents an integer of 1 to 16) Particularly preferably, R _f is a group represented by the above formula in which p and q are integers of 1 to 12.

In the general formula (1) according to the present invention, R _f
Specific examples of the 1-hydroperfluoroethyl group, 1-hydroperfluoropropyl group, 1-hydroperfluorobutyl group, 1-hydroperfluoropentyl group, 1-hydroperfluorohexyl group, 1- Hydroperfluoroheptyl group, 1-hydroperfluorooctyl group, 1-hydroperfluorononyl group, 1-hydroperfluorodecyl group, 1-hydroperfluorododecyl group, 1-hydroperfluorotetradecyl group, 1-
Hydroperfluoropentadecyl group, 1-hydroperfluorohexadecyl group, 1,1-dihydroperfluoroethyl group, 1,1-dihydroperfluoropropyl group,
1,1-dihydroperfluorobutyl group, 1,1-dihydroperfluoropentyl group, 1,1-dihydroperfluorohexyl group, 1,1-dihydroperfluoroheptyl group, 1,1-dihydroperfluorooctyl group,
1,1-dihydroperfluorononyl group, 1,1-dihydroperfluorodecyl group, 1,1-dihydroperfluoroundecyl group, 1,1-dihydroperfluorododecyl group, 1,1-dihydroperfluorotridecyl group Base,
1,1-dihydroperfluorotetradecyl group, 1,1
-Dihydroperfluoropentadecyl group, 1,1-dihydroperfluorohexadecyl group,

1,1,2-trihydroperfluoroethyl group, 1,1,3-trihydroperfluoropropyl group, 1,1,4-trihydroperfluorobutyl group,
1,1,5-trihydroperfluoropentyl group, 1,
1,6-trihydroperfluorohexyl group, 1,1,
7-trihydroperfluoroheptyl group, 1,1,8-
Trihydroperfluorooctyl group, 1,1,9-trihydroperfluorononyl group, 1,1,11-trihydroperfluoroundecyl group, 1,1,2,2-tetrahydroperfluoropropyl group, 1, 1,2,2-tetrahydroperfluorobutyl group, 1,1,2,2-tetrahydroperfluoropentyl group, 1,1,2,2-tetrahydroperfluorohexyl group, 1,1,2,2-
Tetrahydroperfluoroheptyl group, 1,1,2,2
-Tetrahydroperfluorooctyl group, 1,1,2,
2-tetrahydroperfluorononyl group, 1,1,2,
2-tetrahydroperfluorodecyl group, 1,1,2,
2-tetrahydroperfluoroundecyl group, 1,1,
2,2-tetrahydroperfluorododecyl group, 1,
1,2,2-tetrahydroperfluorotetradecyl group, 1,1,2,2-tetrahydroperfluoropentadecyl group, 1,1,2,2-tetrahydroperfluorohexadecyl group, 1,1,2,2 , 3-pentahydroperfluoropropyl group, 1,1,2,2,4-pentahydroperfluorobutyl group, 1,1,2,2,5-pentahydroperfluoropentyl group, 1,1,2, 2,7
-Pentahydroperfluoroheptyl group, 1,1,2,
2,8-pentahydroperfluorooctyl group, 1,
1,2,2,10-pentahydroperfluorodecyl group, 1,1,2,2,12-pentahydroperfluorododecyl group, 1,1,2,2,14-pentahydroperfluorotetradecyl group,

1,1,2,2,3,3-hexahydroperfluorobutyl group, 1,1,2,2,3,3-hexahydroperfluoropentyl group, 1,1,2,2,3 ，
3-hexahydroperfluorohexyl group, 1,1,
2,2,3,3-hexahydroperfluoroheptyl group, 1,1,2,2,3,3-hexahydroperfluorooctyl group, 1,1,2,2,3,3-hexahydroperfluoro Nonyl group, 1,1,2,2,3,3-hexahydroperfluorodecyl group, 1,1,2,2,3
3-hexahydroperfluoroundecyl group, 1,1,
2,2,3,3-hexahydroperfluorododecyl group, 1,1,2,2,3,3-hexahydroperfluorotetradecyl group, 1,1,2,2,3,3-hexahydroper Fluoropentadecyl group, 1,1,2,2
2,3,3-hexahydroperfluorohexadecyl group, 1,1,2,2,3,3,4-heptahydroperfluorobutyl group, 1,1,2,2,3,3,5-hepta Hydroperfluoropentyl group, 1,1,2,2,3,
3,7-heptahydroperfluoroheptyl group, 1,
1,2,2,3,3,8-heptahydroperfluorooctyl group, 1,1,2,2,3,3,10-heptahydroperfluorodecyl group, 1,1,2,2,3,3 Three
4,4-octahydroperfluoropentyl group, 1,
1,2,2,3,3,4,4-octahydroperfluorohexyl group, 1,1,2,2,3,3,4,4-octahydroperfluoroheptyl group, 1,1,2, Two
3,3,4,4-octahydroperfluorooctyl group, 1,1,2,2,3,3,4,4-octahydroperfluorodecyl group, 1,1,2,2,3,3,3 4,4
-Octahydroperfluoroundecyl group, 1,1,
2,2,3,3,4,4-octahydroperfluorododecyl group, 1,1,2,2,3,3,4,4-octahydroperfluorotetradecyl group,

1,1,2,2,3,3,4,4,5-nonahydroperfluoropentyl group, 1,1,2,2
3,3,4,4,6-nonahydroperfluorohexyl group, 1,1,2,2,3,3,4,4,8-nonahydroperfluorooctyl group, 1,1,2,2 3,3
4,4,10-nonahydroperfluorodecyl group, 1,
1,2,2,3,3,4,4,14-nonahydroperfluorotetradecyl group, 1,1,2,2,3,3,4,
4,5,5-decahydroperfluorohexyl group, 1,
1,2,2,3,3,4,4,5,5-decahydroperfluorooctyl group, 1,1,2,2,3,3,4
4,5,5-decahydroperfluorodecyl group, 1,
1,2,2,3,3,4,4,5,5-decahydroperfluorotetradecyl group, 6-perfluoromethylhexyl group, 6-perfluoroethylhexyl group, 6-perfluorobutylhexyl group, 6 -Perfluorohexylhexyl group, 7-perfluoromethylheptyl group, 8-
Named perfluoromethyloctyl group, 8-perfluorobutyloctyl group, 9-perfluoropropylundecyl group, 10-perfluoropentyldecyl group, 11-perfluorooctylundecyl group, 12-perfluorobutyldodecyl group You can

Further, in the general formula (1) according to the present invention, A represents a phenylene group, a naphthylene group or a biphenylene group, and these groups are an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms. It may be mono- or polysubstituted with a group or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), and specific examples thereof include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4 phenylene group. -Phenylene group, 1,2-naphthylene group, 1,3-naphthylene group,
1,4-naphthylene group, 1,5-naphthylene group, 1,6
-Naphthylene group, 1,8-naphthylene group, 2,3-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group, 2,2'-biphenylene group, 2,4'-biphenylene group, 3, 3'-biphenylene group, 3,4'-biphenylene group, 4,4'-biphenylene group or their C1-8 alkyl substitution, C1-8 alkoxy substitution, halogen substitution derivative can be mentioned. , And more preferably 1,4-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group,
2,7-naphthylene group, 4,4'-biphenylene group or alkyl substitution thereof having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Is an alkoxy-substituted or halogen-substituted derivative of.

Suitable endcapping agents for use in producing an aromatic polycarbonate having at least one of the terminal groups of the present invention having a group represented by the general formula (1) include those represented by the general formula (1-A The compound represented by these can be mentioned. _{Y-A-OR f (1} -A) ( wherein, R _f and A are as defined above, Y is -OH
Group, -OM group, -OCOZ group, -COOH group, -COO
M group or -COZ group, M represents a metal ion, Z represents a halogen atom) In the compound represented by the general formula (1-A) according to the present invention, Y is -OH group, -OM group,- OC
OZ group, -COOH group, -COOM group or -COZ group, M represents a metal ion, Z represents a halogen atom,
M is preferably a monovalent or divalent alkali metal ion or an alkaline earth metal ion, and specific examples thereof include lithium, sodium, potassium and calcium ions, and Z is preferably
Fluorine atom, chlorine atom, bromine atom can be mentioned,
More preferably, it is a chlorine atom.

The compound represented by the general formula (1-A) according to the present invention can be produced by a known method. For example, in the general formula (1-A), the compound in which Y is represented by -OH group or -COOH group can be produced by the method described in U.S. Pat. No. 4,886,619. In the general formula (1-A), Y is a compound represented by an —OCOZ group, for example, a compound in which Z is a chlorine atom is produced by reacting phosgene with a compound in which Y is an —OH group. be able to. In the compound represented by the general formula (1-A), in which Y is a —COZ group, for example, a compound in which Z is a chlorine atom is a compound in which Y is a —COOH group, for example, thionyl chloride or oxalyl chloride. Can be applied to manufacture. In the general formula (1-A), the compound in which Y is an -OM group is a compound in which Y is an -OH group, and is, for example, an alkali such as sodium hydroxide, potassium hydroxide or calcium hydroxide in an aqueous solution. It can be produced by reacting a metal base or an alkaline earth base. In the general formula (1-A),
In a compound in which Y is represented by a -COOM group, Y is -COOH.
It can be produced by reacting the group compound with an alkali metal base such as sodium hydroxide, potassium hydroxide or calcium hydroxide or an alkaline earth base in an aqueous solution.

In the aromatic polycarbonate in which at least one of the terminal groups of the present invention has a group represented by the general formula (1), the group represented by the general formula (1) is typically shown below. Examples thereof include, but the present invention is not limited thereto. Example number Example group 1.2- (1'-hydroperfluorobutyloxy) phenyl group 2.2- (1 ', 1'-dihydroperfluorohexyloxy) phenyl group 3.2- (1', 1'- Dihydroperfluorododecyloxy) phenyl group 4.3- (1 ′, 1′-dihydroperfluorononyloxy) phenyl group 5.3- (1 ′, 1′-dihydroperfluorotetradecyloxy) phenyl group 6.3 -(1 ', 1', 2 ', 2'-tetrahydroperfluoropentyloxy) phenyl group 7.4- (1'-hydroperfluoroethyloxy) phenyl group 8.4- (1'-hydroperfluorobutyl) (Oxy) phenyl group 9.4- (1'-hydroperfluorooctyloxy)
Phenyl group 10.4- (1 ', 1'-dihydroperfluoroethyloxy) phenyl group

11.4- (1 ', 1'-Dihydroperfluorobutyloxy) phenyl group 12.4- (1', 1'-dihydroperfluorohexyloxy) phenyl group 13.4- (1 ', 1) '-Dihydroperfluorooctyloxy) phenyl group 14.4- (1', 1 ', 7'-trihydroperfluoroheptyloxy) phenyl group 15.4- (1', 1 ', 11'-trihydroper Fluoroundecyloxy) phenyl group 16.4- (1 ′, 1 ′, 2 ′, 2′-tetrahydroperfluorobutyloxy) phenyl group 17.4- (1 ′, 1 ′, 2 ′, 2′-tetrahydro Perfluoropentyloxy) phenyl group 18.4- (1 ′, 1 ′, 2 ′, 2′-tetrahydroperfluorohexyloxy) phenyl group 19.4- (1 ′, 1 ′, 2 ′, 2′-tetrahydro Perfluorode Luoxy) phenyl group 20.4- (1 ', 1', 2 ', 2', 8'-pentahydroperfluorooctyloxy) phenyl group 21.4- (1 ', 1', 2 ', 2', 3 ', 3'-hexahydroperfluorobutyloxy) phenyl group 22.4- (1', 1 ', 2', 2 ', 3', 3 ',
4 ', 4'-octahydroperfluorooctyloxy) phenyl group 23.4- (1', 1 ', 2', 2 ', 3', 3 ',
4 ', 4', 5 ', 5'-decahydroperfluorodecyloxy) phenyl group 24.4- (7-perfluoroethylheptyloxy)
Phenyl group 25.4- (11-perfluorooctylundecyloxy) phenyl group

26.4- (1 ', 1'-Dihydroperfluorohexyloxy) -3-methylphenyl group 27.4- (1', 1'-dihydroperfluorobutyloxy) -3-methoxyphenyl group 28 4- (1 ', 1'-dihydroperfluorohexyloxy) -2-fluorophenyl group 29.4- (1', 1'-dihydroperfluoropropyloxy) -2-chlorophenyl group 30.4- (1 ', 1'-Dihydroperfluorohexyloxy) -3-chlorophenyl group 31.1- (1', 1'-dihydroperfluoroethyloxy) -2-naphthyl group 32.2- (1 ', 1', 2 ', 2', 4'-Pentahydroperfluorobutyloxy) -1-naphthyl group 33.3- (1 ', 1'-dihydroperfluorobutyloxy) -1-naphthyl group 34.3- (1', 1 '-Dihydroperfluoropropyloxy) -2-naphthyl group 35.3- (1', 1 ', 2', 2'-tetrahydroperfluorohexyloxy) -2-naphthyl group 36.3- (1 ', 1 ', 2', 2 ', 3', 3 ',
7'-heptahydroperfluoroheptyloxy) -2
-Naphthyl group 37.4- (1'-hydroperfluorobutyloxy)
-1-naphthyl group 38.4- (1 ', 1'-dihydroperfluorobutyloxy) -1-naphthyl group 39.4- (1', 1'-dihydroperfluorohexyloxy) -1-naphthyl group 40 4- (1 ', 1'-dihydroperfluorooctyloxy) -2-chloro-1-naphthyl group

41.4- (6'-perfluoromethylhexyloxy) -1-naphthyl group 42.4- (1 ', 1', 8'-trihydroperfluorooctyloxy) -1-naphthyl group 43. 5- (1'-hydroperfluoroethyloxy)
-1-naphthyl group 44.5- (1'-hydroperfluorobutyloxy)
-1-Naphthyl group 45.5- (1 ', 1'-dihydroperfluorobutyloxy) -1-naphthyl group 46.5- (1', 1'-dihydroperfluorohexyloxy) -1-naphthyl group 47 .5- (1 ', 1'-Dihydroperfluorooctyloxy) -1-naphthyl group 48.5- (1', 1 ', 7'-Trihydroperfluoroheptyloxy) -1-naphthyl group 49.6 -(1'-hydroperfluoroethyloxy)
-1-naphthyl group 50.6- (1'-hydroperfluorobutyloxy)
2-naphthyl group 51.6- (1'-hydroperfluorohexyloxy) -2-naphthyl group 52.6- (1 ', 1'-dihydroperfluoropentyloxy) -2-naphthyl group 53.6- (1 ′, 1′-Dihydroperfluorohexyloxy) -2-naphthyl group 54.6- (1 ′, 1′-dihydroperfluorooctyloxy) -1-ethyl-2-naphthyl group 55.6- (1 ', 1', 7'-Trihydroperfluoroheptyloxy) -2-naphthyl group

56.6- (1 ', 1', 2 ', 2'-Tetrahydroperfluoroheptyloxy) -2-naphthyl group 57.6- (1', 1 ', 2', 2 ', 3' , 3'-hexahydroperfluorohexyloxy) -2-naphthyl group 58.6- (1 ', 1', 2 ', 2', 3 ', 3',
4 ', 4'-octahydroperfluorohexyloxy) -2-naphthyl group 59.7- (1'-hydroperfluoropropyloxy) -2-naphthyl group 60.7- (1'-hydroperfluoropentyloxy ) -2-naphthyl group 61.7- (1 ′, 1′-dihydroperfluorobutyloxy) -2-naphthyl group 62.7- (1 ′, 1′-dihydroperfluorooctyloxy) -2-naphthyl group 63.7- (1 ', 1', 2 ', 2', 3 ', 3',
4 ', 4'-octahydroperfluoropentyloxy) -2-naphthyl group 64.8- (1', 1'-dihydroperfluorobutyloxy) -1-naphthyl group 65.2- [2 '-(1 ', 1'-Dihydroperfluorohexyl) oxyphenyl] biphenyl 66.2- [4'-(1 ', 1'-dihydroperfluorooctyl) oxyphenyl] phenyl group 67.3- [3'-(1 ' , 1'-dihydroperfluorobutyloxy) phenyl] phenyl group 68.4- [3 '-(6'-perfluorobutylhexyloxy) phenyl] phenyl group 69.3- [4'-(1'-hydroper Fluoroethyloxy) phenyl] phenyl group 70.4- [4 ′-(1′-hydroperfluoroethyloxy) phenyl] phenyl group 71.4- [4 ′-(1′-hydroperfluorobutyi) Oxy) phenyl] phenyl group 72.4- [4 ′-(1 ′, 1′-dihydroperfluorobutyloxy) phenyl] phenyl group 73.4- [4 ′-(1 ′, 1′-dihydroperfluorooctyl) Oxy) phenyl] phenyl group 74.4- [4 '-(1', 1 ', 11'-trihydroperfluoroundecyloxy) phenyl] phenyl group 75.4- [4'-(1 ', 1' , 2 ', 2'-Tetrahydroperfluoroheptyloxy) phenyl] phenyl group 76.4- [4'-(1 ', 1'-dihydroperfluorooctyloxy) phenyl] -3-chlorophenyl group 77.4- [ 4 '-(1'-hydroperfluorobutyloxy) phenyl] -3-methylphenyl group

The aromatic polycarbonate of the present invention can be produced from at least one aromatic dihydroxy compound, a carbonate precursor and at least one compound represented by the general formula (1-A). For this, an interfacial polymerization method, a solution polymerization method, or a transesterification method known to those skilled in the art can be used. In particular, the interfacial polymerization method is a preferred production method. In producing the aromatic polycarbonate having a novel end group of the present invention,
The compound represented by the general formula (1-A) acts as a terminal blocking agent and serves to control or adjust the molecular weight of the aromatic polycarbonate in the process for producing the aromatic polycarbonate of the present invention. These end-capping agents and aromatic dihydroxy compounds form a carbonate bond or an ester bond by the action of a carbonate precursor to form an aromatic polycarbonate having an end group represented by the general formula (1) of the present invention. To generate. In the compound represented by the general formula (1-A), Y is —OH in the carbonate bond.
Group, -OM group or -OCOZ group is formed by using a compound, while Y is
It is formed by using a compound which is a -COOH group, a -COOM group or a -COZ group.

The weight average molecular weight of the aromatic polycarbonate of the present invention can be any weight average molecular weight depending on the amount of the compound represented by the general formula (1-A) used in the production. Considering various physical properties such as moldability and impact resistance, the weight average molecular weight is preferably about 15,000 to about 150,000, more preferably about 20.
000 to about 100,000 weight average molecular weight. The weight average molecular weight generally depends on the amount of the compound represented by the general formula (1-A) used in producing the aromatic polycarbonate. Generally, the larger the amount of the compound represented by the general formula (1-A) used, the smaller the weight average molecular weight of the aromatic polycarbonate, and conversely, the amount of the compound represented by the general formula (1-A) used. When the amount is small, the weight average molecular weight of the aromatic polycarbonate becomes large. Generally, the amount of the compound represented by the general formula (1-A) used is about 1.2 to about 1 with respect to the amount of the aromatic dihydroxy compound used.
0.0 mol% is preferable, and about 1.5
More preferably, about 7.0 mol%.

The end-capping agent represented by the general formula (1-A) is generally used in the reaction of an aromatic dihydroxy compound with a carbonate precursor first, that is, prior to the addition of the carbonate precursor. It may be present together with the dihydroxy compound, or it may be sequentially and continuously supplied with the addition of the carbonate precursor. In the production of the polycarbonate of the present invention, the general formula (1-
The compound represented by A) can be used alone or in combination. When only one type is used, the end groups of the aromatic polycarbonate are all groups having the same structure. When a plurality of compounds are used in combination, the general formula (1
Various end groups are mixed depending on the number, amount and type of the compound represented by -A). Furthermore, the general formula (1-
The compound represented by A) can also be used in combination with other known end-capping agents within a range that does not impair the desired effects of the present invention. When the compound represented by the general formula (1-A) and another known end-capping agent are used together in the production of the aromatic polycarbonate of the present invention, the compound represented by the general formula (1 The ratio of the compound represented by -A) is 3
It is preferably 0 mol% or more, more preferably 50 mol% or more, and particularly preferably 60 mol% or more.

Examples of the terminal blocking agent other than the compound represented by the general formula (1-A) include monovalent hydroxyaromatic compounds, monovalent hydroxyaromatic compound chloroformates, and monovalent hydroxyaromatic compounds. Examples thereof include a compound having a carboxylic acid group and a monovalent carboxylic acid chloride compound. Examples of the monovalent hydroxyaromatic compound include phenol, p-cresol, o-ethylphenol, p-ethylphenol, p-isopropylphenol and p-tert.
-Butylphenol, p-cumylphenol, p-cyclohexylphenol, p-octylphenol, p-
Nonylphenol, 2,4-xylenol, p-methoxyphenol, p-hexyloxyphenol, p-decyloxyphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, p-bromophenol, pentabromophenol, penta Chlorophenol, p-phenylphenol, p-isopropenylphenol, 2,4-di (1-methyl-1-phenylethyl) phenol, β-naphthol, α-naphthol,
p- (2 ', 4', 4'-trimethylchromanyl) phenol, 2- (4'-methoxyphenyl) -2- (4 "
-Hydroxyphenyl) propane and other phenols.

Examples of the monovalent hydroxyaromatic compound chloroformate compound include the above-mentioned monovalent hydroxyaromatic compound chloroformate derivatives. Also, 1
Examples of the compound having a divalent carboxylic acid group include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid, and 3
-Methylbutyric acid, 3,3-dimethylbutyric acid, 4-methylvaleric acid, 3,3-dimethylvaleric acid, 4-methylcaproic acid,
Fatty acids such as 2,4-dimethylvaleric acid, 3,5-dimethylcaproic acid and phenoxyacetic acid, benzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, p-propyloxybenzoic acid, p-butoxy Benzoic acids such as benzoic acid, p-hexyloxybenzoic acid, p-octyloxybenzoic acid, p-phenylbenzoic acid, p-benzylbenzoic acid and p-chlorobenzoic acid. Examples of the monovalent carboxylic acid chloride compound include chloride derivatives of the above-mentioned compounds having a monovalent carboxylic acid group. In addition, the above 1
Alkali metal (eg, lithium, sodium, potassium) salts of divalent hydroxyaromatic compounds or compounds having a monovalent carboxylic acid group, alkaline earth metals (eg,
Calcium) salts can also be used as endcapping agents.

Examples of the aromatic dihydroxy compound used in producing the aromatic polycarbonate compound of the present invention include compounds represented by the general formula (2). HO-R-OH (2) (In the formula, R is an aromatic hydrocarbon group or a substituted aromatic having a substituent such as an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a halogen atom, a nitro group or an alkoxy group. each (3) (wherein, Ar ¹ and Ar ² - in group is a hydrocarbon group) in the above general formula (2), the group R is preferably of the general formula (3) -Ar ¹ -B-Ar ² It is a monocyclic divalent aromatic group,
B is a group that connects Ar ¹ and Ar ² ). In the general formula (3), Ar ¹ and Ar ² are
Each is a monocyclic divalent aromatic group, preferably a phenylene group or a substituted phenylene group having a substituent,
Examples of the substituent include a hydrocarbon group such as an alkyl group, a cycloalkyl group, an alkenyl group and an aryl group, a halogen group, a nitro group and an alkoxy group.

Both Ar ¹ and Ar ² are p-phenylene groups, m
-Phenylene group or o-phenylene group, or one is a p-phenylene group, one is preferably an m-phenylene group or an o-phenylene group, especially both Ar ¹ and Ar ² are p-phenylene group Preferably. B
Is a group that connects Ar ¹ and Ar ² , and is a single bond or a divalent hydrocarbon group, and further —O—, —S—, —SO—,
It may be a group containing atoms other than carbon and hydrogen, such as —SO ₂ — and —CO—. Examples of the divalent hydrocarbon group include a saturated hydrocarbon group, for example, an alkylidene group such as methylene, ethylene, 2,2-propylidene, cyclohexylidene and the like, but a group substituted with an aryl group is also included. Further, it may be a hydrocarbon group containing an aromatic group or other unsaturated hydrocarbon group.

Specific examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane and bis (2
-Methyl-4-hydroxy) methane, bis (3-methyl-4-hydroxy) methane, 1,1-bis (4'-hydroxyphenyl) ethane, 1,2-bis (4'-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl)
Diphenylmethane, bis (4-hydroxyphenyl)-
1-naphthylmethane, 1,1-bis (4'-hydroxyphenyl) -1-phenylethane, 2,2-bis (4 '
-Hydroxyphenyl) propane ["bisphenol A"], 1,1-bis (4'-hydroxyphenyl)-
3-methylpropane, 1,3-bis (4'-hydroxyphenyl) -1,1-dimethylpropane, 2- (4'-
Hydroxyphenyl) -2- (3′-hydroxyphenyl) propane, 2,2-bis (4′-hydroxyphenyl) butane, 1,1-bis (4′-hydroxyphenyl) -3-methylbutane, 2,2- Bis (4′-hydroxyphenyl) pentane, 2,2-bis (4′-hydroxyphenyl) -4-methylpentane, 2,2-bis (4′-hydroxyphenyl) hexane, 4,4-bis (4 ′) -Hydroxyphenyl) heptane, 2,2-bis (4'-hydroxyphenyl) octane, 2,2-bis (4'-hydroxyphenyl) nonane, bis (3,5-
Dimethyl-4-hydroxyphenyl) methane, 2,2-
Bis (3′-methyl-4′-hydroxyphenyl) propane,

2,2-bis (3'-ethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-n-)
Propyl-4'-hydroxyphenyl) propane, 2,
2-bis (3'-isopropyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-sec-butyl-
4'-hydroxyphenyl) propane, 2,2-bis (3'-tert-butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-cyclohexyl-4'-
Hydroxyphenyl) propane, 2,2-bis (3'-
Allyl-4'-hydroxyphenyl) propane, 2,2
-Bis (3'-methoxy-4'-hydroxyphenyl)
Propane, 2,2-bis (3 ', 5'-dimethyl-4'
-Hydroxyphenyl) propane, 2,2-bis (2 ', 3', 5 ', 6'-tetramethyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-chloro-4'-hydroxy) Phenyl) propane, 2,2-bis (3 ', 5'-dichloro-4'-hydroxyphenyl) propane, 2,2-bis (3'-bromo-4'-hydroxyphenyl) propane, 2,2-bis (3 ',
5'-dibromo-4'-hydroxyphenyl) propane, 2,2-bis (2 ', 6'-dibromo-3', 5 '
Dimethyl-4′-hydroxyphenyl) propane, bis (4-hydroxyphenyl) cyanomethane, 1-cyano-3,3-bis (4′-hydroxyphenyl) butane,
Bis (hydroxyaryl) alkanes such as 2,2-bis (4′-hydroxyphenyl) hexafluoropropane,

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (3'-methyl-4'-hydroxyphenyl) cyclohexane , 1,
1-bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) cyclohexane, 1,1-bis (3', 5'-
Dichloro-4′-hydroxyphenyl) cyclohexane, 1,1-bis (4′-hydroxyphenyl) -4-
Methylcyclohexane, 1,1-bis (4′-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4′-hydroxyphenyl) cycloheptane, 1,1-bis (4′-hydroxy) Phenyl)
Cyclooctane, 1,1-bis (4'-hydroxyphenyl) cyclononane, 1,1-bis (4'-hydroxyphenyl) cyclododecane, 2,2-bis (4'-hydroxyphenyl) norbornane, 8,8- Screw (4'-
Hydroxyphenyl) tricyclo [5.2.1.
0 ^2.6 ] Bis (hydroxyaryl) cycloalkanes such as decane and 2,2-bis (4′-hydroxyphenyl) adamantane, 4,4′-dihydroxydiphenyl ether, 3,3′-dimethyl-4,4′-dihydroxy Bis (hydroxyaryl) ethers such as diphenyl ether and ethylene glycol bis (4-hydroxyphenyl) ether,

4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dicyclohexyl-
4,4'-dihydroxydiphenyl sulfide, 3,
3'-diphenyl-4,4'-dihydroxydiphenyl sulfide, 3,3 ', 5,5'-tetramethyl-4,
Bis (hydroxyaryl) sulfides such as 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-
Bis (hydroxyaryl) sulfoxides such as 4,4′-dihydroxy-diphenyl sulfoxide, 4,4′-
Dihydroxydiphenyl sulfone, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfone, 3,
Bis (hydroxyaryl) such as 3'-diphenyl-4,4'-dihydroxydiphenyl sulfone and 3,3'-dichloro-4,4'-dihydroxydiphenyl sulfone
Sulfones, bis (4-hydroxyphenyl) ketone,
Bis (hydroxyaryl) ketones such as bis (3-methyl-4-hydroxyphenyl) ketone,

Further, 6,6'-dihydroxy-2,
2 ', 3,3'-tetrahydro-3,3,3', 3'-
Tetramethyl-1,1'-spirobi (1H-indene)
["Spirobiindane bisphenol"], 7,7-dihydroxy-3,3 ', 4,4'-tetrahydro-4,
4,4 ', 4'-Tetramethyl-2,2'-spirobi (2H-1-benzopyran) ["spirobichroman"], trans-2,3-bis (4'-hydroxyphenyl) -2-butene , 9,9-bis (4'-hydroxyphenyl) fluorene, 3,3-bis (4'-hydroxyphenyl) -2-butanone, 1,6-bis (4'-
Hydroxyphenyl) -1,6-hexanedione, 1,
1-dichloro-2,2-bis (4'-hydroxyphenyl) ethylene, 1,1-dibromo-2,2-bis (4 '
-Hydroxyphenyl) ethylene, 1,1-dichloro-
2,2-bis (3′-phenoxy-4′-hydroxyphenyl) ethylene, α, α, α ′, α′-tetramethyl-α, α′-bis (4-hydroxyphenyl) -p-xylene, α , Α, α ', α'-tetramethyl-α, α'
-Bis (4-hydroxyphenyl) -m-xylene,

3,3-bis (4-hydroxyphenyl)
Phthalide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathiin, 2,7-dihydroxy-
9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, 4,4′-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene , 2,7-dihydroxynaphthalene, 2,7-dihydroxypyrene and the like. In addition to the above aromatic dihydroxy compounds,
Hydroquinone, resorcin, etc. are also used. Furthermore, for example, bisphenols (aromatic dihydroxy compounds) containing an ester bond, which can be produced by reacting 2 mol of bisphenol A with 1 mol of isophthaloyl chloride or terephthaloyl chloride, are also useful. You may use these individually or in mixture of 2 or more types. A particularly preferred aromatic dihydroxy compound is bisphenol A.

Examples of the carbonate precursor include carbonyl halides, haloformate compounds, dialkyl carbonate compounds, diaryl carbonate compounds and alkylaryl carbonate compounds, and carbonyl halides and haloformate compounds are preferred. As the carbonyl halide,
Carbonyl chloride called phosgene is used, but it may be a carbonyl halide derived from a halogen other than chlorine, such as carbonyl bromide, carbonyl iodide, carbonyl fluoride, or a mixture thereof. Further, a compound having the ability to form a haloformate group, for example, trichloromethylchloroformate which is a dimer of phosgene, bis (trichloromethyl) carbonate which is a trimer of phosgene, etc. may be used. Preference is given to using phosgene. As the haloformate compound, a bis or monohaloformate compound and an oligomeric bis or monohaloformate compound are used, and typically, the compound represented by the general formula (4) (formula 1) can be mentioned. .

[0032]

[Chemical 1] (In the formula, X represents a hydrogen atom or a halocarbonyl group,
At least one X is a halocarbonyl group, R ′ represents a divalent aliphatic group or aromatic group, and n represents 0 or a positive integer) The compound represented by the general formula (4) is A bishaloformate compound and an oligomeric bishaloformate compound derived from an aliphatic dihydroxy compound, and a bishaloformate compound and an oligomeric bishaloformate compound derived from an aromatic dihydroxy compound. In the general formula (4), examples of the divalent aliphatic group R ′ include an alkylene group having 2 to 20 carbon atoms and a cycloalkylene group having 4 to 12 carbon atoms, and examples thereof include linear or branched ethylene. Group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group,
A divalent hydrocarbon group such as an undecylene group or a dodecylene group,
Further, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cycloundecylene group, a cyclododecylene group or a divalent cyclic hydrocarbon group thereof optionally substituted. Is.

Specific examples of these aliphatic dihydroxy compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,
6-hexanediol, 1,5-hexanediol,
1,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, neopentyl glycol, 2-ethyl-
1,6-hexanediol, 2-methyl-1,3-propanediol, 1,3-cyclohexanediol, 1,
4-cyclohexanediol, 2,2-bis (4'-hydroxycyclohexyl) propane, etc. can be mentioned. The divalent aliphatic group R ′ also includes a group represented by the general formula (5). -R "-Ar ³ -R"-(5) (In the formula, R "represents an alkylene group having 1 to 6 carbon atoms, and
r ³ represents a divalent aromatic group having 6 to 12 carbons) In the general formula (5), the R ″ group represents an alkylene group having 1 to 6 carbons, for example, a linear or branched methylene group. Group, ethylene group, propylene group, butylene group, pentylene group,
Examples thereof include a divalent hydrocarbon group of a hexylene group, and the Ar ³ group represents a divalent aromatic group having 6 to 12 carbon atoms, and examples thereof include a phenylene group, a substituted phenylene group and a naphthylene group.

Specific examples of this type of aliphatic dihydroxy compound include xylylenediol and 1,4-bis (2 ').
-Hydroxyethyl) benzene, 1,4-bis (3'-
Hydroxypropyl) benzene, 1,4-bis (4'-
Examples thereof include hydroxybutyl) benzene, 1,4-bis (5′-hydroxypentyl) benzene, and 1,4-bis (6′-hydroxyhexyl) benzene.
In the general formula (4), examples of the aromatic dihydroxy compound in which the R ′ group is an aromatic group include the aromatic dihydroxy compounds described above, such as bisphenol A and hydroquinone. Further, the oligomeric bis or monohaloformate compound may have R ′ groups having different structures in the same molecule. These haloformate compounds may be used alone, in a mixture, or in a mixture with a carbonyl halide. Examples of the dialkyl carbonate compound, the diaryl carbonate compound, and the alkylaryl carbonate compound include dimethyl carbonate,
Examples thereof include diphenyl carbonate, a methylphenyl carbonate compound, diphenyl carbonate substituted with a halogen atom, a nitro group and the like, and a mixture thereof.

When the aromatic polycarbonate of the present invention is produced by the interfacial polymerization method, a carbonyl halide and / or a halogenate compound is preferably used as the carbonate precursor. The carbonate precursor may be used in any of a gas state, a liquid state and a solid state.However, when a carbonyl halide is used, it is used in a gas state or in a state of being dissolved in an organic solvent. It is preferably used as a solvent solution, and when a haloformate compound is used, it is preferably used as an organic solvent solution in a solid state or in a state of being dissolved in an organic solvent. When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method, a known method for producing an aromatic polycarbonate can be used. For example, in a two-phase mixed solvent of at least one aromatic dihydroxy compound and an alkali metal or alkaline earth metal base, water and an organic solvent which is substantially insoluble in water, a carbonyl halide or / and a halogenate compound are represented by the general formula A method for producing an aromatic polycarbonate by allowing it to act in the presence of a compound represented by (1-A), and more preferably a method for producing an aromatic polycarbonate in the presence of a polycarbonate-forming catalyst.

In the production of the aromatic polycarbonate of the present invention by the interfacial polymerization method, when a carbonate carbonyl compound, for example, is used as the carbonate precursor, the amount thereof is about 1 relative to the amount of the aromatic dihydroxy compound. It is preferred to use an amount of from 0.0 to about 1.3 times the molar amount. The use of a carbonyl halide compound in an amount extremely smaller than 1.0 times the molar amount results in generation of unreacted aromatic dihydroxy compound, which is a factor of producing an aromatic polycarbonate having a poor color tone. Further, the use of a carbonyl halide compound in an excessively larger amount than 1.3 times by mole results in the production of a large amount of oligomers whose terminals are terminated by haloformate end groups, and as a result, haloformate end groups of oligomers in the reaction system O
The proportion of H groups (or phenolate groups) is not preferable, since the haloformate end groups become excessive, and the normal polymerization time results in the formation of an aromatic polycarbonate having a small molecular weight that is terminated by haloformate end groups.

Any organic solvent may be used as long as it is substantially insoluble in water, inert to the reaction, and capable of dissolving the aromatic polycarbonate. For example, dichloromethane, chloroform, 1,2-
Aliphatic chlorinated compounds such as dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane, dichloropropane, etc., or chlorinated hydrocarbons such as chlorobenzene, aromatic chlorinated compounds such as dichlorobenzene, or a mixture thereof as a suitable organic solvent. Can be mentioned. Further, an organic solvent in which an aromatic hydrocarbon such as toluene, xylene, ethylbenzene, etc., an aliphatic hydrocarbon such as hexane, heptane, cyclohexane, etc. are mixed with these chlorinated hydrocarbons or a mixture thereof may be used. A particularly preferred organic solvent is dichloromethane.

The amount of the organic solvent used is usually preferably such that the concentration of the aromatic polycarbonate in the organic solvent solution containing the aromatic polycarbonate at the end of the polymerization is about 5 to about 35% by weight. . When the concentration of the aromatic polycarbonate is extremely low, a large amount of organic solvent is required, which is not preferable from the viewpoint of productivity. Further, when the concentration of the aromatic polycarbonate is close to the saturation concentration, the viscosity of the organic solvent solution of the aromatic polycarbonate becomes very high, so that the reaction efficiency of the interfacial polymerization is lowered and the handleability of the organic solvent solution after the polymerization is deteriorated. It is not preferable because of problems such as the above. It is particularly preferable to use the organic solvent so that the concentration of the aromatic polycarbonate in the organic solvent solution of the aromatic polycarbonate at the end of the polymerization is about 10 to about 20% by weight. The amount of organic solvent used also depends on the amount of water used. The reaction mixture may be in an amount necessary to maintain a substantially uniform emulsified state, and generally, the volume ratio of the organic phase to the water is preferably about 0.4 to 1.5: 1. When the organic solvent is less than the above range, hydrolysis of the carbonate precursor and the haloformate group is increased, and a large amount of stirring power is required to form a uniform emulsified state,
Further, when the amount of the organic solvent is larger than the above range, a larger stirring power is required, which is not preferable from the viewpoint of productivity.

The alkali metal or alkaline earth metal base (hereinafter abbreviated as a base) used in producing the aromatic polycarbonate of the present invention is usually an alkali such as sodium hydroxide, potassium hydroxide or calcium hydroxide. Among the hydroxides of metals or alkaline earth metals, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable, from the viewpoint of being relatively easily available. The base is usually used in the form of an aqueous solution, and it is preferable to dissolve the aromatic dihydroxy compound in this aqueous solution and use it in the reaction. In this case, since the basic aqueous solution of the aromatic dihydroxy compound is generally easily colored, the reducing agent such as sodium sulfite, sodium hydrosulfite or sodium borohydride is added as an antioxidant to make the basic aromatic dihydroxy compound basic. An aqueous solution may be prepared. Suitable polycarbonate production catalyst (also called polymerization catalyst or polycondensation catalyst) used in the interfacial polymerization method
Examples thereof include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, nitrogen-containing heterocyclic compounds and salts thereof, imino ethers and salts thereof, and compounds having an amide group. Preferably, it is a trialkylamine which is a tertiary amine, more preferably it has no branch on the carbon atoms at the 1- and 2-positions, and the alkyl group is C
1 to C4 trialkylamines such as triethylamine, tri-n-propylamine, diethyl-n-propylamine, tri-n-butylamine and the like, which are easily available and have excellent catalytic effect. Triethylamine is particularly preferable in that it is present. The amount of the polycarbonate-forming catalyst used is preferably about 0.0005 to about 0.7 mol% based on the number of moles of the aromatic dihydroxy compound.
When the amount of the catalyst is excessively less than 0.0005 mol%, the catalytic effect for forming an aromatic polycarbonate is not sufficient and a very long polymerization time is required, which is not economical and is not preferable. Further, if the amount of the catalyst is excessively larger than 1.5 mol%, there is no effect of particularly accelerating the polymerization reaction, and the excess polycarbonate-forming catalyst is wasted, which is not preferable. The polycarbonate generation catalyst can be added before or during the reaction when producing the aromatic polycarbonate of the present invention.

In the interfacial polymerization method, the reaction temperature is about 1.
It is preferable to produce the aromatic polycarbonate of the present invention at 0 ° C to the boiling temperature of the organic solvent used for the reaction. 10
At a reaction temperature extremely lower than ℃, the reaction rate becomes slow,
The reaction efficiency becomes poor. Further, it becomes impractical such as requiring a cooling medium or a cooling device. When the organic solvent used is dichloromethane, it can be carried out at a reflux temperature of about 39 ° C. at atmospheric pressure. In practice, the reaction is usually initiated near room temperature and then raised to near reflux temperature by the heat of reaction. The reaction is usually carried out at atmospheric pressure, but if desired, the reaction may be carried out under pressure or under reduced pressure.

The aromatic polycarbonate of the present invention can be made into a branched aromatic polycarbonate by adding a branching agent, if desired.
Suitable branching agents for the aromatic polycarbonates of the present invention include, for example, compounds having three or more aromatic hydroxy groups, chloroformates, carboxylic acid groups, carboxylic acid chloride groups and also active halogen atoms. The specific examples include phloroglucinol,
1,1,4,4-Tetrakis (4′-hydroxyphenyl) cyclohexane, 1,3,5-tris (4′-hydroxyphenyl) benzene, 1,1,2-tris (4 ′)
-Hydroxyphenyl) propane, α, α, α ', α'
-Tetrakis (4'-hydroxyphenyl) -1,4-
Diethylbenzene, 1-hydroxy-2,4-bis [α
-Methyl-α- (4'-hydroxyphenyl) ethyl]
Benzene, 2,2,5,5-tetrakis (4'-hydroxyphenyl) hexane, 1,1,2,3-tetrakis (4'-hydroxyphenyl) propane, 2- (4'-
Hydroxyphenyl) -2- (2 ", 4" -dihydroxyphenyl) propane, 4,6-dimethyl-2,4,6
-Tris (4'-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) heptane, 1,4-bis (4 ',
4 "-dihydroxytriphenylmethyl) benzene,
3,3 ′, 5,5′-tetrahydroxydiphenyl ether, tris (4-hydroxyphenyl) phosphine,
Trimesic acid trichloride, cyanuric acid chloride,
3,3-bis (4'-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3,3-bis (4 '
-Hydroxy-3-methylphenyl) -2-oxo-
2,3-dihydroindole and the like can be mentioned.

When a branching agent is used, its amount can be changed according to the degree of branching of the desired aromatic polycarbonate, but it is usually 0.05 to 0.05 with respect to the aromatic dihydroxy compound. It is preferable to use about 2.0 mol%.

Further, the aromatic polycarbonate of the present invention also includes an aromatic polyester carbonate, and comprises at least one aromatic dihydroxy compound [for example, a compound represented by the general formula (2)], a carbonate precursor. Body (eg phosgene), divalent carboxylic acid or derivative of said compound (eg US Pat. No. 3,169,91)
Aromatic polyester carbonates can be preferably produced using the compound represented by the general formula (1-A), such as isophthalic acid, terephthalic acid, isophthalic acid dichloride, and terephthalic acid dichloride described in No. 21).
At this time, the amount of the divalent carboxylic acid or the derivative of the compound used is 30 to 80 relative to the aromatic dihydroxy compound.
It is preferable to use about mol%.

In producing the aromatic polycarbonate of the present invention, a solution polymerization method already known to those skilled in the art can be used. For example, in a pyridine solution, an aromatic dihydroxy compound or a carbonate precursor can be prepared. A carbonyl halide or / and a haloformate compound and a compound represented by the general formula (1-A) by about 0 to 5
It can be produced by acting at 0 ° C. Using a dialkyl carbonate compound, an alkylaryl carbonate compound and / or a diaryl carbonate compound, an aromatic dihydroxy compound and a general formula (1
When the aromatic polycarbonate of the present invention is produced from the compound represented by -A), a dialkyl carbonate compound, an alkylaryl carbonate compound or /
And a diaryl carbonate compound, a mixture of an aromatic dihydroxy compound and a compound represented by the general formula (1-A), at a temperature of about 60 to about 300 ° C. under normal pressure, increased pressure or reduced pressure, if necessary. In the presence of a transesterification catalyst (eg, metal oxide, hydroxide, carbonate, etc.), it can be produced by a transesterification method already known to those skilled in the art. When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method or a solution polymerization method, usually, an organic solvent solution containing the aromatic polycarbonate is separated from an aqueous layer, and then washed with water until the electrolyte substantially disappears. After washing, the organic solvent is removed from the organic solvent solution by a known method to obtain the aromatic polycarbonate of the present invention. Further, the aromatic polycarbonate produced by the transesterification method may be obtained by directly pelletizing or processing the aromatic polycarbonate melted under the transesterification condition into a molded product.

The aromatic polycarbonate of the present invention is soluble in a specific organic solvent (for example, a halogenated hydrocarbon solvent such as dichloromethane), and can be processed into a molded product such as a film from the organic solvent. The aromatic polycarbonate of the present invention is thermoplastic and can be easily molded from a melt by a known molding method such as injection molding, extrusion molding, blow molding, or lamination.

The aromatic polycarbonate of the present invention may be mixed with another aromatic polycarbonate or polyester such as polyethylene terephthalate or poly (1,4-butylene terephthalate). Further, in the aromatic polycarbonate of the present invention, in order to impart thermal stability, light resistance, weather resistance, flame resistance, release property and other properties to the aromatic polycarbonate, A very wide range of additives, stabilizers, flame retardants and fillers in known manner during or after manufacture, namely processing and heat stabilizers, antioxidants, hydrolysis stabilizers, impact stabilizers, UV absorbers, Release agents, organic halogen compounds, alkali metal sulfonates, glass fibers, glass beads, barium sulfate, TiO2, etc. may be added.

[0047]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples. Example 1 Production of Aromatic Polycarbonate having an End Group of Exemplification No. 7 A 10 l baffled flask was equipped with a three-stage six-blade stirrer and a reflux condenser, and 912 g (4.0 mol) of bisphenol A was added to this flask. 4- (1'-hydroperfluoroethyloxy) benzoic acid 32.4 g (0.1
36 mol, 3.4 mol% relative to bisphenol A),
4 l of dichloromethane and 4 l of deionized water were added to make a suspension, and a nitrogen purge was performed to remove oxygen in the flask. Next, 1.2 g of sodium hydrosulfite and 432 g (10.8 mol) of caustic soda were added to the above suspension.
2.2 l of an aqueous solution in which was dissolved was supplied, and bisphenol A was dissolved at 15 ° C. To this solution, 495 g of phosgene
(5.0 mol) was fed at a rate of 8.25 g / min. The reaction temperature rose to 39 ° C., and reflux of dichloromethane was confirmed. After the supply of phosgene was completed, 0.64 g of triethylamine was added, and the reaction solution was stirred for another 90 minutes to carry out a polymerization reaction. Then, the reaction solution was allowed to stand still, the organic layer was separated, neutralized with hydrochloric acid, and washed with deionized water until the electrolyte was exhausted. To the dichloromethane solution of the aromatic polycarbonate thus obtained, 2 l of toluene and 5 l of water were added, and the mixture was heated to 98 ° C. to distill off the dichloromethane and toluene to obtain an aromatic polycarbonate powder. The obtained aromatic polycarbonate has a number average molecular weight of 20,900 and a weight average molecular weight of 51.
It was 200. The glass transition point was 149 ° C.

Example 2 Preparation of Aromatic Polycarbonate Having an End Group of Exemplification No. 8 In Example 1, instead of using 4- (1′-hydroperfluoroethyloxy) benzoic acid, 4- (1′-
Hydroperfluorobutyloxy) benzoic acid 46.0 g
An aromatic polycarbonate was produced in the same manner as in Example 1 except that (3.4 mol% based on bisphenol A) was used. The obtained aromatic polycarbonate had a number average molecular weight of 21,100 and a weight average molecular weight of 50,900.
The glass transition point was 147 ° C.

Example 3 Production of Aromatic Polycarbonate having an End Group of Exemplified No. 12 Instead of using 4- (1′-hydroperfluoroethyloxy) benzoic acid in Example 1, 4- (1 ′,
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 53.3 g of 1′-dihydroperfluorohexyloxy) phenol (3.4 mol% based on bisphenol A) was used. The obtained aromatic polycarbonate has a number average molecular weight of 20,800 and a weight average molecular weight of 507.
It was 00. The glass transition point was 144 ° C.

Example 4 Preparation of Aromatic Polycarbonate Having End Group No. 14 In Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid, 4- (1 ',
1 ', 7'-trihydroperfluoroheptyloxy)
Phenol 57.7 g (3.
Aromatic polycarbonate was produced in the same manner as in Example 1 except that 4 mol%) was used. The obtained aromatic polycarbonate had a number average molecular weight of 21,100 and a weight average molecular weight of 5,1200. The glass transition point was 143 ° C.

Example 5 Preparation of Aromatic Polycarbonate having End Group No. 23 In Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid, 4- (1 ',
1 ', 2', 2 ', 3', 3 ', 4', 4 ', 5',
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 57.3 g of 5'-decahydroperfluorodecyloxy) phenol (3.2 mol% based on bisphenol A) was used. The obtained aromatic polycarbonate has a number average molecular weight of 22,000 and a weight average molecular weight of 550.
It was 00. The glass transition point was 141 ° C.

Example 6 Preparation of Aromatic Polycarbonate Having End Group No. 26 In Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid, 4- (1 ',
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 55.2 g of 1′-dihydroperfluorohexyloxy) -3-methylphenol (3.4 mol% based on bisphenol A) was used. The obtained aromatic polycarbonate had a number average molecular weight of 20,600 and a weight average molecular weight of 5,700. The glass transition point is 144 ° C.
Met.

Example 7 Preparation of Aromatic Polycarbonate having an Exemplified No. 30 End Group Instead of using 4- (1′-hydroperfluoroethyloxy) benzoic acid in Example 1, 4- (1 ′,
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 58.1 g (3.4 mol% based on bisphenol A) of 1′-dihydroperfluorohexyloxy) -3-chlorophenol was used. The number average molecular weight of the obtained aromatic polycarbonate was 20,500, and the weight average molecular weight was 50,500. The glass transition point is 144 ° C.
Met.

Example 8 Production of Aromatic Polycarbonate Having End Group No. 38 In Example 1, instead of using 4- (1′-hydroperfluoroethyloxy) benzoic acid, 4- (1 ′,
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 46.5 g (3.4 mol% based on bisphenol A) of 1′-dihydroperfluorobutyloxy) -1-naphthol was used. The obtained aromatic polycarbonate has a number average molecular weight of 20,900 and a weight average molecular weight of 51.
It was 200. The glass transition point was 146 ° C.

Example 9 Preparation of Aromatic Polycarbonate Having End Group No. 46 In Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid, 5- (1 ',
6'g of 1'-dihydroperfluorohexyloxy) -1-naphthol (3.4 relative to bisphenol A
Aromatic polycarbonate was produced in the same manner as in Example 1 except that (mol%) was used. The obtained aromatic polycarbonate has a number average molecular weight of 20,700 and a weight average molecular weight of 5
It was 0900. The glass transition point was 145 ° C.

Example 10 Preparation of Aromatic Polycarbonate Having End Group No. 52 In Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid, 6- (1 ',
53.3 g of 1'-dihydroperfluoropentyloxy) -2-naphthol (3.4 with respect to bisphenol A)
Aromatic polycarbonate was produced in the same manner as in Example 1 except that (mol%) was used. The number average molecular weight of the obtained aromatic polycarbonate was 20,900, and the weight average molecular weight was 5.
It was 1200. The glass transition point was 144 ° C.

Example 11 Preparation of Aromatic Polycarbonate having End Group No. 60 In Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid, 7- (1'-
Hydroperfluoropentyloxy) -2-naphthol 55.8 g (3.4 mol% based on bisphenol A)
An aromatic polycarbonate was produced in the same manner as in Example 1 except that was used. The obtained aromatic polycarbonate has a number average molecular weight of 20400 and a weight average molecular weight of 50600.
Met. The glass transition point was 144 ° C.

Example 12 Production of Aromatic Polycarbonate having an End Group No. 70 In Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid, 4- [4'-
(1'-hydroperfluoroethyloxy) phenyl]
Phenol 38.9 g (3.
Aromatic polycarbonate was produced in the same manner as in Example 1 except that 4 mol%) was used. The obtained aromatic polycarbonate had a number average molecular weight of 20,600 and a weight average molecular weight of 51,100. The glass transition point was 149 ° C.

Example 13 Preparation of Aromatic Polycarbonate having End Group No. 72 In Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid, 4- [4'-
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 50.0 g of (1 ′, 1′-dihydroperfluorobutyloxy) phenyl] phenol (3.4 mol% based on bisphenol A) was used. The number average molecular weight of the obtained aromatic polycarbonate was 20,800 and the weight average molecular weight was 50,700. The glass transition point is 14
It was 7 ° C.

Comparative Example 1 For comparison, in Example 1, instead of using 4- (1′-hydroperfluoroethyloxy) benzoic acid,
Example 1 except that 20.4 g of p-tert-butylphenol (3.4 mol% with respect to bisphenol A) was used.
An aromatic polycarbonate was prepared in the same manner as in. The number average molecular weight of the obtained aromatic polycarbonate is 21,000,
The weight average molecular weight was 5,1200. The glass transition point was 148 ° C.

Comparative Example 2 For comparison, in Example 1, instead of using 4- (1'-hydroperfluoroethyloxy) benzoic acid,
An aromatic polycarbonate was produced in the same manner as in Example 1 except that 26.4 g of 4- (n-hexyloxy) phenol (3.4 mol% based on bisphenol A) was used. The obtained aromatic polycarbonate had a number average molecular weight of 20,800 and a weight average molecular weight of 51100.
The glass transition point was 138 ° C.

The molecular weight of each aromatic polycarbonate produced in each of the examples and comparative examples is GPC [gel permeation chromatography, manufactured by Showa Denko KK,
GPC system-11]. Also,
The glass transition point (Tg, ° C) of each aromatic polycarbonate produced in each example and each comparative example uses DSC [manufactured by Mac Science Co., Ltd., DSC-3100], and the heating rate is 16 ° C / min. It was measured under the conditions. In addition, Table 1 (Table 1) shows the hydrolysis stability test results of the aromatic polycarbonates produced in Examples and Comparative Examples. For the hydrolysis stability test, cast films (thickness 30 μm) of each aromatic polycarbonate
The weight average molecular weight (Mw) after immersion in hot water of 0 ° C. for 120 hours was measured, and the reduction rate (%) from the weight average molecular weight before the test (before immersion) was determined by the following formula. The smaller the value, the better the hydrolysis stability.

[0063]

[Table 1] From the results shown in Table 1, the aromatic polycarbonate of the present invention shows that p-tert-butylphenol or 4- (n-
It can be seen that the hydrolysis stability is superior to that of the aromatic polycarbonate end-capped with hexyloxy) phenol.

[0064]

According to the present invention, it is possible to provide an aromatic polycarbonate having excellent hydrolysis stability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomonori Ito 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Within the corporation

Claims (2)

[Claims] 1. An aromatic polycarbonate having at least one of terminal groups having a group represented by the general formula (1). -A-OR _f (1) [In the formula, A represents a phenylene group, a naphthylene group, or a biphenylene group, and R _f represents a-(CHR ₁ ) R ₂ group (R ₁ represents a hydrogen atom or a fluorine atom, R ₂ represents an alkyl group which may contain a fluorine atom, and when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having at least one fluorine atom)) 2. The aromatic polycarbonate according to claim 1, wherein in the general formula (1), R _f is a group represented by the following formula. -(CHR ₁ ) [C _p (R ₃ R ₄ ) _p ] (C _q F _2q ) R ₅ (wherein R ₁ , R ₃ , R ₄ , and R ₅ each represent a hydrogen atom or a fluorine atom, and p And q represents an integer of 1 to 16)