JP3300445B2 - Aromatic polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to aromatic polycarbonates. More specifically, the present invention relates to an aromatic polycarbonate having a group having a specific structure as a terminal group.

[0002]

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

Furthermore, it has been reported that compounds having various structures are useful as terminal blocking agents. For example, alkanolamines (US Pat. No. 3,085,992)
Imides (US Pat. No. 3,399,172), aniline, methylaniline (US Pat. No. 3,275,601)
), Ammonium compounds, primary or secondary amines (U.S. Pat. No. 4,111,910) have been proposed for use as terminal blocking agents. But on the other hand,
It is 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. 3,223,678). Thus, although various reports have been made on the end capping agent of polycarbonate, what kind of compound or compound group effectively functions as an end capping agent is as follows.
It is not yet fully understood. Furthermore, even if a compound having a specific structure is useful as an end capping agent, it is not possible to predict at all what properties or functions a polycarbonate having such a compound as an end group has. In order to elucidate the chemistry further, a further approach by experimental methodologies is needed.

[0004]

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

[0005]

Means for Solving the Problems The present inventors have made intensive studies on aromatic polycarbonates, and as a result, have reached the present invention. 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) wherein, A is a naphthylene group or a biphenylene group table
And, the R _f - (CHR ₁₎ represents an R ₂ group (R ₁ is a hydrogen atom or a fluorine atom, R ₂ represents an alkyl group which may contain a fluorine atom, when R ₁ is a hydrogen atom Is R ₂
The alkyl represents a group) The compound represented by the general formula (1) according to the present invention having at least Ke fluorine atoms, _{R f, - (CHR 1)} R 2 group (R _1, R ₂ Represents the same meaning as described above), and more preferably, 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, R 5 are each a hydrogen atom or <br/> fluorine Represents an atom, and p and q represent an integer of 1 to 16). Particularly preferably, R _f is a group represented by the above formula wherein p and q are an integer of 1 to 12.

In the general formula (1) according to the present invention, R _f
Specific examples of 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,
1,1-dihydroperfluorotetradecyl group, 1,1
-Dihydroperfluoropentadecyl group, 1,1-dihydroperfluorohexadecyl group,

A 1,1,2-trihydroperfluoroethyl group, a 1,1,3-trihydroperfluoropropyl group, a 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
2-tetrahydroperfluorodecyl group, 1,1,2,2
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 2,7
-Pentahydroperfluoroheptyl group, 1,1,2,2
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,
4,4-octahydroperfluoropentyl group, 1,
1,2,2,3,3,4,4-octahydroperfluorohexyl group, 1,1,2,2,3,3,4,4-octahydroperfluoroheptyl group, 1,1,2,2 2,
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
An 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,
1,2,2,3,3,4,4,14-nonahydroperfluorotetradecyl group, 1,1,2,2,3,3,4
4,5,5-decahydroperfluorohexyl group,
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-
Perfluoromethyloctyl, 8-perfluorobutyloctyl, 9-perfluoropropylundecyl, 10-perfluoropentyldecyl, 11-perfluorooctylundecyl, and 12-perfluorobutyldodecyl Can be.

[0010]

In the general formula (1) according to the present invention, A represents a naphthylene group or a biphenylene group , and these groups include an alkyl group having 1 to 8 carbon atoms and a group having 1 to 8 carbon atoms.
An alkoxy group, a halogen atom (for example, a fluorine atom,
Mono- or polysubstituted with a chlorine atom or a bromine atom). Specific examples include a 1,2-naphthylene group,
3-naphthylene group, 1,4-naphthylene group, 1,5-na
Butylene group, 1,6-naphthylene group, 1,8-naphthyl
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
And alkyl-substituted C1-C8, alkoxy-substituted C1-C8, and halogen-substituted derivatives thereof , more preferably 1,4-naphthylene.
Group, 1,5-naphthylene group, 2,6-naphthylene group,
A 2,7-naphthylene group, a 4,4′-biphenylene group or an alkyl-substituted group having 1 to 4 carbon atoms,
Is an alkoxy-substituted or halogen-substituted derivative of

A preferred terminal blocking agent used in producing an aromatic polycarbonate having at least one terminal group represented by the general formula (1) according to the present invention includes a compound represented by the general formula (1-A) )). _{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 represents a group or a -COZ group, M represents a metal ion, and Z represents a halogen atom. In the compound represented by the general formula (1-A) according to the present invention, Y represents -OH group, -OM group,- OC
An OZ group, a -COOH group, a -COOM group or a -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. As Z, preferably,
It can be exemplified fluorine atom, chlorine atom, a bromine atom,
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), a compound in which Y is represented by an —OH group or a —COOH group can be produced, for example, by the method described in US Pat. No. 4,866,619. In the general formula (1-A), a compound in which Y is represented by an -OCOS group, for example, a compound in which Z is a chlorine atom, is produced by reacting, for example, phosgene with a compound in which Y is an -OH group. be able to. In the general formula (1-A), in a compound in which Y is represented by 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, a thionyl chloride or oxalyl chloride Can be produced. In the general formula (1-A), a compound in which Y is a -OM group is a compound in which Y is an -OH group, for example, an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide in an aqueous solution. It can be produced by the action of a metal base or an alkaline earth base. In the general formula (1-A),
Compounds wherein Y is a -COOM group are those wherein Y is -COOH
The compound can be produced by allowing an alkali metal base such as sodium hydroxide, potassium hydroxide, calcium hydroxide or the like or an alkaline earth base to act on the compound as a group in an aqueous solution.

In the aromatic polycarbonate having at least one terminal group of the present invention having a group represented by the general formula (1), the group represented by the general formula (1) is typically represented by the following: Although the group can be mentioned, of course, the present invention is not limited to these. Example number Example group

[0014]

1 . 1- (1 ', 1'-dihydro perfluoroethyl) -2-naphthyl 2. 2- (1 ', 1', 2 ', 2', 4'-penta hydro perfluorobutyl oxy) -1-naphthyl group 3. 3- (1 ', 1'-dihydro perfluorobutyl oxy) -1-naphthyl group 4. 3- (1 ', 1'-dihydro perfluoropropyl) -2-naphthyl group 5. 3- (1 ', 1', 2 ', 2'-tetrahydropyran perfluorohexyl) -2-naphthyl group 6. 3- (1 ', 1', 2 ', 2', 3 ', 3', 7 '
- hepta hydro perfluoroalkyl heptyloxy) -2-naphthyl group 7. 4- (1'-hydroperfluorobutyloxy)-
1-naphthyl group 8. 4- (1 ', 1'-dihydro perfluorobutyl oxy) -1-naphthyl group 9. 10. 4- (1 ′, 1′-dihydroperfluorohexyloxy) -1-naphthyl group 4- (1 ′, 1′-dihydroperfluorooctyloxy) -2-chloro-1-naphthyl group

11 . 12. 4- (6′-perfluoromethylhexyloxy) -1-naphthyl group 4- (1 ', 1', 8'-trihydrofluoride perfluorooctyl) -1- naphthyl group 13. 5- (1'-hydroperfluoroethyloxy)
-1-naphthyl group 14 . 5- (1'-hydroperfluorobutyloxy)
-1-naphthyl group 15 . 5- (1 ', 1'-dihydro perfluorobutyl oxy) -1-naphthyl group 16. 5- (1 ', 1'-dihydro perfluoro hexyloxy) -1-naphthyl group 17. 18. a 5- (1 ', 1'-dihydroperfluorooctyloxy) -1-naphthyl group; 5- (1 ', 1', 7'-trihydrofluoride perfluoro heptyloxy) -1- naphthyl group 19. 6- (1′-hydroperfluoroethyloxy)
-1-naphthyl group 20 . 6- (1′-hydroperfluorobutyloxy)
-2-naphthyl group 21 . 22. 6- (1′-hydroperfluorohexyloxy) -2-naphthyl group 6- (1 ', 1'-dihydro perfluoro pentyl) -2-naphthyl group 23. 6- (1 ', 1'-dihydro perfluorohexyl) -2-naphthyl group 24. 6- (1 ', 1'-dihydro perfluorooctyl oxy) -1-ethyl-2-naphthyl group 25. 6- (1 ′, 1 ′, 7′-trihydroperfluoroheptyloxy) -2-naphthyl group

26 . 27. 6- (1 ′, 1 ′, 2 ′, 2′-tetrahydroperfluoroheptyloxy) -2-naphthyl group 28. 6- (1 ′, 1 ′, 2 ′, 2 ′, 3 ′, 3′-hexahydroperfluorohexyloxy) -2-naphthyl group 6- (1 ′, 1 ′, 2 ′, 2 ′, 3 ′, 3 ′,
4 ', 4'-octahydro perfluorohexyl) -2-naphthyl group 29. 30. 7- (1′-hydroperfluoropropyloxy) -2-naphthyl group 7- (1'-hydro perfluorobutyl) -2-naphthyl group 31. 7- (1 ', 1'-dihydro perfluorobutyl) -2-naphthyl group 32. 7- (1 ', 1'-dihydro perfluorooctyl) -2-naphthyl group 33. 7- (1 ', 1', 2 ', 2', 3 ', 3',
4 ', 4'-octahydro perfluorobutyl) -2-naphthyl group 34. 8- (1 ′, 1′-dihydroperfluorobutyloxy) -1-naphthyl group 35 . 2- [2 ′-(1 ′, 1′-dihydroperfluorohexyl) oxyphenyl] biphenyl 36 . 2- [4 '- (1', 1'-dihydro perfluorooctyl) oxyphenyl] phenyl 37. 3- [3 '- (1', 1'-dihydro perfluorobutyl) phenyl] phenyl 38. 4- [3 '- (6'-perfluoro butyl hexyl) phenyl] phenyl 39. 3- [4 '- (1'hydro perfluoroethyl) phenyl] phenyl 40. 4- [4 '- (1'hydro perfluoroethyl) phenyl] phenyl 41. 4- [4 ′-(1′-hydroperfluorobutyloxy) phenyl] phenyl group 42 . 4- [4 '- (1', 1'-dihydro perfluorobutyl) phenyl] phenyl 43. 4- [4 '- (1', 1'-dihydro perfluorooctyl) phenyl] phenyl 44. 4- [4 '- (1', 1 ', 11'-tri hydro perfluoroalkyl undecyloxy) phenyl] phenyl 45. 4- [4 '- (1', 1 ', 2', 2'-tetrahydropyran perfluoroheptyl) phenyl] phenyl 46. 4- [4 '- (1', 1'-dihydro perfluorooctyl) phenyl] -3-chlorophenyl group 47. 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). As a method known in the art, an interfacial polymerization method, a solution polymerization method, or a transesterification method can be used. In particular, the interfacial polymerization method is a preferable production method. When producing an aromatic polycarbonate having a novel terminal group of the present invention,
The compound represented by the general formula (1-A) acts as a terminal blocking agent, and is useful for controlling or adjusting the molecular weight of the aromatic polycarbonate in the production process of the aromatic polycarbonate of the present invention. The terminal blocking agent and the aromatic dihydroxy compound form a carbonate bond or an ester bond by the action of a carbonate precursor to form an aromatic polycarbonate having a terminal group represented by the general formula (1) of the present invention. Generate. Note that, in the carbonate bond, in the compound represented by the general formula (1-A), Y is -OH
Group is formed by using a compound that is a group, a -OM group or a -OCOZ group, while the ester bond is
It is formed by using a compound that 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 an arbitrary weight average molecular weight depending on the amount of the compound represented by the general formula (1-A) used in the production. In consideration of 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 to about 150,000.
It has a weight average molecular weight of 000 to about 100,000. The weight average molecular weight generally depends on the amount of the compound represented by the general formula (1-A) used when producing the aromatic polycarbonate. Generally, as the amount of the compound represented by the general formula (1-A) increases, the weight average molecular weight of the aromatic polycarbonate decreases, and conversely, the amount of the compound represented by the general formula (1-A) decreases When the weight average molecular weight decreases, the weight average molecular weight of the aromatic polycarbonate increases. Generally, the amount of the compound represented by the general formula (1-A) is about 1.2 to about 1 based on the amount of the aromatic dihydroxy compound used.
0.0 mol%, and more preferably about 1.5 mol%.
~ 7.0 mol% is more preferred.

The terminal blocking 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 may be supplied sequentially and continuously with the addition of the carbonate precursor. In producing the polycarbonate of the present invention, the general formula (1-
One or more compounds represented by A) can be used. When only one kind is used, the terminal groups of the aromatic polycarbonate are all groups having the same structure. When two or more are used together, the general formula (1
Depending on the number, amount and type of the compounds represented by -A), various terminal groups are mixed. Furthermore, the general formula (1-
The compound represented by A) can be used in combination with other known terminal blocking agents as long as the desired effects of the present invention are not impaired. When the compound represented by the general formula (1-A) is used in combination with another known terminal blocking agent in producing the aromatic polycarbonate of the present invention, the compound represented by the general formula (1) The proportion of the compound represented by -A) is 3
It is preferably at least 0 mol%, more preferably at least 50 mol%, particularly preferably at least 60 mol%.

Examples of the terminal blocking agent other than the compound represented by the general formula (1-A) include a monovalent hydroxy aromatic compound, a monovalent hydroxy aromatic compound chloroformate compound, and a monovalent hydroxy aromatic compound. Examples thereof include compounds having a carboxylic acid group and monovalent carboxylic acid chloride compounds. Examples of the monovalent hydroxy aromatic compound include phenol, p-cresol, o-ethylphenol, p-ethylphenol, p-isopropylphenol, 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 the like.

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 bivalent carboxylic acid group include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2,2-dimethylpropionic acid,
-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. Note that the above 1
Alkali metal (e.g., lithium, sodium, potassium) salts, alkaline earth metals (e.g., trivalent hydroxyaromatic compounds or compounds having a monovalent carboxylic acid group)
Calcium) salts can also be used as endcaps.

The aromatic dihydroxy compound used for producing the aromatic polycarbonate compound of the present invention includes a compound represented by the general formula (2). HO-R-OH (2) (wherein, 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. In the above general formula (2), which is a group hydrocarbon group, the group R is preferably a general formula (3) -Ar ¹ -B-Ar ^2- (3) (wherein, Ar ¹ and Ar ² are each A monocyclic divalent aromatic group,
B is a group linking Ar ¹ and Ar ² ). In the above 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, a nitro group, and an alkoxy group.

Ar ¹ and Ar ² are both p-phenylene groups, m
-A phenylene group or an o-phenylene group, or one is a p-phenylene group, and one is an m-phenylene group or an o-phenylene group, and particularly, both Ar ¹ and Ar ² are p-phenylene groups. Preferably it is. B
Is a group linking Ar ¹ and Ar ² , and is a single bond or a divalent hydrocarbon group, furthermore, —O—, —S—, —SO—,
It may be a group containing atoms other than carbon and hydrogen, such as —SO ₂ — and —CO—. The divalent hydrocarbon group includes a saturated hydrocarbon group, for example, an alkylidene group such as methylene, ethylene, 2,2-propylidene, cyclohexylidene, etc., but also includes a group substituted with an aryl group or the like. Alternatively, a hydrocarbon group containing an aromatic group or another unsaturated hydrocarbon group may be used.

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 ] decane, bis (hydroxyaryl) cycloalkanes such as 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'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 3,3'-dimethyl-
Bis (hydroxyaryl) sulfoxides such as 4,4'dihydroxy-diphenylsulfoxide;
Dihydroxydiphenylsulfone, 3,3′-dimethyl-4,4′-dihydroxydiphenylsulfone, 3,
Bis (hydroxyaryl) such as 3'-diphenyl-4,4'-dihydroxydiphenylsulfone and 3,3'-dichloro-4,4'-dihydroxydiphenylsulfone
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-dihydroxyphenoxatiin, 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 and the like are also used. Further, 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. These may be used alone or in combination of two or more. A particularly preferred aromatic dihydroxy compound is bisphenol A.

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

[0032]

Embedded image (Wherein, X represents a hydrogen atom or a halocarbonyl group,
At least one X is a halocarbonyl group, R ′ represents a divalent aliphatic group or an aromatic group, and n represents 0 or a positive integer) The compound represented by the general formula (4) 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. Group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group,
Divalent hydrocarbon groups such as undecylene and dodecylene groups,
In addition, 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 optionally substituted with these groups It 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 and the like can be mentioned. Further, the divalent aliphatic group R ′ also includes a group represented by the general formula (5). ^{-R "-Ar 3 -R" - (} 5) ( wherein, R "represents an alkylene group having 1 to 6 carbon atoms, A
r ³ represents a divalent aromatic group having 6 to 12 carbon atoms) In the general formula (5), the R ″ group represents an alkylene group having 1 to 6 carbon atoms, for example, a linear or branched methylene group Group, ethylene group, propylene group, butylene group, pentylene group,
A hexylene group is a divalent hydrocarbon group, and an Ar ³ group is a divalent aromatic group having 6 to 12 carbon atoms, such as a phenylene group, a substituted phenylene group, and a naphthylene group.

Specific examples of this type of aliphatic dihydroxy compound include xylylene diol, 1,4-bis (2 ′
-Hydroxyethyl) benzene, 1,4-bis (3′-
Hydroxypropyl) benzene, 1,4-bis (4′-
(Hydroxybutyl) benzene, 1,4-bis (5′-hydroxypentyl) benzene, 1,4-bis (6′-hydroxyhexyl) benzene, and the like.
In the general formula (4), examples of the aromatic dihydroxy compound in which the R ′ group is an aromatic group include the above-mentioned aromatic dihydroxy compounds, for example, 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 or as a mixture, or may be used as a mixture with a carbonyl halide. Dialkyl carbonate compounds, diaryl carbonate compounds, alkylaryl carbonate compounds include dimethyl carbonate,
Examples include diphenyl carbonate, methylphenyl carbonate compounds, diphenyl carbonate substituted with a halogen atom, a nitro group, and the like, and mixtures thereof.

When the aromatic polycarbonate of the present invention is produced by an interfacial polymerization method, a carbonyl halide and / or a haloformate compound is preferably used as a carbonate precursor. The carbonate precursor may be used in any state of gas, liquid and solid.However, when carbonyl halide is used, it is used in gaseous state or dissolved in an organic solvent to form 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 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, a carbonyl halide and / or a haloformate compound is represented by the general formula (II) 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 substantially insoluble in water. This is a method of producing an aromatic polycarbonate by acting in the presence of the compound represented by (1-A), and more preferably a method of producing an aromatic polycarbonate in the presence of a polycarbonate-forming catalyst.

When an aromatic polycarbonate of the present invention is produced by an interfacial polymerization method, for example, when a carbonyl halide compound is used as a carbonate precursor, the amount of the carbonyl compound to be used is about 1 to the amount of the aromatic dihydroxy compound. It is preferred to use an amount of from about 0.0 to about 1.3 moles. The use of an extremely small amount of the carbonyl halide compound less than 1.0 mole results in the production of an unreacted aromatic dihydroxy compound, which is a factor of producing an aromatic polycarbonate having a poor color tone. Also, the use of an excessive amount of the carbonyl halide compound in excess of 1.3 times leads to the production of a large amount of the oligomer terminated with a haloformate terminal group. As a result, the use of the haloformate terminal group of the oligomer in the reaction system becomes difficult. O
Since the ratio of the H group (or phenolate group) becomes excessive in the haloformate terminal group, an ordinary polymerization time is not preferable because an aromatic polycarbonate having a small molecular weight terminated by the haloformate terminal group is formed.

The organic solvent can be arbitrarily used as long as it is substantially insoluble in water and inert to the reaction and dissolves the aromatic polycarbonate. For example, dichloromethane, chloroform, 1,2-
Dichloroethane, 1,2-dichloroethylene, trichloroethane, tetrachloroethane, aliphatic chlorinated products such as dichloropropane, or chlorobenzene, chlorinated hydrocarbons such as aromatic chlorinated products 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 and ethylbenzene, an aliphatic hydrocarbon such as hexane, heptane, cyclohexane and the like may be mixed with the chlorinated hydrocarbon 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 an organic solvent is required, which is not preferable in terms of productivity. Also, 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 extremely high, so that the reaction efficiency of the interfacial polymerization decreases, and the handleability of the organic solvent solution after polymerization deteriorates. And the like, which is not preferable. It is particularly preferred to use an organic solvent such 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 the organic solvent used also depends on the amount of water used. Any amount necessary for maintaining the reaction mixture in a substantially uniform emulsified state may be used. Usually, the ratio of water to the organic phase by volume is preferably about 0.4 to 1.5: 1. When the amount of the organic solvent is less than the above range, the hydrolysis of the carbonate precursor and the haloformate group increases, and a large 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 base) used for producing the aromatic polycarbonate of the present invention is usually an alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide or the like. Sodium hydroxide and potassium hydroxide are preferred because they are hydroxides of metals or alkaline earth metals and are relatively easily available, and sodium hydroxide is particularly preferred. The base is usually used in the form of an aqueous solution, and it is preferable to dissolve the aromatic dihydroxy compound in the aqueous solution before use in the reaction. In this case, since the basic aqueous solution of the aromatic dihydroxy compound generally tends to be colored, a basic agent of the aromatic dihydroxy compound is added by adding a reducing agent such as sodium sulfite, sodium hydrosulfite or sodium borohydride as an antioxidant. An aqueous solution may be prepared. Suitable polycarbonate forming catalyst used in the interfacial polymerization method (also referred to as polymerization catalyst or polycondensation catalyst)
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. It is preferably a trialkylamine which is a tertiary amine, and more preferably has no branch on the carbon atom at the 1- and 2-position, and the alkyl group has a C
1 to C4 trialkylamines, for example, triethylamine, tri-n-propylamine, diethyl-n-propylamine, tri-n-butylamine, etc. In particular, triethylamine is particularly preferred. The amount of the polycarbonate-forming catalyst used is preferably from about 0.0005 to about 0.7 mol% based on the number of moles of the aromatic dihydroxy compound.
If the amount of the catalyst is excessively less than 0.0005 mol%, the catalytic effect for forming the aromatic polycarbonate is not sufficient, and a very long polymerization time is required. 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 production catalyst is wasted, which is not preferable. The timing of adding the polycarbonate-forming 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 a temperature of 0 ° C. to the boiling point of the organic solvent used for the reaction. 10
At a reaction temperature extremely lower than ℃, the reaction rate becomes slow,
The reaction efficiency deteriorates. In addition, it is not practical because a cooling medium or a cooling device is required. If the organic solvent used is dichloromethane, it can be carried out at atmospheric pressure and at a reflux temperature of about 39 ° C. In practice, the reaction usually starts around room temperature and is then raised to near reflux by the heat of reaction. The reaction is usually carried out at atmospheric pressure, but if desired, the reaction may be carried out under increased or reduced pressure.

The aromatic polycarbonate of the present invention can be converted 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, chloroformate groups, carboxylic acid groups, carboxylic acid chloride groups and even active halogen atoms. 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 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. It is preferable to use about 2.0 mol%.

Further, the aromatic polycarbonate of the present invention includes an aromatic polyester carbonate, and at least one aromatic dihydroxy compound (for example, a compound represented by the general formula (2)), a carbonate precursor (Eg, phosgene), divalent carboxylic acids or derivatives of such compounds (eg, US Pat. No. 3,169,91)
An aromatic polyester carbonate can be suitably produced by using the compound represented by No. 21 (isophthalic acid, terephthalic acid, isophthalic dichloride, terephthalic dichloride, etc.) and the compound represented by the general formula (1-A).
At this time, the amount of the divalent carboxylic acid or the derivative of the compound used is 30 to 80 with respect to the aromatic dihydroxy compound.
It is preferable to use about mol%.

In producing the aromatic polycarbonate of the present invention, those skilled in the art can use a solution polymerization method which is already known, for example, in a pyridine solution, as an aromatic dihydroxy compound or a carbonate precursor. , A carbonyl halide or / and a haloformate compound and a compound represented by the general formula (1-A) from 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 compound represented by the 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 mixture of a diaryl carbonate compound, 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 (for example, 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 the 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 can be directly pelletized or processed into a molded product from the aromatic polycarbonate melted under transesterification conditions.

The aromatic polycarbonate of the present invention is soluble in a specific organic solvent (eg, 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 can be mixed with another aromatic polycarbonate or a polyester such as polyethylene terephthalate or poly (1,4-butylene terephthalate). Further, the aromatic polycarbonate of the present invention, for the purpose of imparting thermal stability during processing to the aromatic polycarbonate, light resistance, weather resistance, flame resistance, mold release and other properties, the aromatic polycarbonate In a known manner during or after production, a very wide range of additives, stabilizers, flame retardants and fillers, namely processing and heat stabilizers, antioxidants, hydrolysis stabilizers, impact stabilizers, UV absorbers, A release agent, an organic halogen compound, an alkali metal sulfonate, glass fiber, glass beads, barium sulfate, TiO2 and the like may be added.

[0047]

The present invention will be described in more detail with reference to the following examples.
However, the present invention is not limited to the following examples.
No.

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

Example 1 Example 1
Manufacture of aromatic polycarbonate In a 10-liter baffled flask, three-stage six-blade stirring
And a reflux condenser.
Noll A 912 g (4.0 mol), 4- (1 ′, 1′-
Dihydroperfluorobutyloxy) -1-naphthol
46.5 g (3.4 mol based on bisphenol A)
%), 4 l of dichloromethane and 4 l of deionized water.
Make a suspension and remove nitrogen from the flask to remove oxygen from the flask.
Did. Next, sodium hadrosulf was added to the above suspension.
1.2 g of graphite and 432 g of caustic soda (10.8
2.2 l of an aqueous solution of
Phenol A was dissolved. This solution contains phosgene 495
g (5.0 mol) was fed at a rate of 8.25 g / min.
The reaction temperature rises to 39 ° C and the reflux of dichloromethane
confirmed. After the phosgene supply is complete, triethyl
Add 0.64 g of amine and allow reaction to run for another 90 minutes
The mixture was stirred to perform a polymerization reaction. After that, the reaction solution is allowed to stand,
Separate the organic layer, neutralize with hydrochloric acid, and lose electrolyte
Until deionized water. Yoshi obtained in this way
Tolue in a dichloromethane solution of aromatic polycarbonate
Add 2 l of water and 5 l of water and heat to 98 ° C.
Dichloromethane and toluene are distilled off to obtain aromatic polycarbonate.
A carbonate powder was obtained. The aromatic polycarbonate obtained
The number average molecular weight of the sheet is 20900, and the weight average molecular weight is 5
1200. The glass transition point was 146 ° C.
Was.

Example 2 Production of an aromatic polycarbonate having a terminal group of Ex. No. 16 In Example 1, 4- (1 ′, 1′-dihydroperf
Use instead of using the Le Oro butyloxy) -1- naphthol, 5- (1 ', 1'-dihydro perfluoro hexyloxy) -1-naphthol 60.1g of (3.4 mol% relative to bisphenol A) Aromatic polycarbonate was produced in the same manner as in Example 1 except for the above. The number average molecular weight of the obtained aromatic polycarbonate was 20,700, and the weight average molecular weight was 50,900. The glass transition point was 145 ° C.

Example 3 Production of an aromatic polycarbonate having a terminal group of Ex. No. 22 In Example 1, 4- (1 ′, 1′-dihydroperf
Instead of using (fluorobutyloxy ) -1-naphthol , 53.3 g of 6- (1 ′, 1′-dihydroperfluoropentyloxy) -2-naphthol (3.4 mol% based on bisphenol A) was used. Aromatic polycarbonate was produced in the same manner as in Example 1 except for the above. The number average molecular weight of the obtained aromatic polycarbonate was 20,900, and the weight average molecular weight was 5,1200. The glass transition point was 144 ° C.

Example 4 Production of an aromatic polycarbonate having a terminal group of Exemplification No. 30 In Example 1, 4- (1 ′, 1′-dihydroperf
Instead of using (fluorobutyloxy ) -1-naphthol , 7- (1′-hydroperfluoropentyloxy)
Aromatic polycarbonate was produced in the same manner as in Example 1, except that 55.8 g of -2-naphthol (3.4 mol% based on bisphenol A) was used. The number average molecular weight of the obtained aromatic polycarbonate was 20,400, and the weight average molecular weight was 50,600. The glass transition point was 144.
° C.

Example 5 Production of an aromatic polycarbonate having a terminal group of Exemplified No. 40 In Example 1, 4- (1 ′, 1′-dihydroperf
Instead of using (fluorobutyloxy ) -1-naphthol , 38.9 g of 4- [4 ′-(1′-hydroperfluoroethyloxy) phenyl] phenol (3.4 mol% based on bisphenol A) was used. Example 1 except for
Aromatic polycarbonate was produced in the same manner as described above. The number average molecular weight of the obtained aromatic polycarbonate is 20,600,
The weight average molecular weight was 51100. The glass transition point was 149 ° C.

Example 6 Production of an aromatic polycarbonate having a terminal group of Exemplified No. 42 In Example 1, 4- (1 ′, 1′-dihydroperf
Instead of using fluorobutyloxy) -1-naphthol , 50.0 g of 4- [4 ′-(1 ′, 1′-dihydroperfluorobutyloxy) phenyl] phenol (3.4 mol% based on bisphenol A) ), Except
An aromatic polycarbonate was produced in the same manner as in Example 1.
The number average molecular weight of the obtained aromatic polycarbonate is 20.
800 and the weight average molecular weight was 50,700. The glass transition point was 147 ° C.

Comparative Example 1 For comparison, in Example 1, 4- (1 ′, 1′-di
Instead of using ( hydroperfluorobutyloxy) -1-naphthol , p-tert-butylphenol 20.4
An aromatic polycarbonate was produced in the same manner as in Example 1, except that g (3.4 mol% based on bisphenol A) was used. The number average molecular weight of the obtained aromatic polycarbonate was 21,000 and the weight average molecular weight was 51200. The glass transition point was 148 ° C.

Comparative Example 2 For comparison, in Example 1, 4- (1 ′, 1′-di
Same as Example 1 except that instead of using ( hydroperfluorobutyloxy) -1-naphthol , 26.4 g of 4- (n-hexyloxy) phenol (3.4 mol% based on bisphenol A) was used. An aromatic polycarbonate was produced. The resulting aromatic polycarbonate had a number average molecular weight of 20,800 and a weight average molecular weight of 511.
00. The glass transition point was 138 ° C.

The molecular weight of each aromatic polycarbonate produced in each of the examples and comparative examples was measured by 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 was measured using DSC (DSC-3100, manufactured by Mac Science Co., Ltd.), and the heating rate was 16 ° C / min. It measured on condition of. Table 1 (Table 1) shows the results of the hydrolysis stability test of each aromatic polycarbonate produced in each of Examples and Comparative Examples. As a hydrolysis stability test, a cast film (thickness: 30 μm) of each aromatic polycarbonate was measured for 8 hours.
The weight-average molecular weight (Mw) after immersion in hot water at 0 ° C. for 120 hours was measured, and the decrease (%) 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, p-tert-butylphenol or 4- (n-
It can be seen that the hydrolysis stability is superior to the aromatic polycarbonate end-blocked by hexyloxy) phenol.

[0064]

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

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Examiner, Mitsui Toatsu Chemicals Co., Ltd. (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (2)

(57) [Claims] 1. An aromatic polycarbonate having at least one terminal group having a group represented by the general formula (1). -A-OR _f (1) In the formulas, A represents a naphthylene group or a biphenylene group, the R _f - a (CHR ₁₎ represents an R ₂ group (R ₁ is a hydrogen atom or a fluorine atom, R ₂ is Represents an alkyl group which may contain a fluorine atom, and when R ₁ is a hydrogen atom, R _{2 represents}
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 q represents an integer of 1 to 16)