Method for continuous production of high molecular weight polycarbonate resin

Patent metadata

Field	Value
Publication number	US-9243106-B2
Application number	US-201314400640-A
Country	US
Kind code	B2
Filing date	May 14, 2013
Priority date	May 18, 2012
Publication date	Jan 26, 2016
Grant date	Jan 26, 2016

Abstract

A high molecular weight polycarbonate resin is continuously produced by subjecting an aromatic polycarbonate prepolymer and an aliphatic diol compound to a linking and highly polymerizing reaction. Even an aliphatic diol compound having a comparatively low boiling point can be allowed to efficiently contribute to the linking and highly polymerizing reaction. An aromatic polycarbonate prepolymer is produced by a polycondensation reaction between an aromatic dihydroxy compound and a diester carbonate, adding an aliphatic diol compound having an aliphatic group bonding to a terminal hydroxyl group to obtain a prepolymer mixture, and subjecting the resulting prepolymer mixture to a linking and highly polymerizing reaction under reduced pressure. The aliphatic diol compound is added at a pressure exceeding 200 torr, and the prepolymer mixture is subjected to a linking and highly polymerizing reaction before the terminal hydroxyl group concentration of the aromatic polycarbonate prepolymer in the prepolymer mixture reaches 2000 ppm.

First claim

The invention claimed is:

1. A method for continuously producing a high molecular weight polycarbonate resin, comprising:
a step (A) for producing an aromatic polycarbonate prepolymer by a polycondensation reaction between an aromatic dihydroxy compound and a diester carbonate,
a step (B) for adding an aliphatic diol compound having an aliphatic group that bonds to a terminal hydroxyl group to the aromatic polycarbonate prepolymer obtained in step (A) to obtain a prepolymer mixture, and
a step (C) for subjecting the prepolymer mixture obtained in step (B) to a linking and highly polymerizing reaction under a reduced pressure condition; wherein,
in step (B), the aliphatic diol compound is added to the aromatic polycarbonate prepolymer obtained in step (A) at a pressure exceeding 200 torr to obtain the prepolymer mixture, and then, the prepolymer mixture is subjected to a linking and highly polymerizing reaction under a reduced pressure condition in step (C) before the terminal hydroxyl group concentration of the aromatic polycarbonate prepolymer in the prepolymer mixture reaches 2000 ppm.

2. The continuous production method according to claim 1 , wherein the prepolymer mixture is subjected to the linking and highly polymerizing reaction in step (C) within 7 minutes from the start of addition of the aliphatic diol compound.

3. The continuous production method according to claim 1 , wherein the aliphatic diol compound is a compound represented by the following general formula (A):
HO—(CR 1 R 2 ) n -Q-(CR 3 R 4 ) n —OH  (A)

wherein, Q represents a hydrocarbon group having 3 or more carbon atoms that may contain a heteroatom,
R 1 , R 2 , R 3 and R 4 respectively and independently represent a group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms,
n and m respectively and independently represent an integer of 0 to 10, provided that n and m respectively and independently represent an integer of 1 to 10 in the case Q does not contain an aliphatic hydrocarbon group that bonds to a terminal OH group, and at least one of R 1 and R 2 and at least one of R 3 and R 4 are respectively selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group.

4. The continuous production method according to claim 1 , wherein the aliphatic diol compound is a primary diol compound.

5. The continuous production method according to claim 1 , wherein the boiling point of the aliphatic diol compound is 350° C. or lower.

6. The continuous production method according to claim 1 , wherein the aliphatic diol compound is a compound selected from the group consisting of pentacyclopentadecane dimethanol, 1,4-cyclohexane dimethanol, 1,3-adamantane dimethanol, decalin-2,6-dimethanol, tricyclodecane dimethanol, 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol.

7. The continuous production method according to claim 1 , wherein the terminal hydroxyl group concentration of the aromatic polycarbonate prepolymer obtained in step (A) is 1500 ppm or less.

8. The continuous production method according to claim 1 , wherein the N value (structural viscosity index) as represented by the following equation (I) of the high molecular weight polycarbonate resin is 1.30 or less
N value=(log( Q 160value)−log( Q 10value))/(log 160−log 10)  (I)

9. The continuous production method according to claim 1 , wherein the weight average molecular weight (Mw) of the high molecular weight polycarbonate resin and the weight average molecular weight (MwPP) of the aromatic polycarbonate prepolymer obtained in step (A) are represented by the following equation (IV):
Mw= k ′×retention time(min)+MwPP  (IV)

wherein, k′ (units: increase in Mw/min) is a numerical number of 500 or more.

10. The continuous production method according to claim 1 , wherein the linking and highly polymerizing reaction under a reduced pressure condition in step (C) is carried out using a linking and highly polymerizing reaction vessel, the linking and highly polymerizing reaction vessel is a single shaft horizontal stirred reaction vessel having a single stirring shaft or a multiple shaft horizontal stirred reaction vessel having a plurality of stirring shafts, at least one of the stirring shafts has a horizontal rotating shaft and mutually discontinuous impellers attached to the horizontal rotating shaft at nearly a right angle, a ratio L/D, when the length of the horizontal rotating shaft is defined as L and the rotating diameter of the impellers is defined as D, is 1 to 15, and an extraction port for the high molecular weight polycarbonate resin formed is provided on the opposite side from a feed port for the aromatic polycarbonate prepolymer.

11. The continuous production method according to claim 1 , wherein the linking and highly polymerizing reaction under a reduced pressure condition in step (C) is carried out using a linking and highly polymerizing reaction vessel, the linking and highly polymerizing reaction vessel is a single shaft horizontal kneading reaction vessel of the continuous screw type having a single stirring shaft or a multiple shaft horizontal kneading reaction vessel of the continuous screw type having a plurality of stirring shafts, a ratio L/D when the length of the stirring shaft is defined as L and the screw diameter is defined as D is 20 to 100, and an extraction port for the high molecular weight polycarbonate resin formed is provided on the opposite side from a feed port for the aromatic polycarbonate prepolymer.

12. The continuous production method according to claim 1 , wherein addition and mixing of the aliphatic diol compound with the aromatic polycarbonate prepolymer in step (B) is carried out using an inline mixer.

13. The continuous production method according to claim 12 , wherein the inline mixer is selected from the group consisting of a static mixer, a kneader and an extruder.

Assignees

• Mitsubishi Gas Chemical Co

Inventors

• Isahaya Yoshinori
• Hirashima Atsushi
• Harada Hidefumi
• Ito Maki
• HAYAKAWA Jun-ya
• Isobe Takehiko
• Tokutake Taichi
• Shinkai Yousuke

Classifications

• C08G64/305

  and alcohols · CPC title

• C08G64/307 Primary

  and phenols · CPC title

• C08G64/1608

  saturated · CPC title

• C08G64/30

  using carbonates · CPC title

• C08G64/06

  not containing aliphatic unsaturation · CPC title