Methods for producing polycarbonate copolymer and polysiloxane compound, polycarbonate copolymer, polysiloxane compound, composition, and molded body

Patent metadata

Field	Value
Publication number	US-12240978-B2
Application number	US-202117492937-A
Country	US
Kind code	B2
Filing date	Oct 4, 2021
Priority date	Mar 22, 2019
Publication date	Mar 4, 2025
Grant date	Mar 4, 2025

Abstract

A method for producing a polycarbonate copolymer which has siloxane constituent units represented by any of formulae (1-1)′ to (1-4)′ and prescribed polycarbonate constituent units, the method having a polymerization step for polymerizing a silane-based compound selected from among a prescribed diaryloxysilane compound, a prescribed dialkoxysilane compound and a prescribed silicon compound, a carbonate compound and a diol compound such as an aromatic diol compound or an alicyclic diol compound in the presence of a transesterification catalyst. The polymerization step is carried out in a molten state under reduced pressure while removing alcohols derived from the carbonate compound.

First claim

What is claimed is:

1. A method for producing a polysiloxane compound, which includes polymerization of monomers comprising:
an oxy silane compound comprising at least any one of a diaryloxy silane compound that is any one of dialkyldiaryloxy silane, diaryldiaryloxy silane and monoalkylmonoaryldiaryloxy silane, and a dialkoxy silane compound that is any one of dialkyldialkoxy silane, diaryldialkoxy silane and monoalkylmonoaryldialkoxy silane; and
a diol compound selected from

wherein
in the polymerization, the oxy silane compound and the diol compound are polymerized using a transesterification catalyst, while removing the generated aryl alcohol and/or alkyl alcohol, in a molten state and under reduced pressure,
the monomers for polymerization do not comprise a carbonate compound, and
the amount of the transesterification catalyst to the diol compound is 0.01 μmol/mol to 16,000 μmol/mol at a molar ratio, so that
a poly(arylene/alkylene) siloxane compound with a weight average molecular weight of 10,000 to 300,000, comprising a constituent unit represented by any one of the following formulae (1-1′) to (1-4′), is produced:

wherein, in the above formulae (1-1) to (1-4) and (1-1′) to (1-4′), R 1 and R 2 each independently represent an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent,
R 3 to R 10 and R 30 to R 33 each independently represent hydrogen, halogen, alkoxy, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group containing 2 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent,
Z 1 and Z 2 each independently represent an alkylene group containing 1 to 5 carbon atoms and optionally having a substituent,
J 1 each independently represent an integer of 0 or more and 5 or less,
K 1 each independently represents an integer of 0 or more and 5 or less,
A 1 and A 2 each independently represent either —O—or —CH—,
L 1 and L 2 each independently represent an integer of 0 or more and 3 or less,
m 1 to m 4 each represent the total number of constituent units in each formula, which is a natural number of 10 or more and 1000 or less, and
X represents a single bond or any one of structural formulae represented by the following formula (2):

wherein R 11 and R 12 each independently represent hydrogen, halogen, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent, or R 11 and R 12 bind to each other to form a carbocyclic or heterocyclic ring containing 1 to 20 carbon atoms and optionally having a substituent,
a and b each independently represent an integer of 0 or 1 or more and 5000 or less;
wherein the transesterification catalyst comprises an alkali metal compound and/or an alkaline-earth metal compound comprising any one or more of a carbonate, a hydroxide and an oxide;
wherein the polymerization is initially carried out at atmospheric pressure followed by a step-wise reduction in pressure to a final pressure of 400 Pa or less; and
in the polymerization, the polysiloxane compound is produced, while removing alcohol generated as a by-product.

2. The method for producing a polysiloxane compound according to claim 1 , wherein the X has a siloxane constituent unit showing a fluorene ring structure formed by the binding of R 11 and R 12 .

3. The method for producing a polysiloxane compound according to claim 1 , wherein the reaction temperature in the polymerization is within a range of 150° C. or higher and 300° C. or lower.

4. The method for producing a polysiloxane compound according to claim 1 , wherein the reaction time before the pressure reduction, which is duration of the polymerization at atmospheric pressure, is 0.5 to 3 hours, and the reaction time after the pressure reduction, which is duration of entirety of the polymerization reaction under reduced pressure, is 1 to 5 hours.

5. The method for producing a polysiloxane compound according to claim 1 , wherein, in the polymerization, the amount of the transesterification catalyst to the aromatic diol compound is 0.1 to 100 umol/mol at a molar ratio.

6. The method for producing a polysiloxane compound according to claim 1 , wherein the transesterification catalyst is the alkali metal compound and/or the alkaline-earth metal compound.

7. The method for producing a polysiloxane compound according to claim 1 , wherein, in the polymerization, a solvent is not used.

8. The method for producing a polysiloxane compound according to claim 1 , wherein the molar ratio between the diaryloxy silane compound and the aromatic diol compound, which are used in the polymerization, is 0.9 or more and 1.2 or less.

9. The method for producing a polysiloxane compound according to claim 1 , wherein, in the polymerization, the oxy silane compound or the diaryloxy silane compound, and the alicyclic diol compound or the aromatic diol compound are polymerized at a reaction temperature of higher than 200° C., and/or under reduced pressure.

10. A composition comprising a polysiloxane compound produced by the following production method and a polycarbonate resin;
wherein the production method includes polymerization of monomers comprising:
an oxy silane compound comprising at least any one of a diaryloxy silane compound that is any one of dialkyldiaryloxy silane, diaryldiaryloxy silane and monoalkylmonoaryldiaryloxy silane, and a dialkoxy silane compound that is any one of dialkyldialkoxy silane, diaryldialkoxy silane and monoalkylmonoaryldialkoxy silane; and
a diol compound selected from

wherein
in the polymerization, the oxy silane compound and the diol compound are polymerized using a transesterification catalyst, while removing the generated aryl alcohol and/or alkyl alcohol, in a molten state and under reduced pressure,
the monomers for polymerization do not comprise a carbonate compound, and
the amount of the transesterification catalyst to the diol compound is 0.01 μmol/mol to 16,000 μmol/mol at a molar ratio, so that
a polysiloxane compound with a weight average molecular weight of 10,000 to 300,000, comprising a constituent unit represented by any one of the following formulae (1-1′) to (1-4′), is produced:

wherein, in the above formulae (1-1) to (1-4) and (1-1′) to (1-4′), R 1 and R 2 each independently represent an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbon atoms and optionally having a substituent,
R 3 to R 10 and R 30 to R 33 each independently represent hydrogen, halogen, alkoxy, an alkyl group containing 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group containing 2 to 20 carbon atoms and optionally having a substituent, or an aryl group containing 6 to 30 carbo

Assignees

• Mitsubishi Gas Chemical Co

Inventors

• Uera Kazuyoshi
• Kamatani Kohei
• Tomita Keisuke
• AKIMOTO Hisato

Classifications

• C08G77/46

  containing polyether sequences · CPC title

• C08G64/183

  containing polyether sequences · CPC title

• C08G64/307

  and phenols · CPC title

• G02B1/041

  Lenses · CPC title

• C08G64/085

  containing silicon · CPC title