Search

JP-2026076338-A - Method for producing polycarbonate copolymers and polysiloxane compounds, polycarbonate copolymers, polysiloxane compounds, compositions, and molded articles.

JP2026076338AJP 2026076338 AJP2026076338 AJP 2026076338AJP-2026076338-A

Abstract

[Problem] To provide a method for efficiently producing a polycarbonate copolymer having siloxane structural units that has excellent impact resistance and high fluidity when melted. [Solution] The method comprises a polymerization step of polymerizing a silane compound selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane compound, and a predetermined silicon compound, a carbonate compound, and a diol compound including an aromatic diol compound or an alicyclic diol compound, in the presence of a transesterification catalyst, wherein in the polymerization step, under reduced pressure in a molten state, alcohol derived from the carbonate compound is removed, and a polycarbonate copolymer having siloxane constituent units represented by the following formula (1) and polycarbonate constituent units is produced. [Selection Diagram] None

Inventors

  • 上等 和良
  • 釜谷 康平
  • 冨田 恵介
  • 秋元 宣人

Assignees

  • 三菱瓦斯化学株式会社

Dates

Publication Date
20260511
Application Date
20260217
Priority Date
20190322

Claims (20)

  1. In the presence of a transesterification catalyst, A diaryloxysilane compound comprising at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, Dialkoxysilane compounds comprising at least one of dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane, A silane compound selected from a cyclic siloxane compound and a silicon compound containing at least one linear siloxane compound, Carbonate compounds and, The process includes a polymerization step of polymerizing an aromatic diol compound or a diol compound containing an alicyclic diol compound, A method for producing a polycarbonate copolymer having siloxane structural units represented by any of formulas (1-1) to (1-4) and polycarbonate structural units represented by any of formulas (3-1) to (3-4), while removing alcohol derived from the carbonate compound under reduced pressure in a molten state during the polymerization process. (In formulas (1-1) to (1-4), R1 and R2 each independently represent an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents.) R3 to R10 and R30 to R33 each independently represent hydrogen, halogen, alkoxy, optionally substituted C1 to C20 alkyl group, optionally substituted C2 to C20 alkenyl group, or optionally substituted C6 to C30 aryl group. Z1 and Z2 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. Each J1 independently represents an integer between 0 and 5, Each K1 independently represents an integer between 0 and 5, A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, X is either a single bond or one of the structural formulas represented by the following formula (2): (In formula (2), R 11 and R 12 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C30 aryl group, or an optionally substituted C1-C20 carbon ring or heterocycle formed by the bonding of R 11 and R 12 to each other.) a and b each independently represent integers between 0 and 5000 (inclusive). (In formulas (3-1) to (3-4), R13 to R20 and R40 to R51 each independently represent hydrogen, halogen, alkoxy, optionally substituted C1 to C20 alkyl group, optionally substituted C2 to C20 alkenyl group, or optionally substituted C6 to C30 aryl group, Z3 and Z4 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. Each of J2 independently represents an integer between 0 and 5, Each K² independently represents an integer between 0 and 5, A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, Y is either a single bond or one of the structural formulas represented by formula (4). (In the formula, R 21 and R 22 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C30 aryl group, or an optionally substituted C1-C20 carbon ring or heterocycle formed by the bonding of R 21 and R 22 to each other.) c and d each independently represent an integer between 0 and 5000 (inclusive).
  2. Z1 to Z4 are each independently a C1 to C3 alkylene group which may have substituents. J1 and J2 each independently represent integers between 0 and 2, K1 and K2 each independently represent integers between 0 and 2, inclusive. A method for producing a polycarbonate copolymer according to claim 1.
  3. A method for producing a polycarbonate copolymer according to claim 1 or 2, wherein X is a siloxane structural unit representing a fluorene ring structure formed by the bonding of R 11 and R 12 to each other, and/or Y is a polycarbonate structural unit representing a fluorene ring structure formed by the bonding of R 21 and R 22 to each other.
  4. In the presence of a transesterification catalyst, A diaryloxysilane compound comprising at least one of a dialkyldiaryloxysilane, a diaryldiaryloxysilane, and a monoalkylmonoaryldiaryloxysilane, Dialkoxysilane compounds comprising at least one of dialkyldialkoxysilane, diaryldialkoxysilane, and monoalkylmonoaryldialkoxysilane, A silane compound selected from a cyclic siloxane compound and a silicon compound containing at least one linear siloxane compound, The process includes a polymerization step of polymerizing a carbonate compound with a diol compound containing an aromatic diol compound or an alicyclic diol compound. A method for producing a polycarbonate copolymer having siloxane constituent units represented by formula (1) and polycarbonate constituent units represented by formula (3), while removing alcohol derived from the carbonate compound under reduced pressure in a molten state during the polymerization process. (In formula (1), R1 and R2 each independently represent an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents) R3 to R10 each independently represent hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. X is one of the structural formulas represented by the following formula (2): (In formula (2), R 11 and R 12 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C30 aryl group, or an optionally substituted C1-C20 carbon ring or heterocycle formed by the bonding of R 11 and R 12 to each other.) a and b each independently represent integers between 0 and 5000 (inclusive). (In the formula, R13 to R20 each independently represent hydrogen, halogen, alkoxy, optionally substituted C1 to C20 alkyl group, optionally substituted C2 to C20 alkenyl group, or optionally substituted C6 to C30 aryl group) Y is one of the structural formulas represented by equation (4), (In the formula, R 21 and R 22 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C30 aryl group, or an optionally substituted C1-C20 carbon ring or heterocycle formed by the bonding of R 21 and R 22 to each other.) c and d each independently represent an integer between 0 and 5000 (inclusive).
  5. The method for producing a polycarbonate copolymer according to any one of claims 1 to 4, wherein the transesterification catalyst comprises an alkali metal compound and/or an alkaline earth metal.
  6. The method for producing a polycarbonate copolymer according to claim 5, wherein the alkali metal compound and/or alkaline earth metal compound includes a carbonate.
  7. A method for producing a polycarbonate copolymer according to any one of claims 1 to 6, wherein the weight-average molecular weight of the polycarbonate copolymer is 10,000 to 300,000.
  8. A method for producing a polycarbonate copolymer according to any one of claims 1 to 7, wherein in the polymerization step, the amount of the transesterification catalyst relative to the diol compound is 1.0 × 10⁻⁷ to 1.0 × 10⁻² in molar ratio.
  9. A method for producing a polycarbonate copolymer according to any one of claims 1 to 8, wherein the reaction temperature in the polymerization step is in the range of 150°C to 300°C.
  10. A method for producing a polycarbonate copolymer according to any one of claims 1 to 9, further comprising a vacuum step in which the reaction pressure is gradually reduced to 400 Pa or less during the polymerization step.
  11. A method for producing a polycarbonate copolymer according to any one of claims 1 to 10, wherein the polymerization step involves polymerizing the carbonate compound and the diol compound under a pressure of 400 Pa or less.
  12. A method for producing a polycarbonate copolymer according to any one of claims 1 to 11, wherein no solvent is used in the polymerization step.
  13. A method for producing a polycarbonate copolymer according to any one of claims 1 to 12, wherein the ratio of the total number of moles of the carbonate compound and the diaryloxysilane compound used in the polymerization step to the number of moles of the diol compound is 0.9 or more and 1.2 or less.
  14. A method for producing a polycarbonate copolymer according to any one of claims 1 to 13, wherein the number of moles of the siloxane constituent units in the polycarbonate copolymer is 1 to 1000, and the number of moles of the polycarbonate constituent units is 1 to 1000.
  15. A method for producing a polycarbonate copolymer according to any one of claims 1 to 14, wherein the molar ratio of the siloxane constituent unit to the polycarbonate constituent unit is 0.01:99.99 to 99.99:0.01.
  16. A method for producing a polycarbonate copolymer according to any one of claims 1 to 15, wherein the Q value of the polycarbonate copolymer measured under the conditions of 280°C and 160 kgf is 8 (× 10⁻² cm³ s⁻¹ ) or higher.
  17. A polycarbonate copolymer having a siloxane structural unit represented by any of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any of formulas (3-1) to (3-4), wherein the low molecular weight compound with a weight-average molecular weight of 1,000 or less accounts for 30% by weight or less. (In formulas (1-1) to (1-4), R1 and R2 each independently represent an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents.) R3 to R10 and R3 to R33 each independently represent hydrogen, halogen, alkoxy, optionally substituted C1 to C20 alkyl group, optionally substituted C2 to C20 alkenyl group, or optionally substituted C6 to C30 aryl group. Z1 and Z2 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. Each J1 independently represents an integer between 0 and 5, Each K1 independently represents an integer between 0 and 5, A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, X is either a single bond or one of the structural formulas represented by the following formula (2): (In formula (2), R 11 and R 12 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C30 aryl group, or an optionally substituted C1-C20 carbon ring or heterocycle formed by the bonding of R 11 and R 12 to each other.) a and b each independently represent integers between 0 and 5000 (inclusive). (In formulas (3-1) to (3-4), R13 to R20 and R40 to R51 each independently represent hydrogen, halogen, alkoxy, optionally substituted C1 to C20 alkyl group, optionally substituted C2 to C20 alkenyl group, or optionally substituted C6 to C30 aryl group, Z3 and Z4 are each independently alkylene groups having 1 to 5 carbon atoms, which may have substituents. Each of J2 independently represents an integer between 0 and 5, Each K² independently represents an integer between 0 and 5, A1 and A2 each independently represent either -O- or -CH-. L1 and L2 each independently represent integers between 0 and 3, Y is either a single bond or one of the structural formulas represented by formula (4). (In the formula, R 21 and R 22 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C30 aryl group, or an optionally substituted C1-C20 carbon ring or heterocycle formed by the bonding of R 21 and R 22 to each other.) c and d each independently represent an integer between 0 and 5000 (inclusive).
  18. Z1 to Z4 are each independently a C1 to C3 alkylene group which may have substituents. J1 and J2 each independently represent integers between 0 and 2, K1 and K2 each independently represent integers between 0 and 2, inclusive. The polycarbonate copolymer according to claim 17.
  19. The polycarbonate copolymer according to claim 17 or 18, wherein X is a siloxane structural unit representing a fluorene ring structure formed by the bonding of R 11 and R 12 to each other, and/or Y is a polycarbonate structural unit representing a fluorene ring structure formed by the bonding of R 21 and R 22 to each other.
  20. A polycarbonate copolymer having siloxane constituent units represented by formula (1) and polycarbonate constituent units represented by formula (3), wherein the proportion of low molecular weight compounds with a weight-average molecular weight of 1,000 or less, calculated from the GPC area ratio, is 30% by weight or less. (In formula (1), R1 and R2 each independently represent an alkyl group having 1 to 20 carbon atoms which may have substituents, or an aryl group having 6 to 30 carbon atoms which may have substituents) R3 to R10 each independently represent hydrogen, halogen, alkoxy, optionally substituted C1-C20 alkyl group, optionally substituted C2-C20 alkenyl group, or optionally substituted C6-C30 aryl group. X is one of the structural formulas represented by the following formula (2): (In formula (2), R 11 and R 12 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C30 aryl group, or an optionally substituted C1-C20 carbon ring or heterocycle formed by the bonding of R 11 and R 12 to each other.) a and b each independently represent integers between 0 and 5000 (inclusive). (In the formula, R13 to R20 each independently represent hydrogen, halogen, alkoxy, optionally substituted C1 to C20 alkyl group, optionally substituted C2 to C20 alkenyl group, or optionally substituted C6 to C30 aryl group) Y is one of the structural formulas represented by equation (4), (In the formula, R 21 and R 22 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, or an optionally substituted C6-C30 aryl group, or an optionally substituted C1-C20 carbon ring or heterocycle formed by the bonding of R 21 and R 22 to each other.) c and d each independently represent an integer between 0 and 5000 (inclusive).

Description

This invention relates to methods for producing polycarbonate copolymers and polysiloxane compounds, and more particularly to methods for producing polycarbonate copolymers having siloxane structural units, and to polycarbonate copolymers, etc. Thermoplastic polycarbonate resins possess excellent impact resistance and mechanical properties, and can be formed into various molded products using simple and highly productive processing methods such as injection molding. They are used in a wide range of industrial fields, including electrical and electronic equipment, office automation equipment, heavy electrical machinery, precision machinery, and automotive industries. Conventional polycarbonate resins have a drawback of poor fluidity due to their high melt viscosity, which can make injection molding of precision parts and thin materials difficult. Therefore, it was previously necessary to raise the temperature during the molding process. This high-temperature molding process resulted in longer molding cycles, higher costs, and the risk of polycarbonate resin degradation during molding. Attempts have been made to improve the fluidity of polycarbonate resins (Patent Documents 1 and 2), but sufficiently high fluidity without compromising the inherent properties of polycarbonate resin (such as impact resistance) has not always been achieved. In addition to polycarbonate resins, aromatic polysiloxane polymers, also known as polyarylenesiloxanes, are known as materials for molded products produced by molding methods such as injection molding (see, for example, Patent Document 3). In recent years, the importance of polysiloxane compounds such as polyarylenesiloxanes has increased, and they are used, for example, as release layers in photocopying, photoresist materials, plasticizers for polycarbonates, and components of powder surface coating systems. Known methods for producing polysiloxane compounds such as polyarylenesiloxanes include a method in which hydrochloric acid is produced by reacting dimethyldichlorosilane with bisphenol A in a solvent (Non-Patent Document 1), and a method in which the reaction is carried out in a solvent to which acetic acid has been added (Patent Document 4). Furthermore, polycarbonate resins, polysiloxane compounds, etc., that are particularly suitable for specific applications such as optical applications have not yet been realized. Japanese Patent Publication No. 2016-148047Japanese Unexamined Patent Publication No. 62-297319Special Publication No. 08-502537Special Publication No. 2015-512999 Journal of Polymer Science, Vol. 18, 3119-3127 (1980) [I. Polycarbonate Copolymer] The methods for producing polycarbonate copolymers in the present invention all include a polymerization step in which at least one silane compound selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane compound, and a predetermined silicon compound (siloxane compound), a carbonate compound, and an aromatic diol compound are polymerized in the presence of a transesterification catalyst, as will be described in detail later. The polymerization reaction described above can be schematically shown below. For example, when diaryloxysilane compound (Si( CH3 ) 2 (OPh) 2 ), which is an example of a silane compound and has two methyl groups and a phenoxy group, is reacted with diphenyl carbonate (PhO-CO-OPh), which is an example of a carbonate compound, and bisphenol A, which is an example of an aromatic diol compound, the following polycarbonate copolymer is obtained. In other words, it is a polycarbonate copolymer having, for example, a siloxane structural unit produced by the reaction of formula (A) below, and a polycarbonate structural unit produced by, for example, the reaction of formula (B) below. In this polymerization reaction, as described below, alcohols derived from the carbonate compound are produced as by-products. For example, when diaryl carbonate is used as the carbonate compound, aryl alcohols such as phenol (PhOH) are produced. Therefore, in the polymerization step, the mixture of the above components is kept molten, and the polymerization reaction proceeds under reduced pressure while removing the by-product alcohols, such as aryl alcohols such as phenol. The method for producing the polycarbonate copolymer according to the present invention will be described in detail below. <1. Method for producing polycarbonate copolymer> [(I) Silane compounds] The silane compounds used in the polymerization process are used to form siloxane structural units in the polycarbonate copolymer, as shown in formula (A ) above. The type of silane compound is not particularly limited as long as it can form siloxane structural units containing the -OSi( R1R2 )O- moiety in the main chain of the polycarbonate copolymer, as will be described in detail later, but it is selected from predetermined diaryloxysilane compounds, predetermined dialkoxysilane compounds, and predetermined silicon compound