Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/307—General preparatory processes using carbonates and phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
  • C08G63/82—Preparation processes characterised by the catalyst used
  • C08G63/87—Non-metals or inter-compounds thereof

Definitions

• the present invention relates to a method for producing at least one thermoplastic resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate. More specifically, a method for producing at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates using a transesterification catalyst that exhibits excellent reactivity even when added in a small amount and produces a small amount of specific by-products. Regarding.
• the present invention also relates to a compound useful as a transesterification catalyst for producing at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters and polyester carbonates.
• thermoplastic resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate Several methods are known for producing at least one thermoplastic resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate. Among them, a dihydroxy compound (e.g., bisphenol A) and an ester-forming compound (e.g., diaryl carbonate or dicarboxylic acid ester) are reacted by a melt transesterification method in the presence of a transesterification catalyst to produce polycarbonate, polyester, and
• the process for producing at least one thermoplastic resin selected from the group consisting of polyester carbonate does not use solvents that affect the environment; the energy required for production is small; impurities such as contaminating chlorine in the product are small. It is preferred as a commercial process because it has several merits such as;
• a method using a metal-based catalyst such as an alkali metal, an alkaline earth metal, or a transition metal is conventionally known.
• a method using a quaternary onium salt such as a phosphonium salt or an ammonium salt see Patent Document 1
• Patent Document 1 a method using an organic base catalyst such as a nitrogen-containing basic compound
• Patent Documents 2 to 4 the above metal-based A method of combining a catalyst and an organic base catalyst has also been proposed (see Patent Documents 5 to 7, for example).
• Patent Documents 8 and 9 disclose a method using a catalyst having an imidazole structure.
• Patent document 10 discloses a method using a catalyst having a phosphazene structure.
• thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates by transesterification
• a dihydroxy compound and an ester-forming compound are brought into a molten state, and a transesterification catalyst is added to obtain a high Polycondensation is carried out under vacuum conditions while distilling off monohydroxy compounds (such as phenol).
• This method has the problem of causing side reactions due to high temperature conditions and producing coloring components or specific by-products that adversely affect weather resistance and fluidity.
• the color tone of at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates tends to deteriorate, and in particular, by-products tend to form.
• the thermal stability of at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates obtained, particularly color tone stability during melt retention, and hydrolysis resistance at high temperatures. It also has the drawback of being inferior.
• At least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates produced using organic catalysts is selected from the group consisting of polycarbonates, polyesters, and polyester carbonates obtained using metal catalysts. Although it tends to have less by-products than at least one thermoplastic resin, it was still not at a satisfactory level. Since organic catalysts have poor thermal stability compared to metal catalysts, it takes time for at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates to reach the desired molecular weight. longer, i.e. lower reaction activity. Since the organic catalyst has low reaction activity and a long polymerization time, at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates is subject to heat aging, and color tone tends to deteriorate. .
• the polymerization time is improved, but the formation of by-products cannot be suppressed, and at least one selected from the group consisting of polycarbonates, polyesters, and polyester carbonates. cause deterioration of the color tone of the thermoplastic resin.
• the method of combining a metal-based catalyst and an organic catalyst also increases the amount of by-products depending on the amount of the metal-based catalyst blended, and further deteriorates the color tone. For this reason, it is still impossible to balance polymerization activity and quality.
• the time required for at least one thermoplastic resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate to reach the target molecular weight is shortened.
• a method for producing at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates with a small amount of specific by-products, and a compound having this specific structure and used as an organic catalyst is shortened.
• the present inventors have investigated the relationship between the reactivity and side reaction suppression during the production of at least one thermoplastic resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate, the thermal stability of the transesterification catalyst, and the molecular structure.
• thermoplastic resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate
• the thermal stability of the transesterification catalyst and the molecular structure.
• the gist of the present invention is as follows.
• R 1 to R 24 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group, and some of the carbon atoms of the alkyl group and cycloalkyl group are hetero Alkyl groups substituted on the same N atom among R 1 to R 24 may combine to form a ring.
• R 5 , R 6 and R 7 , R 8 and R 1 may be combined to form a ring
• R 9 or R 10 , R 1 or R 2 and R 11 or R 12 are each combined may form a ring
• R 13 or R 14 , R 3 or R 4 , and R 15 or R 16 may each combine to form a ring
• R 17 or R 18 , R 5 or R 6 and R 19 or R 20 may combine to form a ring
• R 21 or R 22 , R 7 or R 8 and R 23 or R 24 may combine to form a ring.
• R 1 or R 2 , R 3 or R 4 , and R 5 or R 6 may each combine to form a ring, and R 3 or R 4 and R 5 or R 6 and R 8 or R 7 may combine to form a ring, and R 5 or R 6 , R 8 or R 7 and R 1 or R 2 may combine to form a ring.
• Each of a to d may independently 0 or 1.
• X ⁇ represents a monovalent anion.
• Ar 1 to Ar 12 each independently represent a substituted or unsubstituted aryl group.
• M ⁇ represents a monovalent anion.
• thermoplastic resin selected from the group consisting of polycarbonates, polyesters and polyester carbonates according to [1], wherein the dihydroxy compound is bisphenol A.
• thermoplastic resin selected from the group consisting of polycarbonates, polyesters and polyester carbonates according to [1] or [2], wherein the diaryl carbonate is diphenyl carbonate.
• thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates according to [6], wherein the formula (1) is represented by the following formula (1B).
• R 29 to R 52 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among R 29 to R 52 , the same alkyl group substituted on the N atom may combine to form a ring, R 30 and R 31 , R 32 and R 33 , R 34 and R 35 , R 36 and R 29 may each combine to form a ring i to l are each independently 0 or 1. Y ⁇ represents a monovalent anion.
• X - is a chloride ion, a bromide ion, a tetraphenylborate ion, a phenolate ion, a BPA monoanion represented by the following formula (3a), and the following formula (3b) Production of at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates according to [6] or [7], which is at least one selected from BPA monoanionic BPA adducts represented by Method.
• X - is selected from phenolate ions, BPA monoanions represented by the formula (3a), and BPA monoanions BPA adducts represented by the formula (3b).
• a method for producing at least one thermoplastic resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate according to [8], which is at least one.
• Z 1- to Z 5- each independently represent a monovalent anion.
• Me represents a methyl group.
• thermoplastic resin selected from the group consisting of polycarbonates, polyesters and polyester carbonates according to [11], wherein Ar 1 to Ar 12 in formula (2) are phenyl groups.
• M- is a chloride ion, a bromide ion, a tetraphenylborate ion, a phenolate ion, a BPA monoanion represented by the following formula (3a), and the following formula (3b) , (3c) which is at least one selected from the BPA monoanionic BPA adducts represented by (3c).
• M- is a phenolate ion
• the BPA monoanion BPA represented by the formulas (3b) and (3c) A method for producing at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters and polyester carbonates according to [13], which is at least one selected from adducts.
• thermoplastic selected from the group consisting of polycarbonates, polyesters, and polyester carbonates according to any one of [1] to [15], wherein the temperature during the melt polycondensation reaction is 200 to 350°C A method for producing resin.
• the viscosity average molecular weight [Mv] of at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates is 5,000 to 40,000 [1] to [16] ]
• Transesterification for producing at least one thermoplastic resin selected from the group consisting of polycarbonate, polyester, and polyester carbonate by melt polycondensation of a dihydroxy compound and a diaryl carbonate and/or a dicarboxylic acid ester
• a transesterification catalyst comprising any one selected from the group of compounds represented by the following formula (1) and the following formula (2).
• R 1 to R 24 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group, and some of the carbon atoms of the alkyl group and cycloalkyl group are hetero Alkyl groups substituted on the same N atom among R 1 to R 24 may combine to form a ring.
• R 5 , R 6 and R 7 , R 8 and R 1 may be combined to form a ring
• R 9 or R 10 , R 1 or R 2 and R 11 or R 12 are each combined may form a ring
• R 13 or R 14 , R 3 or R 4 , and R 15 or R 16 may each combine to form a ring
• R 17 or R 18 , R 5 or R 6 and R 19 or R 20 may combine to form a ring
• R 21 or R 22 , R 7 or R 8 and R 23 or R 24 may combine to form a ring.
• R 1 or R 2 , R 3 or R 4 , and R 5 or R 6 may each combine to form a ring, and R 3 or R 4 and R 5 or R 6 and R 8 or R 7 may combine to form a ring, and R 5 or R 6 , R 8 or R 7 and R 1 or R 2 may combine to form a ring.
• Each of a to d may independently 0 or 1.
• X ⁇ represents a monovalent anion.
• Ar 1 to Ar 12 each independently represent a substituted or unsubstituted aryl group.
• M ⁇ represents a monovalent anion.
• L 1 ⁇ and L 2 ⁇ are a phenolate ion, a BPA monoanion represented by the following formula (3a), and a BPA represented by the following formula (3b) At least one selected from monoanionic BPA adducts.
• L 3 ⁇ to L 5 ⁇ represent monovalent anions.Me represents a methyl group.
• Ar 1 to Ar 12 each independently represent a substituted or unsubstituted aryl group.
• M ⁇ represents a monovalent anion.
• the total amount of the compounds represented by the following formulas (A) to (E) measured for the polycarbonate hydrolyzate is 300 mass ppm or more and 550 mass ppm or less with respect to the polycarbonate resin.
• R a to R f each independently represent a hydrogen atom or a methyl group.
• R a to R f each independently represent a hydrogen atom or a methyl group.
• the hydrogen atom of may be substituted by a substituent.
• the compound represented by the formula (1) and/or the compound represented by the formula (2) as a transesterification catalyst for the melt polycondensation reaction, a small addition amount and a high Side reactions can be suppressed while maintaining reaction activity, and the amount of by-products is reduced. It is possible to produce at least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates, which suppresses the deterioration of heat resistance, transparency and mechanical strength, and has a good color tone.
• At least one thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyester carbonates produced by the present invention is used as a material for manufacturing parts in automobile materials, electrical and electronic equipment materials, housing materials, and other industrial fields.
• the thermoplastic resin can be suitably used alone or as a composition compounded with other resins and additives.
• the compound of the present invention has high thermal stability and can be suitably used as a transesterification catalyst for the production of various thermoplastic resins.
• thermoplastic resin of the present invention comprises dihydroxy A compound and a diaryl carbonate and/or a dicarboxylic acid ester as an ester-forming compound are combined with the compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”) and/or the formula
• compound (1) the compound represented by the formula (1)
• compound (2) the compound represented by the formula (1)
• compound (2) the compound represented by the formula (2)
• thermoplastic resin of the present invention It is a method for producing at least one selected thermoplastic resin (hereinafter sometimes referred to as "thermoplastic resin of the present invention”).
• Compounds (1) and (2) used as transesterification catalysts in the method for producing a thermoplastic resin of the present invention exhibit polycondensation activity without decomposing or volatilizing until the final stage of polycondensation and have a large molecular size. can effectively suppress side reactions.
• Thermoplastic resin of the present invention is a thermoplastic resin obtained through a step of melt polycondensation of a dihydroxy compound and a diaryl carbonate and/or a dicarboxylic acid ester in the presence of an ester exchange catalyst.
• Specific examples include polycarbonate, polyester carbonate, and polyester.
• the thermoplastic resin of the present invention is not particularly limited, but polycarbonate is particularly preferable, and aromatic polycarbonate obtained by melt polycondensation of an aromatic dihydroxy compound and diaryl carbonate in the presence of the transesterification catalyst is particularly preferred. preferable.
• dihydroxy compound In the method for producing a thermoplastic resin of the present invention, a dihydroxy compound and a diaryl carbonate and/or a dicarboxylic acid ester are used as raw materials.
• the dihydroxy compound is not particularly limited, and examples thereof include the following, but are not limited to the following.
• Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl; 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy) dihydroxy diaryl ethers such as benzene, 1,3-bis(4-hydroxyphenoxy)benzene; 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as "BPA"), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methoxy-4 -hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-ter
• dihydroxy compound in particular, when bisphenol A is used, diaryl carbonate and/or dicarboxylic acid ester and melt polymerization are performed in the presence of a transesterification catalyst selected from compound (1) and/or compound (2). Condensation is preferable because the content of specific by-products in the obtained thermoplastic resin can be reduced.
• diaryl carbonate, dicarboxylic acid ester In the method for producing a thermoplastic resin of the present invention, a dihydroxy compound and a diaryl carbonate and/or a dicarboxylic acid ester are used as raw materials.
• the diaryl carbonate preferably includes a compound represented by the following formula (4).
• R 53 and R 54 each independently represent a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, represents a 20 cycloalkyl group or an aryl group having 6 to 20 carbon atoms, and p and q each independently represents an integer of 0 to 5.
• diaryl carbonate examples include diphenyl carbonate (hereinafter sometimes referred to as "DPC"), bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate, bis(4-fluorophenyl) carbonate. , bis(2-chlorophenyl) carbonate, bis(2,4-difluorophenyl) carbonate, bis(4-nitrophenyl) carbonate, bis(2-nitrophenyl) carbonate, bis(methylsalicylphenyl) carbonate, ditolyl carbonate, etc. of (substituted) diaryl carbonates. Among them, diphenyl carbonate is preferred.
• These diaryl carbonates can be used individually or in mixture of 2 or more types.
• dicarboxylic acid ester is not particularly limited, diphenyl terephthalate and diphenyl isophthalate are preferably used.
• the ratio of diaryl carbonate to dicarboxylic acid ester is not particularly limited.
• the dicarboxylic acid ester is 50 mol % or less, more preferably 30 mol % or less, relative to the diaryl carbonate.
• the ratio of the raw material dihydroxy compound to the diaryl carbonate and/or dicarboxylic acid ester is arbitrary as long as the desired thermoplastic resin of the present invention can be obtained.
• diaryl carbonate and/or dicarboxylic acid ester is polycondensed with a dihydroxy compound, it is preferable to use an excess of the dihydroxy compound as a raw material.
• the amount of diaryl carbonate and/or dicarboxylic acid ester to be used is preferably at least 1.01 times (molar ratio), more preferably at least 1.02 times the amount of the dihydroxy compound.
• the obtained thermoplastic resin of the present invention has good thermal stability.
• the amount of diaryl carbonate and/or dicarboxylic acid ester to be used is preferably 1.30 times (molar ratio) or less, more preferably 1.20 times or less, relative to the dihydroxy compound.
• transesterification catalyst In the method for producing a thermoplastic resin of the present invention, a compound (1) having a specific structure represented by the following formula (1) and/or a specific structure represented by the following formula (2) is used as a transesterification catalyst. It is characterized by using a catalyst composed of the compound (2) having. As the transesterification catalyst, compound (1) may be used alone or in combination of two or more. Compound (2) may also be used alone or in combination of two or more. Also, one or more of compound (1) and one or more of compound (2) may be mixed and used.
• R 1 to R 24 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group, and some of the carbon atoms of the alkyl group and cycloalkyl group are hetero Alkyl groups substituted on the same N atom among R 1 to R 24 may combine to form a ring.
• R 5 , R 6 and R 7 , R 8 and R 1 may be combined to form a ring
• R 9 or R 10 , R 1 or R 2 and R 11 or R 12 are each combined may form a ring
• R 13 or R 14 , R 3 or R 4 , and R 15 or R 16 may each combine to form a ring
• R 17 or R 18 , R 5 or R 6 and R 19 or R 20 may combine to form a ring
• R 21 or R 22 , R 7 or R 8 and R 23 or R 24 may combine to form a ring.
• R 1 or R 2 , R 3 or R 4 , and R 5 or R 6 may each combine to form a ring, and R 3 or R 4 and R 5 or R 6 and R 8 or R 7 may combine to form a ring, and R 5 or R 6 , R 8 or R 7 and R 1 or R 2 may combine to form a ring.
• Each of a to d may independently 0 or 1.
• X ⁇ represents a monovalent anion.
• the formula (1) is more preferably a structure represented by the following formula (1B).
• Y - has the same meaning as X - in the formula (1).
• R 29 to R 52 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Among R 29 to R 52 , the same alkyl group substituted on the N atom may combine to form a ring, R 30 and R 31 , R 32 and R 33 , R 34 and R 35 , R 36 and R 29 may each combine to form a ring i to l are each independently 0 or 1. Y ⁇ represents a monovalent anion.
• X ⁇ is not particularly limited as long as it is a monovalent anion, but is not limited to chloride ion, bromide ion, tetraphenylborate ion, phenolate ion, BPA represented by the following formula (3a) It is preferably at least one selected from monoanions, BPA monoanions and BPA adducts represented by the following formula (3b).
• X 1 ⁇ is at least one selected from phenolate ions, BPA monoanions represented by the above formula (3a), and BPA monoanions represented by the above formula (3b) and BPA adducts.
• Preferred examples of compound (1) include compounds represented by the following formulas (1a) to (1e) (hereinafter sometimes referred to as "compound (1A)").
• compound (1A) has the same meaning as X - in the formula (1).
• Z 1- to Z 5- each independently represent a monovalent anion.
• Me represents a methyl group.
• compound (1) include compounds represented by the following formulas (1a') to (1e'), which are compound (1A) of the present invention.
• L 1 ⁇ and L 2 ⁇ are the phenolate ion, the BPA monoanion represented by the formula (3a), and the BPA represented by the formula (3b) At least one selected from monoanionic BPA adducts.
• L 3 ⁇ to L 5 ⁇ represent monovalent anions. The monovalent anions are represented by formula (1 ), and the preferred ones are also the same.Me represents a methyl group.
• Compound (1) can be obtained or produced, for example, by the following method.
• the method for producing compound (1) is not limited to the following method.
• a commercially available organic reagent having a structure other than that of formula (1) is used as a raw material to produce compound (1).
• the anion of a compound having an anion different from the anion (X ⁇ ) of formula (1) is converted to the anion (X ⁇ ) of formula (1) before use.
• the commercially available compound (1) is used as it is.
• Ar 1 to Ar 12 each independently represent a substituted or unsubstituted aryl group.
• M ⁇ represents a monovalent anion.
• examples of the aryl group for Ar 1 to Ar 12 include a phenyl group and a naphthyl group.
• the substituents that the aryl groups Ar 1 to Ar 12 may have include one or more of alkyl groups having 1 to 20 carbon atoms.
• the aryl group may have only one of these substituents, or may have two or more.
• Ar 1 to Ar 12 are each independently preferably an unsubstituted aryl group, particularly preferably an unsubstituted phenyl group.
• M ⁇ is not particularly limited as long as it is a monovalent anion, and is represented by the following formula (3a): chloride ion, bromide ion, tetraphenylborate ion, phenolate ion. It is preferably at least one selected from BPA monoanions and BPA monoanions represented by the following formulas (3b) and (3c), BPA adducts represented by the following formulas (3b) and (3c), phenolate ions, and represented by the following formula (3a) It is preferably at least one selected from BPA monoanions and BPA monoanions and BPA adducts represented by the following formula (3b).
• compound (2) include the following.
• Compound (2) can be obtained or produced, for example, by the following method.
• the method for producing compound (2) is not limited to the following method. Using commercially available organic reagents as starting materials, compound (2) is produced by the method described in Examples and the like.
• the amount of compound (1) and/or compound (2) used as a transesterification catalyst in the melt polycondensation step is not particularly limited, but is 0 per 1 mol of the dihydroxy compound. It is preferably 0.01 ⁇ mol or more, more preferably 0.1 ⁇ mol or more, and even more preferably 1 ⁇ mol or more. By adjusting the amount to be equal to or higher than the above lower limit, polymerization activity can be obtained, and the desired thermoplastic resin of the present invention having a predetermined high molecular weight can be obtained.
• the amount of compound (1) and/or compound (2) used is preferably 1000 ⁇ mol or less, more preferably 100 ⁇ mol or less, still more preferably 50 ⁇ mol or less, and particularly preferably 1 mol of the dihydroxy compound. 10 ⁇ mol or less, most preferably 5 ⁇ mol or less. Formation of by-products can be suppressed by setting the content to be equal to or less than the above upper limit.
• compound (1) and/or compound Compounds other than (2) may also be used as catalyst components.
• a basic compound different from compound (1) and/or compound (2) may be further added.
• Such compounds include at least one selected from the group consisting of compounds of Group 1 elements of the periodic table (excluding hydrogen), compounds of Group 2 elements of the periodic table, basic boron compounds, and basic phosphorus compounds. and the compound of
• Group 1 elements include, for example, lithium, sodium, potassium, rubidium, and cesium.
• cesium compounds are preferred, and cesium carbonate, cesium hydrogencarbonate, and cesium hydroxide are particularly preferred.
• Examples of the compounds of the Group 2 elements include inorganic compounds such as hydroxides and carbonates of beryllium, magnesium, calcium, strontium, barium, etc.; alcohols, phenols, salts thereof with organic carboxylic acids, etc. is mentioned.
• Basic boron compounds include sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, barium salts, and strontium salts of boron compounds.
• Boron compounds include, for example, tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, Examples include tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron and the like.
• Basic phosphorus compounds include, for example, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, triphenylphosphine, tri-t-butylphenylphosphine and the like.
• Examples include trivalent phosphorus compounds.
• the proportion of catalyst compounds other than compound (1) and/or compound (2) that may be included as catalyst components is compound (1) and/or compound (2).
• other catalyst compound usually in the range of 10000:1 to 3:1, preferably in the range of 5000:1 to 5:1, more preferably in the range of 1000:1 to 10:1. The above range is preferable because the production of by-products can be suppressed.
• any method can be used as the method for adding the transesterification catalyst.
• the transesterification catalyst may be directly mixed with the raw material dihydroxy compound or ester-forming compound, or may be dissolved in a solvent in advance and used as a diluted solution. By using it as a diluted solution, it is possible to improve feed accuracy and dispersibility in raw materials.
• the solvent and catalyst concentration to be used are not particularly limited, and may be appropriately selected according to the solubility. Examples of solvents include water, phenol, acetone, alcohol, toluene, ether, tetrahydrofuran and the like.
• the properties of water are not particularly limited as long as the types and concentrations of impurities contained are constant. Generally, distilled water, deionized water, etc. are preferably used. An additional transesterification catalyst may be added during the polymerization.
• thermoplastic resin In the method for producing a thermoplastic resin of the present invention, the dihydroxy compound and diaryl carbonate and/or dicarboxylic acid ester as raw materials are mixed, and the raw material mixture is polymerized in a polycondensation reactor in the presence of the transesterification catalyst. It is carried out by a condensation reaction.
• a condensation reaction As the reaction system of this polycondensation step, a batch system, a continuous system, a combination thereof, or the like can be used.
• thermoplastic resin of the present invention is produced through the step of forming pellets and the like.
• the polycondensation process is usually carried out continuously in two stages or more, preferably in a multi-stage system of three to seven stages.
• Specific reaction conditions are usually temperature: 150° C. to 350° C., pressure: normal pressure to 0.01 Torr (1.3 Pa), average residence time: 5 minutes to 150 minutes.
• the temperature is increased stepwise and the vacuum is increased within the reaction conditions described above. set.
• the temperature is preferable to set the temperature as low as possible and the residence time as short as possible. From this point of view, the reaction temperature is preferably 150°C to 320°C.
• a plurality of reactors including a vertical reactor are provided to increase the average molecular weight of the thermoplastic resin of the present invention.
• 3 to 6 reactors, preferably 4 to 5 reactors are installed.
• reactors include stirred tank reactors, thin film reactors, centrifugal thin film evaporation reactors, surface renewal twin-screw kneading reactors, horizontal twin-screw stirring reactors, wet-wall reactors, and free-falling reactors.
• a perforated plate reactor for polymerization, a perforated plate reactor with a wire for polymerizing while falling along a wire, and the like are used.
• Examples of the type of stirring blades of the vertical reactor include turbine blades, paddle blades, Faudler blades, anchor blades, full zone blades (manufactured by Shinko Pantec Co., Ltd.), sunmera blades (manufactured by Mitsubishi Heavy Industries, Ltd.), and max. Blend blades (manufactured by Sumitomo Heavy Industries, Ltd.), helical ribbon blades, twisted lattice blades (manufactured by Hitachi Ltd.), and the like can be mentioned.
• a horizontal reactor is one in which the rotating shaft of the stirring blade is horizontal (horizontal direction).
• the stirring blades of the horizontal reactor include uniaxial stirring blades such as disk type and paddle type, HVR, SCR, N-SCR (manufactured by Mitsubishi Heavy Industries, Ltd.), and Bivolak (manufactured by Sumitomo Heavy Industries, Ltd.). (manufactured by Hitachi, Ltd.), or biaxial stirring blades such as spectacle blades and lattice blades (manufactured by Hitachi, Ltd.).
• the molecular weight of the thermoplastic resin of the present invention obtained by the method for producing the thermoplastic resin of the present invention is arbitrary and may be appropriately selected and determined.
• the viscosity average molecular weight [Mv] converted from the solution viscosity of the thermoplastic resin of the present invention is usually 5,000 or more, preferably 10,000 or more, more preferably 15,000 or more, and usually 40,000 or less. Yes, preferably 30,000 or less, more preferably 24,000 or less.
• the intrinsic viscosity [ ⁇ ] is a value calculated by the following formula after measuring the specific viscosity [ ⁇ sp ] at each solution concentration [C] (g/dl).
• the terminal hydroxyl group concentration of the thermoplastic resin of the present invention is not particularly limited, it is preferably 1500 ppm or less, more preferably 1000 ppm or less, still more preferably 800 ppm or less, and particularly preferably 600 ppm or less. As the terminal hydroxyl group concentration becomes lower, the retention heat stability of the thermoplastic resin of the present invention tends to be further improved.
• the terminal hydroxyl group concentration of the thermoplastic resin of the present invention is preferably 50 ppm or more, more preferably 100 ppm or more, still more preferably 150 ppm or more, and particularly preferably 200 ppm or more. Color tone tends to be improved as the terminal hydroxyl group concentration increases.
• the unit of terminal hydroxyl group concentration is the weight of terminal hydroxyl groups expressed in ppm with respect to the weight of the thermoplastic resin of the present invention.
• the measurement method is colorimetric determination by the titanium tetrachloride/acetic acid method (the method described in Macromol. Chem. 88, 215 (1965)).
• thermoplastic resin of the present invention when used as a raw material dihydroxy compound, when the resulting thermoplastic resin of the present invention is hydrolyzed, it may contain by-products such as those represented by the following formulas (A) to (E). be.
• the presence of these by-products means that the structural units of the resulting thermoplastic resin contain heterogeneous structural units derived from bisphenol A.
• R a to R f each independently represent a hydrogen atom or a methyl group.
• one or more hydrogen atoms bonded to the benzene ring are alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, phenyl groups, and vinyl groups. , a cyano group, an ester group, an amide group, a nitro group, or the like.
• the content of these by-products can be measured by analyzing the thermoplastic resin of the present invention after hydrolysis.
• the total amount of by-products represented by the above formulas (A) to (E) is preferably 1000 ppm or less, preferably 800 ppm or less, relative to the entire thermoplastic resin obtained before hydrolysis. More preferably, it is 600 ppm or less.
• the thermoplastic resin of the present invention has good color tone and light resistance.
• the total amount of the by-products represented by the above formulas (A) to (E) is preferably 0 ppm. As a result, there is a problem that the color tone is deteriorated. For this reason, from the viewpoint of product color tone, it is usually preferably 100 ppm or more.
• the thermoplastic resin of the present invention has a good color tone.
• the pellet YI is usually 15 or less, preferably 10 or less, more preferably 8 or less.
• the pellet YI was evaluated by measuring the YI value (yellow index value) of the thermoplastic resin pellet in reflected light according to ASTM D1925.
• a spectrophotometer CM-5 manufactured by Konica Minolta Co., Ltd. was used as an apparatus, and a measurement diameter of 30 mm and SCE were selected as measurement conditions.
• a calibration glass CM-A212 for petri dish measurement was fitted into the measurement part, and a zero calibration box CM-A124 was placed over it to perform zero calibration, followed by white calibration using a built-in white calibration plate.
• L * is 99.40 ⁇ 0.05, a * is 0.03 ⁇ 0.01, b * is -0.43 ⁇ 0.01, YI is - It was confirmed to be 0.58 ⁇ 0.01.
• the pellets were measured by packing them into a cylindrical glass container having an inner diameter of 30 mm and a height of 50 mm to a depth of about 40 mm. The operation of taking out the pellets from the glass container and measuring again was repeated twice, and the average value of the measured values of a total of three times was used. The smaller the YI value, the less yellowish the resin and the better the color tone.
• thermoplastic resin of the present invention is, if necessary, the thermoplastic resin of the present invention, that is, at least one selected from the group consisting of polycarbonates, polyesters, and polyester carbonates produced by the method for producing a thermoplastic resin of the present invention.
• a thermoplastic resin composition may be used by blending other components such as a polycarbonate resin, a polyester resin, other resins, and various resin additives other than the thermoplastic resin.
• One or more of the other components may be contained in any combination and ratio.
• Examples of other resins include polyolefin resins such as polyethylene resins and polypropylene resins; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; .
• resins may be contained alone, or two or more may be contained in any combination and ratio.
• Resin additives include, for example, thermal stability agents, antioxidants, ultraviolet absorbers, release agents, lubricants, dyes and pigments, antistatic agents, antifog agents, antiblocking agents, fluidity improvers, plasticizers, dispersants agents, antibacterial agents, impact modifiers, flame retardants, reinforcing materials such as glass fiber and carbon fiber, and fillers such as talc, mica and silica.
• One type of resin additive may be contained, or two or more types may be contained in any combination and ratio.
• L 1 ⁇ and L 2 ⁇ are a phenolate ion, a BPA monoanion represented by the following formula (3a), and a BPA represented by the following formula (3b) At least one selected from monoanionic BPA adducts.
• L 3 ⁇ to L 5 ⁇ represent monovalent anions. The monovalent anions are represented by formula (1 ), and the preferred ones are also the same.Me represents a methyl group.
• L 3- is chloride ion, bromide ion, tetraphenylborate ion, phenolate ion, BPA monoanion represented by formula (3a), and formula (3b). is preferably at least one selected from the BPA monoanion BPA adduct represented by the phenolate ion, the BPA monoanion represented by formula (3a), and the BPA monoanion BPA adduct represented by formula (3b) At least one selected from is more preferable.
• L 4- is chloride ion, bromide ion, tetraphenylborate ion, phenolate ion, BPA monoanion represented by formula (3a), and formula (3b).
• L 5- is chloride ion, bromide ion, tetraphenylborate ion, phenolate ion, BPA monoanion represented by formula (3a), and formula (3b). It is preferably at least one selected from BPA monoanions BPA adducts, phenolate ions, BPA monoanions represented by formula (3a), and BPA monoanions BPA adducts represented by formula (3b) At least one selected is more preferable.
• the compound (1A) of the present invention represented by formulas (1a') to (1e') is particularly useful as a transesterification catalyst in the method for producing a thermoplastic resin of the present invention, that is, as a transesterification catalyst of the present invention.
• Ar 1 to Ar 12 each independently represent a substituted or unsubstituted aryl group.
• M ⁇ represents a monovalent anion.
• examples of the aryl group for Ar 1 to Ar 12 include a phenyl group and a naphthyl group.
• the substituents that the aryl groups Ar 1 to Ar 12 may have include one or more of alkyl groups having 1 to 20 carbon atoms.
• the aryl group may have only one of these substituents, or may have two or more.
• Ar 1 to Ar 12 are each independently preferably an unsubstituted aryl group, particularly preferably an unsubstituted phenyl group.
• M ⁇ is not particularly limited as long as it is a monovalent anion, and is represented by the following formula (3a): chloride ion, bromide ion, tetraphenylborate ion, phenolate ion. It is preferably at least one selected from BPA monoanions and BPA monoanions represented by the following formulas (3b) and (3c), BPA adducts represented by the following formulas (3b) and (3c), phenolate ions, and represented by the following formula (3a) It is preferably at least one selected from BPA monoanions and BPA monoanions and BPA adducts represented by the following formula (3b).
• Specific examples of the compound (2) of the present invention represented by formula (2) include the specific examples of the compound (2) described above.
• the compound (2) of the present invention represented by formula (2) is particularly useful as a transesterification catalyst in the method for producing a thermoplastic resin of the present invention, that is, as a transesterification catalyst of the present invention.
• the polycarbonate of the present invention is a polycarbonate produced by the method for producing a thermoplastic resin of the present invention, and has a viscosity-average molecular weight [Mv] defined as above of 14,000 or more and 30,000 or less,
• Mv viscosity-average molecular weight
• the total amount of the compounds represented by the following formulas (A) to (E) (hereinafter sometimes referred to as "specific compounds") measured on the hydrolyzate of the polycarbonate is 300 mass with respect to the polycarbonate resin. ppm or more and 550 mass ppm or less.
• the viscosity-average molecular weight [Mv] of the solution viscosity of the polycarbonate of the present invention is preferably 15,000 or more, more preferably 18,000 or more, and preferably 29,000 or less, more preferably 23,000 or less.
• the viscosity-average molecular weight is at least the lower limit of the above range, the mechanical strength of the polycarbonate of the present invention can be further improved, which is more preferable when used in applications requiring high mechanical strength.
• the viscosity-average molecular weight By setting the viscosity-average molecular weight to the upper limit of the above range or less, the decrease in fluidity of the polycarbonate of the present invention can be suppressed and improved, and the moldability can be enhanced to facilitate molding.
• R a to R f each independently represent a hydrogen atom or a methyl group.
• one or more hydrogen atoms bonded to the benzene ring are alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, phenyl groups, and vinyl groups. , a cyano group, an ester group, an amide group, a nitro group, or the like. It may be substituted with a substituent such as an ano group, an ester group, an amide group, or a nitro group.
• the content of these specific compounds can be measured by hydrolyzing the polycarbonate of the present invention and then analyzing it. More preferably, the total amount of specific compounds is 500 ppm or less relative to the entire polycarbonate obtained before hydrolysis.
• the polycarbonate of the present invention has good color tone and light resistance.
• the total amount of the specific compounds is preferably 0 ppm, but if it is attempted to be extremely reduced, the polymerization activity must be lowered and the reaction must be carried out for a long time, resulting in a problem of deterioration in color tone. Therefore, from the viewpoint of product color tone, the content of the specific compound is preferably 100 ppm or more.
• the terminal hydroxyl group concentration of the polycarbonate of the present invention is not particularly limited, it is preferably 1000 ppm or less, more preferably 800 ppm or less, still more preferably 700 ppm or less, and particularly preferably 600 ppm or less. As the terminal hydroxyl group concentration becomes lower, the residence heat stability of the polycarbonate of the present invention tends to be further improved.
• the terminal hydroxyl group concentration of the polycarbonate of the present invention is preferably 250 ppm or more, more preferably 300 ppm or more, still more preferably 350 ppm or more, and particularly preferably 400 ppm or more. Color tone tends to be improved as the terminal hydroxyl group concentration increases.
• Terminal hydroxyl group content of thermoplastic resin The terminal hydroxyl group content of the thermoplastic resin was measured by a colorimetric method using titanium tetrachloride/acetic acid according to the method described below.
• thermoplastic resin (4) Content of by-products (specific compounds) represented by formulas (A) to (E) contained in thermoplastic resin
• methanol 45 mL and 25 weight % sodium hydroxide aqueous solution was added and stirred at 70° C. for 30 minutes for hydrolysis (methylene chloride solution).
• 6 N hydrochloric acid was added to this methylene chloride solution to adjust the pH of the solution to about 2, and the volume was adjusted to 100 mL with pure water.
• Example 1 Synthesis of catalyst A> By treating 388 mg (0.50 mmol) of tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium chloride (hereinafter sometimes abbreviated as P5-Cl) (manufactured by Sigma-Aldrich) according to Synthesis Example 1, A catalyst A (hereinafter sometimes abbreviated as P5-BPA 2 ) represented by the following structural formula was obtained with a yield of 53%.
• P2(CyNH)-BF 4 1,1,1,3,3,3-hexakis(cyclohexylamino)-1 ⁇ 5 ,3 ⁇ 5 -diphosphazenium tetrafluoroborate
• Step 3 1,1,1,3,3,3-hexakis(cyclohexyl(methyl)amino)-1 ⁇ 5 ,3 ⁇ 5 -diphosphazenium tetrafluoroborate (hereinafter abbreviated as P2(CyNMe)-BF 4 Synthesis of) P2(CyNH)-BF 4 (1.33 g, 1.77 mmol) was dissolved in 10 mL of chlorobenzene. Next, 10 mL of 50% sodium hydroxide aqueous solution and dimethyl sulfate (manufactured by Merck) (1.61 g, 12.7 mmol) were added in order.
• P2(CyNMe)-BF 4 1,1,1,3,3,3-hexakis(cyclohexyl(methyl)amino)-1 ⁇ 5 ,3 ⁇ 5 -diphosphazenium tetrafluoroborate
• Step 4 1,1,1,3,3,3-hexakis(cyclohexyl(methyl)amino)-1 ⁇ 5 ,3 ⁇ 5 -diphosphazenium 4-(2-(4-hydroxyphenyl)propane-2- yl) Synthesis of phenolate ion BPA adduct (hereinafter sometimes abbreviated as (P2( CyNMe )-BPA2))
• P2( CyNMe )-BPA2 phenolate ion BPA adduct
• Example 15 Synthesis of catalyst G> (Step 1: Synthesis of tetrakis[(triphenylphosphoranylidene)amino]phosphonium tetrafluoroborate (hereinafter sometimes abbreviated as P5(Ph) -BF4 ))
• Literature M. Taillefer, N. Rahier, A. Hameau and J.-N. Volle, Chem. Commun. 2006, 3238-3239; M. G. Davidson, A. E. Goeta, J. A. K. Howard , CW Lehmann, GM McIntyre and RD Price , J. Organomet.
• Step 2 Tetrakis[(triphenylphosphoranylidene)amino]phosphonium 4-(2-(4-hydroxyphenyl)propan-2-yl)phenolate BPA adduct (hereinafter P5(Ph)-BPA 1.67 and may be abbreviated))
• P5(Ph)-BF 4 0.74 g, 0.61 mmol
• K-BPA 2 potassium tert-butoxide (68 mg, 0.61 mmol) and BPA (68 mg, 0.61 mmol) in 5 mL of methanol). 278 mg, 1.22 mmol)
• the mixture was stirred at room temperature for 1 hour.
• Residual solvent in the filtrate was removed on a rotary evaporator and the solid was extracted with DCM.
• DCM in the solution was removed with a rotary evaporator, and catalyst H (sometimes abbreviated as 2-Et-1,4-Ad 2 -3-Me-imy-BPA, purity 85%) represented by the following structural formula was obtained. 670 mg of was obtained.
• Precipitated ammonium salt was removed with a filter.
• DCM was distilled off from the solution and the resulting solution was separated on a silica gel column.
• the product was eluted with a mixture of hexane and ethyl acetate (4:1 weight ratio) to give 3.2 g of a bluish yellow liquid.
• 2.5 g of the resulting liquid was then mixed with 10.3 g of acetic anhydride and 0.84 mL of 37% aqueous hydrogen chloride solution was added.
• the mixture was stirred at room temperature for 14 hours and 50 mL of diethyl ether was added.
• the organic solution layer was collected and washed twice with 2 mL of diethyl ether.
• the resulting oily substance was mixed with 20 mL of toluene and 2.0 g of mesitylamine and stirred at room temperature for 3 hours. After washing with 50 mL of anhydrous diethyl ether, 6 mL of acetic anhydride, 20 mL of toluene and 1.3 mL of 37% hydrogen chloride aqueous solution were mixed and stirred at 110° C. for 14 hours. Removal of the solvent on a rotary evaporator gave 1.4 g of white 2,4,5-Me 3 -1,3-Mes 2 -imy-Cl.
• BEMP 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine
• TMAH tetramethylammonium hydroxide
• thermoplastic resin ⁇ Example 7> 116.71 g (about 0.51 mol) of BPA and 117.95 (about 0.55 mol) of DPC were added to a 150 mL glass reactor equipped with a reactor stirrer, a reactor heating device, and a reactor pressure regulator, and the ester was A mixture was prepared by adding 3 ⁇ mol of catalyst A as an exchange catalyst to 1 mol of BPA.
• the pressure inside the glass reactor was reduced to about 100 Pa (0.75 Torr), and then the pressure was restored to atmospheric pressure with nitrogen, which was repeated three times to replace the inside of the reactor with nitrogen.
• the external temperature of the reactor was set to 220° C., and the internal temperature of the reactor was gradually increased to dissolve the mixture.
• the stirrer was rotated at 100 rpm.
• the pressure inside the reactor was increased from 101.3 kPa (760 Torr) to 13.3 kPa in absolute pressure over 40 minutes while distilling off the phenol that was a by-product of the oligomerization reaction of BPA and DPC that took place inside the reactor.
• the pressure was reduced to (100 Torr).
• the pressure in the reactor was maintained at 13.3 kPa, and transesterification was carried out for 80 minutes while further distilling off phenol.
• the temperature outside the reactor was raised to 290° C.
• the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in absolute pressure over 40 minutes, and the distilled phenol was removed from the system.
• the absolute pressure in the reactor was reduced to 30 Pa (about 0.2 Torr) to carry out a polycondensation reaction.
• the polycondensation reaction was terminated when the stirrer of the reactor reached a predetermined stirring power.
• the reaction time from the start of the reaction to the end of the reaction was measured and shown in Table 2 as the polymerization time (unit: minutes).
• Example 8 In Example 7, the same as in Example 7 except that 116.71 g (about 0.51 mol) of BPA and 117.73 g (about 0.55 mol) of DPC were added, and 2 ⁇ mol of catalyst A was added to 1 mol of BPA. Then, the polycarbonate resin was polymerized. Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 9 In Example 7, the same as in Example 7 except that 116.71 g (about 0.51 mol) of BPA and 116.85 g (about 0.55 mol) of DPC were added, and catalyst A was added so as to be 1 ⁇ mol per 1 mol of BPA. Then, the polycarbonate resin was polymerized. Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 10 ⁇ Example 10>
• 116.71 g (about 0.51 mol) of BPA and 118.28 g (about 0.55 mol) of DPC were added, and transesterification catalyst B was added so as to be 2.5 ⁇ mol with respect to 1 mol of BPA.
• Polymerization of a polycarbonate resin was carried out in the same manner as in Example 7.
• Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 11 ⁇ Example 11> In Example 7, 116.71 g (about 0.51 mol) of BPA and 118.28 g (about 0.55 mol) of DPC were added, and instead of catalyst A as a transesterification catalyst, catalyst C was added to 2.5 ⁇ mol per 1 mol of BPA. Polycarbonate resin was polymerized in the same manner as in Example 7, except that it was added to . Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 12 Polymerization of a polycarbonate resin was carried out in the same manner as in Example 7, except that 3 ⁇ mol of catalyst D was used per 1 mol of BPA as a transesterification catalyst instead of catalyst A. Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 13 a polycarbonate resin was polymerized in the same manner as in Example 7, except that 3 ⁇ mol of Catalyst E was used per 1 mol of BPA as a transesterification catalyst instead of Catalyst A. Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 14 a polycarbonate resin was polymerized in the same manner as in Example 7, except that 3 ⁇ mol of Catalyst F was used per 1 mol of BPA as a transesterification catalyst instead of Catalyst A. Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 16 Polymerization of a polycarbonate resin was carried out in the same manner as in Example 7, except that 3 ⁇ mol of catalyst G was used per 1 mol of BPA as a transesterification catalyst instead of catalyst A. Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 7 116.71 g (about 0.51 mol) of BPA and 117.73 g (about 0.55 mol) of DPC were added, and catalyst H was added instead of catalyst A as a transesterification catalyst so that 7.7 ⁇ mol was added to 1 mol of BPA.
• Polycarbonate resin was polymerized in the same manner as in Example 7, except that it was added to .
• Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 7 116.71 g (about 0.51 mol) of BPA and 117.73 g (about 0.55 mol) of DPC were added, and instead of catalyst A, catalyst I was added as a transesterification catalyst so that the amount would be 7 ⁇ mol per 1 mol of BPA.
• a polycarbonate resin was polymerized in the same manner as in Example 7, except that Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 7 116.71 g (approximately 0.51 mol) of BPA and 118.83 g (approximately 0.55 mol) of DPC were added, and Catalyst I was added as a transesterification catalyst instead of Catalyst A in an amount of 5 ⁇ mol per 1 mol of BPA.
• a polycarbonate resin was polymerized in the same manner as in Example 7, except that Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 7 116.71 g (approximately 0.51 mol) of BPA and 117.84 g (approximately 0.55 mol) of DPC were added, and Catalyst J was added as a transesterification catalyst instead of Catalyst A so as to be 7 ⁇ mol per 1 mol of BPA.
• a polycarbonate resin was polymerized in the same manner as in Example 7, except that Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 7 116.71 g (approximately 0.51 mol) of BPA and 117.73 g (approximately 0.55 mol) of DPC were added, and catalyst J was added as a transesterification catalyst instead of catalyst A so as to be 20 ⁇ mol per 1 mol of BPA.
• a polycarbonate resin was polymerized in the same manner as in Example 7, except that Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 7 116.71 g (about 0.51 mol) of BPA and 118.83 g (about 0.55 mol) of DPC were added, and instead of catalyst A as a transesterification catalyst, catalyst K was added so as to be 5 ⁇ mol per 1 mol of BPA.
• a polycarbonate resin was polymerized in the same manner as in Example 7, except that Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 7 116.71 g (approximately 0.51 mol) of BPA and 118.83 g (approximately 0.55 mol) of DPC were added, and Catalyst L was added as a transesterification catalyst in place of Catalyst A so as to be 5 ⁇ mol per 1 mol of BPA.
• a polycarbonate resin was polymerized in the same manner as in Example 7, except that Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Example 7 116.71 g (about 0.51 mol) of BPA and 115.43 g (about 0.54 mol) of DPC were added, and instead of catalyst A as a transesterification catalyst, catalyst M was added so as to be 10 ⁇ mol per 1 mol of BPA.
• a polycarbonate resin was polymerized in the same manner as in Example 7, except that Table 2 shows the polymerization time and the evaluation results of the obtained polycarbonate resin.
• Table 1 shows that the catalyst compounds of the present invention obtained in Examples 1, 2, 4 to 6 and 15 have low decomposition rates and excellent thermal stability.
• catalysts J and M of Comparative Examples 3 and 12 had high decomposition rates and poor thermal stability.
• Comparative Example 7 the same catalyst as in Comparative Example 6 was used, but 5 ⁇ mol, which was less than in Comparative Example 6, and the content of the specific by-product tended to be improved compared to Comparative Example 6, but the polymerization time was longer.
• Comparative Example 8 contains less specific by-products at the same level as in Examples, but the polymerization time is long.
• Comparative Example 9 the same catalyst as in Comparative Example 8 was used in an amount of 20 ⁇ mol, which was more than in Comparative Example 8, but no improvement in reactivity was observed, and the content of specific by-products tended to increase.
• Comparative Examples 10, 11 and 12 used a larger amount of catalyst than the Examples, but the reaction time was longer and the specific by-product content was also higher.

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