Polycarbonate manufacturing method

Abstract

A method for producing a polycarbonate, wherein a dihydroxy component which is composed of at least one nonaromatic dihydroxy compound that is selected from among alicyclic dihydroxy compounds (which may contain an ether oxygen atom) and the like, or a mixture of the nonaromatic dihydroxy compound and an aromatic dihydroxy compound, and a specific fluorine-containing carbonate component which is selected from among compounds represented by formula (1) and the like, are reacted with each other in the presence of a condensation catalyst, and a thus-obtained prepolymer is subjected to solid-phase polymerization.

Description

[Technical Field]

[0001] This invention relates to a method for producing polycarbonate. This application claims priority based on Japanese Patent Application No. 2021-85297, filed in Japan on May 20, 2021, and Japanese Patent Application No. 2021-176302, filed in Japan on October 28, 2021, and the contents thereof are incorporated herein by reference. [Background technology]

[0002] Polycarbonate is an engineering plastic with excellent heat resistance, impact resistance, and transparency, and is widely used in many fields. Polycarbonate is generally manufactured using raw materials derived from petroleum resources. However, in recent years, concerns have arisen about the depletion of petroleum resources, and there is a growing demand for the use of raw materials derived from biomass resources such as plants.

[0003] As an example of polycarbonate made from raw materials derived from biomass resources, polycarbonate made from plant-derived isosorbide is well known. A known method for producing polycarbonate using isosorbide involves melt polycondensation of diphenyl carbonate, isosorbide, and, if necessary, other dihydroxy compounds (transesterification method) (Patent Document 1).

[0004] On the other hand, a method has been proposed for producing aromatic polycarbonates in which a specific fluorine-containing carbonate is reacted with an aromatic dihydroxy compound, and the resulting prepolymer is solid-state polymerized (Patent Document 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2012 / 144573 [Patent Document 2] International Publication No. 2014 / 171367 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, the method of melt polycondensation of diphenyl carbonate and isosorbide, etc., has the following problems. • Transesterification reactions require high temperatures. For example, even with a catalyst, polycondensation occurs at reaction temperatures of 240°C or higher. • Even when the reaction is carried out at high temperatures, the molecular weight does not increase, and high molecular weight products cannot be obtained. • High temperatures during polycondensation cause the polycarbonate to decompose and become discolored. The same problems as described above arise when using alicyclic dihydroxy compounds or linear or branched aliphatic dihydroxy compounds instead of isosorbide. Patent Document 2 does not consider using dihydroxy compounds other than aromatic dihydroxy compounds as the dihydroxy compound.

[0007] The present invention provides a method for producing high molecular weight polycarbonate using non-aromatic dihydroxy compounds as raw materials at a relatively low temperature. [Means for solving the problem]

[0008] The present invention has the following aspects. [1] The following dihydroxy component and the following fluorine-containing carbonate component are reacted in the presence of a condensation catalyst. A method for producing polycarbonate, comprising heating the obtained prepolymer at a temperature below its melting point and solid-phase polymerizing the prepolymer while discharging the by-product fluorine-containing alcohol from the system. Dihydroxy component: at least one non-aromatic dihydroxy compound selected from the group consisting of alicyclic dihydroxy compounds and linear or branched aliphatic dihydroxy compounds, or a mixture of the non-aromatic dihydroxy compound and an aromatic dihydroxy compound, wherein some of the carbon atoms of the alicyclic dihydroxy compound may be substituted with oxygen atoms, and some of the carbon atoms of the linear or branched aliphatic dihydroxy compound may be substituted with oxygen atoms. Fluorine-containing carbonate component: at least one compound selected from the group consisting of the compound represented by the following formula (1), the compound represented by the following formula (2), the compound represented by the following formula (3), and the compound represented by the following formula (4).

[0009]

Chemical formula

[0010] However, R , f , 2 , 1 , , 2 , 6 , 4 , , 3 , 1 , 2 , 4 , 3 , 5 , 2 , 1 , 1 , , 3 , 1 , , 3 , 1 , 6 , 3 , , f , 3 is a group represented by CA 1 B 1 R 4 Two R 1 may be the same or different, R 2 is a group represented by CA 2 B 2 R 5 Two R 2 may be the same or different, R 3 is a hydrogen atom or a group represented by CA 3 B 3 R 6 Two R 3 may be the same or different, A 1 ~A 3 are each independently a hydrogen atom, a fluorine atom or R f and B 1 ~B 3 are each independently a hydrogen atom, a fluorine atom or R f and R 4 ~R 6Each of them independently contains a fluorine atom, R f OR f And, R f This is a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroaryl group having 6 to 10 carbon atoms, and in the fluoroalkyl group having 1 to 12 carbon atoms, some of the carbon atoms may be substituted with oxygen atoms.

[0011] [ka]

[0012] However, R 1 CA 1 B 1 R 4 It is a base represented by, R 2 CA 2 B 2 R 5 It is a base represented by, R 3 is a hydrogen atom or CA 3 B 3 R 6 It is a base represented by, R 7 This is a perfluoroalkylene group having 1 to 5 carbon atoms, and the said perfluoroalkylene group having 1 to 5 carbon atoms may have some of its carbon atoms substituted with oxygen atoms. A 1 ~A 3 These are, independently, a hydrogen atom, a fluorine atom, or R f And, B 1 ~B 3 These are, independently, a hydrogen atom, a fluorine atom, or R f And, R 4 ~R 6 Each of them independently contains a fluorine atom, R f OR f And, R fThis is a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroaryl group having 6 to 10 carbon atoms, and in the fluoroalkyl group having 1 to 12 carbon atoms, some of the carbon atoms may be substituted with oxygen atoms.

[0013] [ka]

[0014] However, R 7 This is a perfluoroalkylene group having 1 to 5 carbon atoms, and has two R 7 These may be the same or different, and the perfluoroalkylene group having 1 to 5 carbon atoms may have some of its carbon atoms substituted with oxygen atoms.

[0015] [ka]

[0016] However, R 9 ~R 13 Each is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, and two R 9 , two R 10 , two R 11 , two R 12 and two R 13 These may be the same or different, and each molecule may have at least one fluorine atom, and the carbon-1 to carbon-6 fluoroalkyl group may have some of its carbon atoms substituted with oxygen atoms. [2] The method for producing the non-aromatic dihydroxy compound according to [1], comprising isosorbide. [3] The method for producing the non-aromatic dihydroxy compound according to [2], wherein the proportion of isosorbide to the total non-aromatic dihydroxy compound is 50 mol% or more. [4] The manufacturing method according to any one of [1] to [3], wherein the dihydroxy component is a mixture of the non-aromatic dihydroxy compound and the aromatic dihydroxy compound. [5] The manufacturing method according to any one of [1] to [4], wherein the weight-average molecular weight of the prepolymer is 500 to 15,000. [6] The manufacturing method according to any one of [1] to [5], wherein the heating temperature when solid-phase polymerization of the prepolymer is 200°C or less. [7] The manufacturing method according to any one of [1] to [6], wherein the weight-average molecular weight of the polycarbonate is 10,000 to 100,000. [8] The manufacturing method according to any one of [1] to [7], wherein the number of carbon atoms in the alicyclic dihydroxy compound is preferably 2 to 20; more preferably 3 to 16; even more preferably 4 to 13; and particularly preferably 5 to 10. [9] The production method according to any one of [1] to [8], wherein the number of carbon atoms in the linear or branched aliphatic dihydroxy compound is preferably 2 to 20; more preferably 3 to 16; even more preferably 4 to 13; and particularly preferably 5 to 10.

[10] The aromatic dihydroxy compound preferably has 4 to 20 carbon atoms; more preferably 6 to 19 carbon atoms; even more preferably 8 to 18 carbon atoms; and particularly preferably 10 to 17 carbon atoms. The manufacturing method according to any one of [1] to [9].

[11] The method for producing the non-aromatic dihydroxy compound according to any one of [1] to

[10] , wherein the proportion of isosorbide to the total dihydroxy component is preferably 40 to 95 mol%; more preferably 50 to 90 mol%.

[12] The method for producing a product according to any one of [1] to

[11] , wherein the dihydroxy component is isosorbide, or a mixture of isosorbide and 1,4-cyclohexanedimethanol or bisphenol A.

[13] The fluorine-containing carbonate component is preferably at least one selected from the group consisting of bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, bis(perfluoro(t-butyl)) carbonate, and bis(2,2,3,3,4,4,5,5,6,6-decafluorocyclohexyl) carbonate; bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate is more preferred, as described in any one of [1] to

[12] .

[14] The condensation catalyst is preferably a tertiary amine; more preferably at least one selected from the group consisting of triethylamine, tripropylamine, tributylamine, triisoamylamine, trihexylamine, triheptylamine, trioctylamine, and toridodecylamine; even more preferably at least one selected from the group consisting of triethylamine and tributylamine; the manufacturing method according to any one of [1] to

[13] .

[15] The reaction to obtain the prepolymer is carried out in a solvent, wherein the solvent is preferably at least one selected from the group consisting of acetonitrile, N,N-dimethylformamide (DMF), 1,4-dioxane, dichloromethane, chloroform, and chlorobenzene; more preferably acetonitrile, DMF, and chlorobenzene; and even more preferably acetonitrile, according to any one of [1] to

[14] .

[16] The weight-average molecular weight of the prepolymer is preferably 500 to 15,000; more preferably 500 to 10,000; particularly preferably 1,000 to 10,000; the manufacturing method according to any one of [1] to

[15] .

[17] The weight-average molecular weight of the polycarbonate is preferably 10,000 to 100,000; more preferably 15,000 to 70,000; particularly preferably 20,000 to 60,000; the manufacturing method according to any one of [1] to

[16] .

[18] A method for producing a solid prepolymer according to any one of [1] to

[17] , wherein the dihydroxy component and the fluorine-containing carbonate component are reacted in the presence of the condensation catalyst, and then the solvent and the by-product fluorine-containing alcohol are removed by distillation.

[19] The manufacturing method according to any one of [1] to

[18] , wherein the heating temperature when solid-phase polymerization of the prepolymer is preferably 200°C or less; more preferably 40°C or more and 200°C or less; and even more preferably 90°C or more and 195°C or less.

[20] A method for producing the prepolymer according to any one of [1] to

[19] , wherein heating is started at a temperature of around 40 to 110°C, the temperature is gradually increased, and finally the temperature is heated to 180 to 200°C.

[21] The heating time for solid-phase polymerization of the prepolymer is preferably 1 to 48 hours; more preferably 2 to 36 hours; and particularly preferably 3 to 24 hours, according to the manufacturing method according to any one of [1] to

[20] .

[22] The manufacturing method according to any one of [1] to

[21] , wherein the pressure when solid-phase polymerization of the prepolymer is preferably 13 kPa (absolute pressure) (100 torr (absolute pressure)) or less; more preferably 1.3 kPa (absolute pressure) (10 torr (absolute pressure)) or less; and particularly preferably 0.67 kPa to 0.013 kPa (absolute pressure) (5 to 0.1 torr (absolute pressure)). Use of polycarbonate obtained by the manufacturing method described in any one of items

[23] [1] to

[22] in the manufacture of optical components (lenses, optical fibers, films, LCD backlight diffusers, photoreceptors, etc.), DVD / CD discs, electronic component housings (mobile phones, etc.), windows for transport equipment, transparent roofing materials, windshields, screens, bulletproof windows, tableware, suitcases, or helmets.

[24] Fluorine-containing biscarbonate represented by the following formula (m1).

[0017] [ka]

[0018] However, R 1 CA 1 B 1 R 4 It is a group represented by two R 1 They may be the same or different. R 2 CA 2 B 2 R 5 It is a group represented by two R 2 They may be the same or different. R 3 is a hydrogen atom or CA 3 B 3 R 6 It is a group represented by two R 3 They may be the same or different. A 1~A 3 These are, independently, a hydrogen atom, a fluorine atom, or Rf, B 1 ~B 3 These are, independently, a hydrogen atom, a fluorine atom, or R f And, R 4 ~R 6 Each of them independently contains a fluorine atom, R f OR f And, R f This is a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroaryl group having 6 to 10 carbon atoms, and in the fluoroalkyl group having 1 to 12 carbon atoms, some of the carbon atoms may be substituted with oxygen atoms. R a This is a residue obtained by removing two hydroxyl groups from an alicyclic dihydroxy compound or a linear or branched aliphatic dihydroxy compound, wherein the alicyclic dihydroxy compound may have some carbon atoms substituted with oxygen atoms, and the linear or branched aliphatic dihydroxy compound may have some carbon atoms substituted with oxygen atoms.

[25] A method for producing a fluorine-containing biscarbonate according to

[24] , comprising reacting the following dihydroxy component with the following fluorine-containing carbonate component in the presence of a condensation catalyst, and then distilling off the by-product fluorine-containing alcohol. Dihydroxy component: At least one selected from the group consisting of alicyclic dihydroxy compounds and linear or branched aliphatic dihydroxy compounds, wherein the alicyclic dihydroxy compound may have some carbon atoms substituted with oxygen atoms, and the linear or branched aliphatic dihydroxy compound may have some carbon atoms substituted with oxygen atoms. Fluorine-containing carbonate components: Compounds represented by the following formula (1).

[0019] [ka]

[0020] However, R 1 CA 1 B 1R 4 is a group represented by, and the two Rs 1 may be the same or different, R 2 is a group represented by CA 2 B 2 R 5 is a group represented by, and the two Rs 2 may be the same or different, R 3 is a hydrogen atom or a group represented by CA 3 B 3 R 6 is a group represented by, and the two Rs 3 may be the same or different, A 1 ~A 3 are each independently a hydrogen atom, a fluorine atom or R f and, B 1 ~B 3 are each independently a hydrogen atom, a fluorine atom or R f and, R 4 ~R 6 are each independently a fluorine atom, R f or OR f and, R f is a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroaryl group having 6 to 10 carbon atoms, and in the fluoroalkyl group having 1 to 12 carbon atoms, some of the carbon atoms may be substituted with oxygen atoms.

[26] A fluorine-containing biscarbonate represented by the following formula.

[0021]

Chemical formula

[0022]

[27] A method for producing the fluorine-containing biscarbonate according to

[26] , which comprises reacting isosorbide and bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate in the presence of a condensation catalyst and then distilling off the by-produced fluorine-containing alcohol.

Advantages of the Invention

[0023] According to the present invention's method for producing polycarbonate, high molecular weight polycarbonate can be produced at a relatively low temperature using a non-aromatic dihydroxy compound as a raw material. [Modes for carrying out the invention]

[0024] In this specification, the compound represented by formula (1) will be referred to as compound (1). Other compounds represented by other formulas will be referred to similarly. The meanings and definitions of terms used in this invention are as follows: "Etheric oxygen atom" refers to an oxygen atom that forms an ether bond. A "prepolymer" is a solid intermediate product obtained by stopping the condensation reaction between the dihydroxy component and the fluorine-containing carbonate component of the raw materials at an appropriate point. It refers to a polycarbonate with a lower weight-average molecular weight than the high molecular weight polycarbonate obtained by solid-phase polymerization. "Solid-phase polymerization" refers to a polymerization method that obtains high-molecular-weight polycarbonate by polymerizing a prepolymer while maintaining its solid state. The "melting temperature of the prepolymer" refers to the temperature at which the prepolymer melts, becomes liquid, or softens. This temperature is determined by heating the prepolymer to a predetermined temperature and visually observing when it becomes liquid or softens. "Weight-average molecular weight" and "number-average molecular weight" are values ​​converted to standard polystyrene, measured by gel permeation chromatography (GPC). The "glass transition temperature" is the temperature measured by differential scanning calorimetry (DSC) as the intermediate glass transition temperature, in accordance with JIS K 7121:1987. "Crystallization" refers to the process of increasing the crystallinity of a polymer. A "perfluoroalkylene group" refers to an alkylene group in which all hydrogen atoms are replaced by fluorine atoms. "Fluoroalkyl group" refers to a group in which some or all of the hydrogen atoms of an alkyl group are replaced by fluorine atoms. The "~" symbol indicating a numerical range means that the numbers before and after it are included as the lower and upper limits, respectively.

[0025] A method for producing polycarbonate according to one aspect of the present invention comprises the following steps a and b. Step a: A step of reacting a specific dihydroxy component with a specific fluorine-containing carbonate component in the presence of a condensation catalyst to obtain a prepolymer. Step b: A step to obtain polycarbonate by solid-phase polymerization of the prepolymer.

[0026] (Dihydroxy component) The dihydroxy component is at least one non-aromatic dihydroxy compound selected from the group consisting of alicyclic dihydroxy compounds (which may contain an etheric oxygen atom) and linear or branched aliphatic dihydroxy compounds (which may contain an etheric oxygen atom), or a mixture of this non-aromatic dihydroxy compound and an aromatic dihydroxy compound.

[0027] Examples of alicyclic dihydroxy compounds (which may contain an etheric oxygen atom) include compounds having an alicyclic structure (which may contain an etheric oxygen atom) and two hydroxyl groups directly or via linking groups attached to its ring skeleton. Examples of linking groups include alkylene groups (methylene group, 1,1-dimethylethylene group, 2,2-dimethylpropylene group, etc.). The alicyclic structure may be monocyclic or polycyclic. The rings constituting the alicyclic structure (or, in the case of polycyclic, each of the multiple rings constituting the alicyclic structure) may be, for example, 4- to 7-membered rings. The number of etheric oxygen atoms that the alicyclic structure may contain may be, for example, 1 to 2 per ring constituting the alicyclic structure. Other substituents may be attached to the cyclic skeleton of the alicyclic structure. Examples of other substituents include alkyl groups (methyl group, ethyl group, etc.) and alkenyl groups (vinyl group, allyl group, etc.).

[0028] Specific examples of alicyclic dihydroxy compounds (which may contain an etheric oxygen atom) include the following: Cycloalkane dimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, pentacyclodecanepentadimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, and 1,3-adamantanedimethanol; cycloalkanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, tricyclodecanediol, pentacyclodecanediol, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol, 2,3-norbornanediol, 2,5-norbornanediol, and 1,3-adamantanediol; isosorbides, dioxaneglycols, spiroglycols, etc.

[0029] Examples of linear or branched aliphatic dihydroxy compounds (which may contain an etheric oxygen atom) include compounds having an alkylene group (which may contain an etheric oxygen atom) and two hydroxyl groups bonded to the alkylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is, for example, 1 to 10. The number of etheric oxygen atoms that the alkylene group may contain is, for example, 1 to 3.

[0030] Specific examples of linear or branched aliphatic dihydroxy compounds (which may contain an etheric oxygen atom) are listed below. Alkanediols such as ethylenediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol; polyethylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol.

[0031] As a non-aromatic dihydroxy compound, isosorbide is preferred due to the availability of plant-derived raw materials. Isosorbide may be used in combination with other non-aromatic dihydroxy compounds. As the other non-aromatic dihydroxy compounds, alicyclic dihydroxy compounds other than isosorbide (however, they may contain etheric oxygen atoms) are preferred because they result in a relatively high glass transition temperature of the prepolymer and facilitate solid-phase polymerization, cycloalkanedimethanol or cycloalkanediol are more preferred, and cycloalkanedimethanol is even more preferred.

[0032] The proportion of isosorbide to the total non-aromatic dihydroxy compound is preferably 50 mol% or more, more preferably 80 mol% or more, and may be 100 mol%. If the proportion of isosorbide is above the lower limit mentioned above, the proportion of plant-derived components can be increased.

[0033] When isosorbide is used in combination with other non-aromatic dihydroxy compounds, the proportion of isosorbide to the total non-aromatic dihydroxy compounds is preferably 50 mol% or more, more preferably 70 mol% or more, and preferably 95 mol% or less. If the proportion of isosorbide is above the lower limit, the proportion of plant-derived components can be increased, and if it is below the upper limit, the moldability is improved.

[0034] When the dihydroxy component is a mixture of non-aromatic dihydroxy compounds and aromatic dihydroxy compounds, the performance of the polycarbonate (heat resistance, rigidity, toughness, etc.) tends to be superior compared to when the dihydroxy component consists solely of non-aromatic dihydroxy compounds. As the aromatic dihydroxy compound, an aromatic compound having two phenolic hydroxyl groups is preferred.

[0035] Specific examples of aromatic dihydroxy compounds include the following: 2,2-bis(4-hydroxyphenyl)propane (hereinafter also referred to as bisphenol A), 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (hereinafter also referred to as bisphenol AF), hydroquinone, 4,4'-dihydroxybiphenyl, 9,9-bis(4-hydroxyphenyl)fluorene, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)thioether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, etc.

[0036] As for the aromatic dihydroxy compound, bisphenol A or bisphenol AF is preferred, with bisphenol A being particularly preferred, due to the ease of obtaining the raw materials and the usefulness of polycarbonate.

[0037] When the dihydroxy component is a mixture of a non-aromatic dihydroxy compound and an aromatic dihydroxy compound, and the non-aromatic dihydroxy compound contains isosorbide, the proportion of isosorbide to the total dihydroxy component is preferably 40 to 95 mol%, and more preferably 50 to 90 mol%. If the proportion of isosorbide is above the lower limit, the proportion of plant-derived components can be increased, and if it is below the upper limit, the moldability is improved.

[0038] In a preferred embodiment, the dihydroxy component is isosorbide.

[0039] In another preferred embodiment, the dihydroxy component is a mixture of isosorbide and an aromatic dihydroxy compound. Preferably, the aromatic dihydroxy compound is bisphenol A or bisphenol AF, and particularly preferably, the aromatic dihydroxy compound is bisphenol A. In this embodiment, the proportion of isosorbide to the total dihydroxy component is preferably 40 to 95 mol%, and more preferably 50 to 90 mol%.

[0040] In another preferred embodiment, the dihydroxy component is a mixture of isosorbide and an alicyclic dihydroxy compound that does not contain an etheric oxygen atom. In particular, the alicyclic dihydroxy compound is cycloalkanedimethanol, and the alicyclic dihydroxy compound is 1,4-cyclohexanedimethanol. In this embodiment, the proportion of isosorbide to the total dihydroxy component is preferably 40 to 95 mol%, and more preferably 50 to 90 mol%.

[0041] In another preferred embodiment, the dihydroxy component is a mixture of isosorbide, an alicyclic dihydroxy compound that does not contain an etheric oxygen atom, and an aromatic dihydroxy compound. In particular, the aromatic dihydroxy compound is bisphenol A or bisphenol AF and the alicyclic dihydroxy compound is cycloalkanedimethanol, and the aromatic dihydroxy compound is bisphenol A and the alicyclic dihydroxy compound is 1,4-cyclohexanedimethanol. In this embodiment, the proportion of isosorbide to the total dihydroxy component is preferably 40 to 95 mol%, and more preferably 50 to 90 mol%. The proportion of aromatic dihydroxy compound to the total dihydroxy component is preferably 5 to 60 mol%, and more preferably 10 to 50 mol%.

[0042] (Fluorine carbonate component) The fluorine-containing carbonate component is at least one compound selected from the group consisting of compound (1), compound (2), compound (3), and compound (4).

[0043] [ka]

[0044] However, R 1 CA 1 B 1 R 4 It is a group represented by two R 1 They may be the same or different, R2 CA 2 B 2 R 5 It is a group represented by two R 2 They may be the same or different, R 3 is a hydrogen atom or CA 3 B 3 R 6 It is a group represented by two R 3 They may be the same or different, A 1 ~A 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f B 1 ~B 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f And R 4 ~R 6 is a fluorine atom, R f OR f And R f This is a fluoroalkyl group having 1 to 12 carbon atoms (which may include an etheric oxygen atom) or a fluoroaryl group having 6 to 10 carbon atoms.

[0045] [ka]

[0046] However, R 1 CA 1 B 1 R 4 It is a group represented by R 2 CA 2 B 2 R 5 It is a group represented by R 3 is a hydrogen atom or CA 3 B 3 R 6 It is a group represented by R 7 A is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may also contain an etheric oxygen atom), and 1 ~A 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f B 1 ~B 3These are, respectively, a hydrogen atom, a fluorine atom, or R f And R 4 ~R 6 is a fluorine atom, R f OR f And R f This is a fluoroalkyl group having 1 to 12 carbon atoms (which may include an etheric oxygen atom) or a fluoroaryl group having 6 to 10 carbon atoms.

[0047] [ka]

[0048] However, R 7 This is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may also contain an etheric oxygen atom), and has two R 7 They may be the same or different.

[0049] [ka]

[0050] However, R 9 ~R 13 Each of these is a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms (however, it may also contain an etheric oxygen atom), and the two R 9 , two R 10 , two R 11 , two R 12 and two R 13 Each of these elements may be identical or different, and each molecule contains at least one fluorine atom.

[0051] Specific examples of fluorinated carbonate components include the following: Bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, ((CF3CF2)(CF3)CHO)2CO, ((CF3CF2)2CHO)2CO, bis(perfluoro(t-butyl)) carbonate, bis(2,2,3,3,4,4,5,5-octafluorocyclopentyl) carbonate, bis(2,2,3,3,4,4,5,5,6,6-decafluorocyclohexyl) carbonate, bis(perfluorophenyl) carbonate, bis(m-trifluoromethylphenyl) carbonate, bis(o-trifluoromethylphenyl) carbonate, bis(p-trifluoromethylphenyl) carbonate, etc.

[0052] As the fluorine-containing carbonate component, bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, bis(perfluoro(t-butyl)) carbonate, or bis(2,2,3,3,4,4,5,5,6,6-decafluorocyclohexyl) carbonate are preferred from the viewpoint of transesterification reaction rate.

[0053] As the fluorinated carbonate component, bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate is particularly preferred due to its availability as a raw material, ease of manufacture, and the ability to produce high molecular weight polycarbonates.

[0054] The fluorine-containing carbonate component is preferably obtained by a reaction using a fluorine-containing alcohol as a starting material. As the fluorine-containing alcohol, at least one selected from the group consisting of compound (5) and compound (6) is preferred.

[0055] [ka]

[0056] However, R 1 CA 1 B 1 R 4 It is a group represented by R 2 CA2 B 2 R 5 It is a group represented by R 3 is a hydrogen atom or CA 3 B 3 R 6 It is a group represented by R 7 A is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may also contain etheric oxygen), and 1 ~A 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f B 1 ~B 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f And R 4 ~R 6 is a fluorine atom, R f OR f And R f This is a fluoroalkyl group having 1 to 12 carbon atoms (which may include an etheric oxygen atom) or a fluoroaryl group having 6 to 10 carbon atoms.

[0057] As for fluorine-containing alcohols, those with a higher degree of acid dissociation than aromatic dihydroxy compounds are preferred in order to improve the transesterification reaction rate. Therefore, secondary or tertiary fluorine-containing alcohols in which a fluoroalkyl group is directly bonded to the α-carbon of the hydroxyl group (hereinafter referred to as α-carbon) are preferred. However, alcohols in which a fluorine atom is directly bonded to the α-carbon are undesirable because they are prone to decomposition reactions via de-HF reactions.

[0058] As for compound (5), the degree of acid dissociation of the fluorine-containing alcohol increases as the number of fluoroalkyl groups bonded to the α-carbon increases, 3 CA 3 B 3 R 6 A group represented by , i.e., a tertiary fluorine-containing alcohol, is preferred. From the viewpoint of the stability of the fluorine-containing carbonate component, R 3 A hydrogen atom is preferred, i.e., a secondary fluorine-containing alcohol is preferred.

[0059] The pKa of a fluorine-containing alcohol can be used as a measure of the degree of acid dissociation. The pKa of the fluorinated alcohol is preferably 12 or less, more preferably 11 or less, and particularly preferably 10 or less, from the viewpoint of improving the transesterification reaction rate. The pKa of the fluorinated alcohol is preferably 5 or more from the viewpoint of raw material availability and ease of production of the fluorinated carbonate component.

[0060] The carbon number of the fluorinated alcohol is preferably 2 to 10. If the carbon number of the fluorinated alcohol is 2 or more, a stable fluorinated alcohol can be selected in which the fluorine atom is not directly bonded to the α-position of the hydroxyl group. If the carbon number of the fluorinated alcohol is 10 or less, the boiling point will be such that the fluorinated alcohol that dissociates during the transesterification reaction can be easily removed under mild conditions, thus eliminating the need to apply high temperatures during the transesterification reaction and enabling the production of high-quality polycarbonate.

[0061] Specific examples of fluorine-containing alcohols include the following: 1,1,1,3,3,3-Hexafluoroisopropanol (pKa: 9.4), (CF3CF2)(CF3)CHOH (pKa: 9.5), (CF3CF2)2CHOH (pKa: 10.6), perfluoro(t-butyl) alcohol (pKa: 5.3), 2,2,3,3,4,4,5,5-Octafluorocyclopentanol, 2,2,3,3,4,4,5,5,6,6-Decafluorocyclohexanol, etc.

[0062] As for fluorine-containing alcohols, 1,1,1,3,3,3-hexafluoroisopropanol, perfluoro(t-butyl) alcohol, or 2,2,3,3,4,4,5,5,6,6-decafluorocyclohexanol are preferred from the viewpoint of acid dissociation degree.

[0063] As a fluorinated alcohol, 1,1,1,3,3,3-hexafluoroisopropanol is particularly preferred due to its availability and ease of production of the fluorinated carbonate component.

[0064] One method for producing fluorine-containing carbonate components is to react a fluorine-containing alcohol with phosgenes, dialkyl carbonates, compound (7), etc.

[0065] [ka]

[0066] However, X 11 ~X 13 These are either a hydrogen atom or a halogen atom, and X 11 ~X 13 At least one of them is a halogen atom, X 14 ~X 16 These are either a hydrogen atom or a halogen atom, and X 14 ~X 16 At least one of them is a halogen atom. 11 ~X 16 It is preferable that all of the atoms are halogen atoms, more preferably that they are all fluorine atoms or chlorine atoms, and particularly preferable that they are all chlorine atoms, since chloroform can be obtained as a by-product.

[0067] As a specific method for obtaining fluorinated carbonate components using a secondary fluorinated alcohol with a high degree of acid dissociation as a starting material, the reaction with phosgenes is preferred in terms of yield, and the reaction with triphosgene is more preferred in terms of ease of handling. In the presence of a base catalyst, a fluorine-containing alcohol and triphosgene can be reacted in a solvent. Toluene is preferred as the solvent because it is easy to purify. As the base catalyst, at least one selected from the group consisting of tertiary amines, alkali metal hydrides, alkaline earth metal hydrides, alkali metals, and alkaline earth metals is preferred. The reaction temperature is preferably -50 to 60°C.

[0068] (Condensation catalyst) Examples of condensation catalysts include basic transesterification catalysts. Examples of basic transesterification catalysts include nitrogen-containing compounds, alkali metal compounds, and alkaline earth metal compounds. Examples of nitrogen-containing compounds include amines, quaternary ammonium hydroxides, and salts of amines. Examples of alkali metal compounds or alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals. The condensation catalyst may be used individually or in combination of two or more types. As condensation catalysts, amines are preferred due to their high polymerization activity and excellent applicability to solution polymerization for producing prepolymers.

[0069] Specific examples of nitrogen-containing compounds include tertiary amines (triethylamine, tripropylamine, tributylamine, triisoamylamine, trihexylamine, triheptylamine, trioctylamine, toridodecylamine, etc.), secondary amines (diethylamine, dibutylamine, etc.), primary amines (propylamine, butylamine, etc.), imidazoles (2-methylimidazole, 2-phenylimidazole, benzimidazole, etc.), and quaternary ammonium hydroxides having alkyl and / or aryl groups (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc.).

[0070] Specific examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenylborohydrate, sodium phenylborohydrate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium phenyl phosphate, sodium gluconate, disodium salts of bisphenol A (disodium, dipotassium, 2cesium, and 2lithium salts), and sodium, potassium, cesium, and lithium salts of phenol.

[0071] Specific examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenylphosphate.

[0072] (Step a) A prepolymer is obtained by reacting a dihydroxy component with a fluorine-containing carbonate component in the presence of a condensation catalyst. Specifically, for example, a dihydroxy component and a fluorine-containing carbonate component are reacted in a solvent in the presence of a condensation catalyst, and then the solvent and the by-product fluorine-containing alcohol are removed by distillation to obtain a solid prepolymer. It is preferable to dry the prepolymer at a temperature below its glass transition temperature.

[0073] Examples of solvents include acetonitrile, N,N-dimethylformamide (DMF), 1,4-dioxane, dichloromethane, chloroform, and chlorobenzene. As solvents, acetonitrile, DMF, and chlorobenzene are preferred from the viewpoint of solubility of the raw materials.

[0074] In step a, the molar ratio of the fluorinated carbonate component to the dihydroxy component (fluorinated carbonate component / dihydroxy component) is preferably 1 / 1 to 2 / 1, more preferably 1 / 1 to 1.3 / 1, and particularly preferably 1.02 / 1 to 1.2 / 1. If the molar ratio of the fluorinated carbonate component to the dihydroxy component is within the above range, it is easy to obtain a prepolymer having constituent units derived from the fluorinated carbonate component at its ends. As will be described later, a prepolymer having constituent units derived from the fluorinated carbonate component at its ends is prone to solid-phase polymerization without crystallization. Furthermore, solid-phase polymerization proceeds even at temperatures below the glass transition temperature of the prepolymer.

[0075] The weight-average molecular weight of the prepolymer is preferably 500 to 15,000, more preferably 500 to 10,000, and particularly preferably 1,000 to 10,000. If the weight-average molecular weight of the prepolymer is within this range, the prepolymer will be in a powder state and solid-phase polymerization in step b will proceed easily.

[0076] The glass transition temperature of the prepolymer is preferably 60°C or higher, more preferably 70°C or higher, and particularly preferably 80°C or higher. Furthermore, the glass transition temperature of the prepolymer is preferably 160°C or lower. If the glass transition temperature of the prepolymer is above the lower limit and below the upper limit, the prepolymer will not melt, and solid-phase polymerization in step b will proceed at a low temperature.

[0077] The molar ratio (fluorine-containing alkoxy end groups / hydroxyl groups) of the prepolymer obtained in step a, which is encapsulated by the fluorine-containing carbonate component, is preferably 0.8 / 1 to 1.4 / 1, more preferably 0.9 / 1 to 1.3 / 1, and particularly preferably 0.95 / 1 to 1.25 / 1. If the content of fluorine-containing alkoxy end groups is above the lower limit, it is possible to suppress the high concentration of hydroxyl groups at the ends of the polycarbonate obtained by solid-phase polymerization in step b. If the content of fluorine-containing alkoxy end groups is below the upper limit, it is easy to obtain polycarbonate with a sufficiently high molecular weight. In this specification, the above molar ratio at the end groups of a polymer (including prepolymers and high molecular weight polycarbonates) is the 1 Analysis by H-NMR is preferable. 1 The 1H-NMR analysis method is as described in the examples in International Publication No. 2014 / 171367.

[0078] The prepolymer obtained in step a is usually obtained in solution because a solvent is used during manufacturing. Therefore, the solvent and by-product fluorine-containing alcohol are removed by distillation to isolate the solid prepolymer. It is preferable to remove any remaining solvent, etc., by vacuum drying the prepolymer at a low temperature. The prepolymer may be in a state such as powder or candy. A powder state is preferred because it facilitates solid-phase polymerization in step b. Powdered prepolymers can be obtained, for example, by pulverizing the solid prepolymer obtained as described above. Various known methods can be used for pulverization, such as mechanical grinding or mechanical grinding under freezing conditions.

[0079] The average particle size of the powdered prepolymer is preferably 0.1 μm to 1 mm, more preferably 1 μm to 500 μm, and particularly preferably 3 μm to 200 μm. If the average particle size is within this range, the powdered prepolymer can be obtained with simple operations. Furthermore, solid-phase polymerization in step b proceeds more easily.

[0080] (Step b) Without going through a crystallization process for the prepolymer, the prepolymer is heated at a temperature below its melting point, and the prepolymer is solid-phase polymerized while the by-product fluorine-containing alcohol is discharged from the system to obtain polycarbonate.

[0081] The heating temperature is below the melting temperature of the prepolymer, preferably 200°C or lower, and more preferably 195°C or lower. If the heating temperature is below the melting temperature, the reaction proceeds in the solid phase. In particular, if the heating temperature is 200°C or lower, discoloration of the carbonate due to heat can be suppressed. The heating temperature is preferably 40°C or higher, and more preferably 90°C or higher. If the heating temperature is above the lower limit mentioned above, the reaction proceeds easily, and the productivity of polycarbonate is high.

[0082] In step b, it is preferable to start heating at a temperature of around 40-110°C, gradually increase the temperature, and finally reach a temperature of 180-200°C. By heating the prepolymer in this way, solid-phase polymerization proceeds easily, and high molecular weight polycarbonate with suppressed discoloration is obtained. In addition, the productivity of polycarbonate is high.

[0083] The heating time is preferably 1 to 48 hours, more preferably 2 to 36 hours, and particularly preferably 3 to 24 hours. If the heating time falls within the above range, the productivity of polycarbonate is high and it is suitable for industrial production.

[0084] Methods for removing fluorine-containing alcohols produced as by-products during solid-phase polymerization include solid-phase polymerization under reduced pressure, solid-phase polymerization while blowing in an inert gas, and methods combining these. The method of introducing an inert gas requires the reuse of the inert gas discharged from the system, which is a complicated process; therefore, solid-phase polymerization under reduced pressure is more preferable.

[0085] When solid-phase polymerization of a prepolymer under reduced pressure, the pressure is preferably in the high vacuum range of 13 kPa (absolute pressure) (100 torr (absolute pressure)) or less, more preferably 1.3 kPa (absolute pressure) (10 torr (absolute pressure)) or less, and particularly preferably 0.67 kPa to 0.013 kPa (absolute pressure) (5 to 0.1 torr (absolute pressure)). If the pressure is within the above range, solid-phase polymerization proceeds quickly. Inert gases are gases that are inert to solid-phase polymerization, and examples include nitrogen, argon, helium, carbon dioxide, lower hydrocarbons, and acetone.

[0086] Known solid-phase polymerization apparatuses can be used. The apparatus can be of any type, including batch, continuous, or a combination of both. Specifically, examples include tumbler type, kiln type, paddle dryer type, screw conveyor type, vibratory type, fluidized bed type, fixed bed type, and mobile bed type. For experimental use, vacuum dryers, such as those used for drying polymers, can also be used.

[0087] The weight-average molecular weight of the final polycarbonate is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and particularly preferably 20,000 to 60,000. If the weight-average molecular weight of the polycarbonate is above the lower limit, the heat resistance, rigidity, and toughness are better, and if it is below the upper limit, the moldability is better.

[0088] (Effects and Benefits) In the polycarbonate manufacturing method described above, a specific dihydroxy component and a specific fluorine-containing carbonate component are reacted in the presence of a condensation catalyst, and the resulting prepolymer is subjected to solid-phase polymerization. Therefore, high molecular weight polycarbonate using a non-aromatic dihydroxy compound as a raw material can be produced at a relatively low temperature below the melting temperature of the prepolymer. Furthermore, because polycarbonate can be produced at a relatively low temperature using this manufacturing method, heat-induced discoloration of the polycarbonate can be suppressed.

[0089] In this manufacturing method, a specific dihydroxy component is reacted with a specific fluorine-containing carbonate component, resulting in a prepolymer having constituent units derived from the fluorine-containing carbonate component at its termini. Because the constituent units derived from the fluorine-containing carbonate component at the termini of this prepolymer have high affinity with other prepolymers and readily undergo transesterification, it is believed that transesterification solid-phase polymerization can proceed even at relatively low temperatures below the melting temperature of the prepolymer (for example, at temperatures below 200°C). On the other hand, prepolymers obtained by reacting a specific dihydroxy component with diaryl carbonates or dialkyl carbonates other than specific fluorine-containing carbonate components are thought to have low affinity for other prepolymers due to the terminal diaryl carbonates or dialkyl carbonates, and are not easily transesterified. Therefore, solid-phase polymerization is not thought to proceed unless the temperature is raised (for example, to 240°C or higher). The inventors had previously believed that the method described in International Publication No. 2014 / 171367 would allow the transesterification reaction to proceed even in solid-phase polymerization due to the stacking of benzene rings in aromatic dihydroxy compounds. It was unexpected that the transesterification reaction could proceed in solid-phase polymerization even without the presence of benzene rings.

[0090] In step a described above, an alicyclic dihydroxy compound (which may contain an etheric oxygen atom) or a linear or branched aliphatic dihydroxy compound (which may contain an etheric oxygen atom) can be used as the dihydroxy component, and by appropriately adjusting the reaction conditions (for example, lowering the reaction temperature or shortening the reaction time), a fluorine-containing biscarbonate represented by the following formulas (m1), (m2), (m3), or (m4) can also be obtained. When producing fluorine-containing biscarbonate, the amount of fluorine-containing carbonate component used should be at least twice the molar amount of the dihydroxy component, but preferably 10 times the molar amount or less, more preferably 7 times the molar amount or less, and particularly preferably 4 times the molar amount or less.

[0091] [ka]

[0092] However, R 1 CA 1 B 1 R 4 It is a group represented by two R 1 They may be the same or different. R 2 CA 2 B 2 R 5 It is a group represented by two R 2 They may be the same or different. R 3 is a hydrogen atom or CA 3 B 3 R 6 It is a group represented by two R 3 They may be the same or different. A 1 ~A 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f And, B 1 ~B 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f And, R 4 ~R 6 is a fluorine atom, R f OR f And, R f This is a fluoroalkyl group having 1 to 12 carbon atoms (which may include an etheric oxygen atom) or a fluoroaryl group having 6 to 10 carbon atoms. R a This is a residue obtained by removing two hydroxyl groups from an alicyclic dihydroxy compound (which may contain an etheric oxygen atom) or a linear or branched aliphatic dihydroxy compound (which may contain an etheric oxygen atom).

[0093] [ka]

[0094] However, R 1 CA 1 B 1 R 4 It is a base represented by, R 2 CA 2 B 2 R 5 It is a base represented by, R 3 is a hydrogen atom or CA 3 B 3 R 6 It is a base represented by, R 7 This is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may also contain an etheric oxygen atom), A 1 ~A 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f And, B 1 ~B 3 These are, respectively, a hydrogen atom, a fluorine atom, or R f And, R 4 ~R 6 is a fluorine atom, R f OR f And, R f This is a fluoroalkyl group having 1 to 12 carbon atoms (which may include an etheric oxygen atom) or a fluoroaryl group having 6 to 10 carbon atoms. R a This is a residue obtained by removing two hydroxyl groups from an alicyclic dihydroxy compound (which may contain an etheric oxygen atom) or a linear or branched aliphatic dihydroxy compound (which may contain an etheric oxygen atom).

[0095] [ka]

[0096] However, R 7This is a perfluoroalkylene group having 1 to 5 carbon atoms (however, it may also contain an etheric oxygen atom), and has two R 7 They may be the same or different. R a This is a residue obtained by removing two hydroxyl groups from an alicyclic dihydroxy compound (which may contain an etheric oxygen atom) or a linear or branched aliphatic dihydroxy compound (which may contain an etheric oxygen atom).

[0097] [ka]

[0098] However, R 9 ~R 13 Each of these is a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms (however, it may also contain an etheric oxygen atom), and the two R 9 , two R 10 , two R 11 , two R 12 and two R 13 Each of them may be the same or different, and each molecule has at least one fluorine atom. R a This is a residue obtained by removing two hydroxyl groups from an alicyclic dihydroxy compound (which may contain an etheric oxygen atom) or a linear or branched aliphatic dihydroxy compound (which may contain an etheric oxygen atom).

[0099] By using the above-mentioned fluorine-containing biscarbonate, high molecular weight polycarbonates can be produced using non-aromatic dihydroxy compounds as raw materials, similar to the manufacturing method described above. For example, a prepolymer is obtained in the same manner as in step a by reacting the above-mentioned fluorine-containing biscarbonate alone or with any dihydroxy compound in the presence of a condensation catalyst. A polycarbonate is obtained in the same manner as in step b by solid-phase polymerization of the prepolymer by heating the obtained prepolymer at a temperature below its melting point and discharging the by-product fluorine-containing alcohol from the system. Examples of any dihydroxy compound include the aforementioned alicyclic dihydroxy compounds, linear or branched aliphatic dihydroxy compounds, and aromatic dihydroxy compounds. [Examples]

[0100] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Examples 1-5 are examples of actual cases.

[0101] ( 1 (H-nuclear magnetic resonance spectrum) Bruker AVANCE III 400 1 Measurements were performed using a 400 MHz resistor (for H) and a deuterated chloroform solution. Tetramethylsilane was used as an internal standard (0 ppm) to calculate the chemical shifts of various hydrogen nuclei.

[0102] (Weight-average molecular weight and number-average molecular weight) Using a liquid chromatography system manufactured by JASCO Corporation (liquid delivery pump PU-4185, column oven CO-4060, ultraviolet absorption detector UV-4075, refractive index detector RI-4035), two Showa Denko Shodex GPC HK-404L columns were connected in series, and GPC measurements were performed at 40°C with chloroform as the developing solvent (flow rate 0.3 mL). Calibration curves for elution time and molecular weight were created using standard polystyrene with known molecular weights, and based on these, the weight-average and number-average molecular weights were calculated from the sample elution curves in polystyrene equivalents.

[0103] (Example 1) 203.7 mg (1.394 mmol) of isosorbide was weighed into a heat-resistant glass test tube (15 / 35 common ground joint) with an outer diameter of 21 mm and a total length of 130 mm. A polytetrafluoroethylene stirrer tip was placed inside, a glass three-way stopcock was attached, and the test tube was dried under vacuum for half a day through a phosphorus pentoxide trap. Next, the test tube was purged with nitrogen, and 0.8 mL of dry acetonitrile, 532 mg (1.469 mmol) of bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, and 13.2 mg (0.0712 mmol) of tri(n-butyl)amine were added under a nitrogen stream to form a homogeneous solution. This homogeneous solution was heated at 90°C for 70 hours while stirring with a magnetic stirrer, and the product became a white solid that adhered to the bottom of the test tube. Acetonitrile was removed under reduced pressure, and 3 mL of dry methylene chloride was added to form a homogeneous solution. A portion of this homogeneous solution was taken, 1 Analysis using 1H nuclear magnetic resonance spectroscopy and GPC revealed the formation of a prepolymer with a weight-average molecular weight of 8832 and a number-average molecular weight of 4203. The homogeneous solution remaining in the test tube was vacuum-dried, resulting in a white, cotton-candy-like substance. Next, after purging the test tube with nitrogen, the mixture was heated in a column tube oven (Shibata Scientific GTO-3000) under vacuum (0.22 kPa) while slowly rotating the test tube (50°C, 70°C, 90°C, 110°C, 130°C for 1 hour each, and 150°C, 170°C, 190°C for 3 hours each). The reactants in the test tube remained solid throughout the reaction. The final product had a weight-average molecular weight of 42395 and a number-average molecular weight of 22417. 1 In the H-nuclear magnetic resonance spectra, signals supporting the corresponding polycarbonate-derived structure were obtained (5.13-5.06 ppm (2H), 4.91-4.86 ppm (1H), 4.56-4.51 ppm (1H), 4.09-3.97 ppm (2H), 3.93-3.88 ppm (2H)) (all as multiple lines).

[0104] (Example 2) 200 mg (1.369 mmol) of isosorbide and 50 mg (0.348 mmol) of 1,4-cyclohexanedimethanol were weighed into a heat-resistant glass test tube (15 / 35 ground joint) with an outer diameter of 21 mm and a total length of 130 mm. After adding a polytetrafluoroethylene stirrer tip, a glass three-way stopcock was attached, and the mixture was dried under vacuum for half a day through a phosphorus pentoxide trap. Next, the test tube was purged with nitrogen, and 1.0 mL of dried acetonitrile, 656 mg (1.812 mmol) of bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, and 12.5 mg (0.0674 mmol) of tri(n-butyl)amine were added under a nitrogen stream to form a homogeneous solution. This homogeneous solution was heated at 90°C for 93 hours while stirring with a magnetic stirrer, and became turbid. Acetonitrile was removed under reduced pressure, and 3 mL of dry methylene chloride was added to obtain a homogeneous solution. A portion of this homogeneous solution was taken. 1 Analysis using 1H nuclear magnetic resonance spectroscopy and GPC revealed the formation of a prepolymer with a weight-average molecular weight of 5945 and a number-average molecular weight of 3202. The homogeneous solution remaining in the test tube was vacuum-dried, resulting in a white powdery substance. Next, after purging the test tube with nitrogen, the mixture was heated in a column tube oven (Shibata Scientific GTO-3000) under vacuum (0.22 kPa) while slowly rotating the test tube, with the temperature gradually increasing (110°C, 120°C, 130°C, 140°C, 150°C, 160°C, and 170°C for 1 hour each). The reactants in the test tube remained in a solid state throughout the reaction. The final product had a weight-average molecular weight of 20746 and a number-average molecular weight of 10699. 1 In the 1H nuclear magnetic resonance spectrum, it provided a signal supporting a structure originating from the copolymerized polycarbonate.

[0105] (Example 3) 199.9 mg (1.368 mmol) of isosorbide and 78.2 mg (0.343 mmol) of bisphenol A were weighed into a heat-resistant glass test tube (15 / 35 with ground joint) with an outer diameter of 21 mm and a total length of 130 mm. After adding a polytetrafluoroethylene stirrer tip, a glass three-way stopcock was attached, and the test tube was dried under vacuum for half a day through a phosphorus pentoxide trap. Next, the test tube was purged with nitrogen, and 1.0 mL of dry acetonitrile, 650.0 mg (1.795 mmol) of bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, and 12.9 mg (0.0696 mmol) of tri(n-butyl)amine were added under a nitrogen stream to form a homogeneous solution. This homogeneous solution was heated at 90°C for 70 hours while stirring with a magnetic stirrer, and a precipitate was formed. Acetonitrile was removed under reduced pressure, and 3 mL of dry methylene chloride was added to obtain a homogeneous solution. A portion of this homogeneous solution was taken. 1 Analysis using 1H nuclear magnetic resonance spectroscopy and GPC revealed the formation of a prepolymer with a weight-average molecular weight of 5867 and a number-average molecular weight of 2719. The homogeneous solution remaining in the test tube was vacuum-dried to obtain a powder. Next, after purging the test tube with nitrogen, the sample was heated in a column tube oven (Shibata Scientific GTO-3000) under vacuum (0.22 kPa) while slowly rotating the test tube, with the temperature gradually increasing (110°C, 130°C, and 150°C for 1 hour each). A portion was taken out, 1 Analysis using 1H nuclear magnetic resonance spectroscopy and GPC revealed that the reaction proceeded and a polymer with a weight-average molecular weight of 14882 and a number-average molecular weight of 7420 was produced. The product was pulverized, the test tube was again purged with nitrogen, and then heated under vacuum (170°C and 190°C for 1 hour each). The reactants in the test tube remained in a solid state throughout the reaction. The final product had a weight-average molecular weight of 32861 and a number-average molecular weight of 16066. 1 In the 1H nuclear magnetic resonance spectrum, it provided a signal supporting a structure originating from the copolymerized polycarbonate.

[0106] (Example 4) 137 mg (0.937 mmol) of isosorbide, 137 mg (0.600 mmol) of bisphenol A, and 22 mg (0.153 mmol) of 1,4-cyclohexanedimethanol were weighed into a heat-resistant glass test tube (15 / 35 with a ground joint) with an outer diameter of 21 mm and a total length of 130 mm. After adding a polytetrafluoroethylene stirrer tip, a glass three-way stopcock was attached, and the mixture was dried under vacuum for half a day through a phosphorus pentoxide trap. Next, the test tube was purged with nitrogen, and 1.0 mL of dry acetonitrile, 641 mg (1.770 mmol) of bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, and 12.7 mg (0.0685 mmol) of tri(n-butyl)amine were added under a nitrogen stream to form a homogeneous solution. This homogeneous solution was heated at 90°C for 70 hours while being stirred with a magnetic stirrer. Acetonitrile was removed under reduced pressure, and 3 mL of dry methylene chloride was added to obtain a homogeneous solution. A portion of this homogeneous solution was taken. 1 Analysis using 1H nuclear magnetic resonance spectroscopy and GPC revealed the formation of a prepolymer with a weight-average molecular weight of 2129 and a number-average molecular weight of 1362. The homogeneous solution remaining in the test tube was vacuum-dried, resulting in a white powdery substance. Next, after purging the test tube with nitrogen, the sample was heated in a column tube oven (Shibata Scientific GTO-3000) under vacuum (0.22 kPa) while slowly rotating the test tube, with the temperature gradually increasing (110°C, 120°C, 130°C, 140°C, and 150°C for 1 hour each). A portion was then taken out. 1 Analysis using 1H nuclear magnetic resonance spectroscopy and GPC revealed that the reaction proceeded and a polymer with a weight-average molecular weight of 34970 and a number-average molecular weight of 16553 was formed. The test tube was again purged with nitrogen and heated under vacuum (170°C and 190°C for 1 hour each). The reactants in the test tube remained in a solid state throughout the reaction. The final product had a weight-average molecular weight of 52250 and a number-average molecular weight of 25361. 1 In the 1H nuclear magnetic resonance spectrum, it provided a signal supporting a structure originating from the copolymerized polycarbonate.

[0107] (Example 5) 100.9 mg (0.690 mmol) of isosorbide was weighed into a heat-resistant glass test tube (15 / 35 with a ground joint), a polytetrafluoroethylene stirrer tip was inserted, a glass three-way stopcock was attached, and the test tube was purged with nitrogen. Under a nitrogen stream, 2.0 mL of dry acetonitrile, 783.8 mg (2.16 mmol) of bis(1,1,1,3,3,3-hexafluoroisopropyl) carbonate, and 2.6 mg (0.0257 mmol) of triethylamine were added to make a homogeneous solution. This homogeneous solution was stirred with a magnetic stirrer at room temperature for 44 hours. A portion of the reaction solution was taken, 1 Analysis using 1H-nuclear magnetic resonance spectroscopy revealed that the target isosorbide biscarbonate was quantitatively produced. Acetonitrile was removed under reduced pressure, 1 mL of dry methylene chloride was added to make a homogeneous solution, and 35.4 mg (H) of strongly acidic ion exchange resin ("Amberlist 15" manufactured by Organo Corporation) was added. + (equivalent to 0.28 mmol) was added and filtered. After drying under reduced pressure, distillation was performed under vacuum (12-13 Pa) using a column tube oven (Shibata Scientific GTO-3000), and the distillate was collected at 250°C to obtain the target isosorbide biscarbonate. The identification data is shown below. 1 H-nuclear magnetic resonance spectrum (400MHz, CDCl3) δppm 3.88(dd,J=11.1,4.8Hz,1H), 4.01(dd,J=11.5,3.2Hz,1H), 4.06-4.18(m,2H), 4.56(d,J=5.1Hz,1H), 5.01(t,J=5.5Hz,1H), 5.16-5.27(m,2H). 13 ¹¹¹ nuclear magnetic resonance spectra (100 MHz, CDCl3) ppm 69.44–71.51 (m), 71.00, 72.69, 78.88, 81.28, 83.00, 85.56, 115.8–124.3 (m), 152.07, 152.34. 19 F-nuclear magnetic resonance spectrum (376 MHz, CDCl3) ppm -73.4 to -73.6 (m).

[0108] [ka] [Industrial applicability]

[0109] The polycarbonate obtained by the manufacturing method of the present invention is useful as an optical component (lens, optical fiber, film, LCD backlight diffuser plate, photoreceptor, etc.), DVD / CD discs, electronic component housings (mobile phones, etc.), windows for transportation equipment, transparent roofing materials, windbreaks, screens, bulletproof windows, tableware, suitcases, helmets, etc.

Claims

1. The following dihydroxy component and the following fluorine-containing carbonate component are reacted in the presence of a condensation catalyst such that the molar ratio of the fluorine-containing carbonate component to the dihydroxy component is between 1 / 1 and 2 / 1. A method for producing polycarbonate, comprising heating the obtained prepolymer at a temperature below its melting point and solid-phase polymerizing the prepolymer while discharging the by-product fluorine-containing alcohol from the system. Dihydroxy component: At least one non-aromatic dihydroxy compound selected from the group consisting of alicyclic dihydroxy compounds and linear or branched aliphatic dihydroxy compounds, or a mixture of the non-aromatic dihydroxy compound and the aromatic dihydroxy compound, wherein the alicyclic dihydroxy compound may have some carbon atoms substituted with oxygen atoms, and the linear or branched aliphatic dihydroxy compound may have some carbon atoms substituted with oxygen atoms. Fluorine-containing carbonate component: At least one compound selected from the group consisting of the compound represented by formula (1), the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (4). 【Chemistry 1】 However, R １ CA １ B １ R ４ It is a group represented by two R １ They may be the same or different. R ２ is a group represented by CA ２ B ２ R ５ and the two Rs ２ may be the same or different R ３ is a hydrogen atom or CA ３ B ３ R ６ It is a group represented by two R ３ They may be the same or different. A １ ~A ３ Each is independently a hydrogen atom, a fluorine atom, or R ｆ And, B １ ~B ３ Each is independently a hydrogen atom, a fluorine atom, or R ｆ And, R ４ ~R ６ Each of these is an independent fluorine atom, R ｆ OR ｆ And, R ｆ This is a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroaryl group having 6 to 10 carbon atoms, and in the fluoroalkyl group having 1 to 12 carbon atoms, some of the carbon atoms may be substituted with oxygen atoms. 【Chemistry 2】 However, R １ CA １ B １ R ４ It is a base represented by, R ２ CA ２ B ２ R ５ It is a base represented by, R ３ is a hydrogen atom or CA ３ B ３ R ６ It is a base represented by, R ７ This is a perfluoroalkylene group having 1 to 5 carbon atoms, and the perfluoroalkylene group having 1 to 5 carbon atoms may have some of its carbon atoms replaced by oxygen atoms. A １ ~A ３ Each is independently a hydrogen atom, a fluorine atom, or R ｆ And, B １ ~B ３ Each is independently a hydrogen atom, a fluorine atom, or R ｆ And, R ４ ~R ６ Each of these is an independent fluorine atom, R ｆ OR ｆ And, R ｆ This is a fluoroalkyl group having 1 to 12 carbon atoms or a fluoroaryl group having 6 to 10 carbon atoms, and in the fluoroalkyl group having 1 to 12 carbon atoms, some of the carbon atoms may be substituted with oxygen atoms. 【Transformation 3】 However, R ７ This is a perfluoroalkylene group having 1 to 5 carbon atoms, and has two R ７ These may be the same or different, and the perfluoroalkylene group having 1 to 5 carbon atoms may have some of its carbon atoms substituted with oxygen atoms. 【Chemistry 4】 However, R ９ ~R １３ Each is independently a hydrogen atom, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, and two R ９ , two R １０ , two R １１ , two R １２ and two R １３ These may be the same or different, and each molecule may have at least one fluorine atom, and the carbon-1 to carbon-6 fluoroalkyl group may have some of its carbon atoms substituted with oxygen atoms.

2. The method for producing the non-aromatic dihydroxy compound according to claim 1, wherein the non-aromatic dihydroxy compound includes isosorbide.

3. The production method according to claim 2, wherein the proportion of isosorbide to the total non-aromatic dihydroxy compound is 50 mol% or more.

4. The manufacturing method according to claim 1, wherein the dihydroxy component is a mixture of the non-aromatic dihydroxy compound and the aromatic dihydroxy compound.

5. The manufacturing method according to claim 1, wherein the weight-average molecular weight of the prepolymer is 500 to 15,000.

6. The manufacturing method according to claim 1, wherein the heating temperature when solid-phase polymerization of the prepolymer is 200°C or less.

7. The manufacturing method according to any one of claims 1 to 6, wherein the weight-average molecular weight of the polycarbonate is 10,000 to 100,000.

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