Method for producing polysiloxane, composition containing polysiloxane, and molded body

Abstract

The present application provides a method capable of improving safety and reducing environmental load, and capable of efficiently producing a polysiloxane having a siloxane structural unit. The above technical problem can be solved by a method including a polymerization step in which a silane-based compound selected from a prescribed diaryloxy silane compound, a prescribed dialkoxy silane compound, and a prescribed silicon compound is polymerized with a dihydroxy compound in the presence of at least an ester exchange catalyst containing a phosphorus compound, and in the polymerization step, a polysiloxane having a siloxane structural unit represented by any one of Formula (1-1) to Formula (1-4) is produced. In the formulae, R 1 ~R 10 , R 30 ~R 33 , Z1, Z2, J1, K1, A1, A2, L1, L2, and X are as described in the specification.

Description

Technical Field

[0001] This invention relates to a method for manufacturing polysiloxanes, and compositions containing polysiloxanes. Background Technology

[0002] As materials for obtaining molded articles using molding methods such as injection molding, polymers of aromatic polysiloxanes, also known as polyarylene siloxanes (e.g., Patent Document 1), are known. In recent years, the importance of polysiloxane compounds such as polyarylene siloxanes has increased, and polyarylene siloxanes are used, for example, as release layers in photocopying, photoresist materials, plasticizers for polycarbonate, or components of powder surface coating systems.

[0003] Methods for manufacturing polysiloxane compounds such as polyarylene siloxanes include the method of reacting dimethyldichlorosilane with bisphenol A in a solvent to generate hydrochloric acid (Non-Patent Document 1) and the method of reacting in a solvent containing acetic acid (Patent Document 2).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Publication No. 08-502537

[0007] Patent Document 2: Japanese Patent Publication No. 2015-512999

[0008] Non-patent literature

[0009] Non-licensed document 1: Journal of Polymer Science, Vol. 18, 3119–3127 (1980) Summary of the Invention

[0010] The technical problem that the invention aims to solve

[0011] It is desirable to provide a method for manufacturing siloxane compounds that does not generate corrosive substances such as hydrochloric acid or acetic acid, does not require the use of solvents, and can reduce environmental impact.

[0012] Furthermore, the reaction rates in existing methods for manufacturing polysiloxane compounds are not high enough, and there is a need to provide a more efficient method for manufacturing polysiloxane compounds.

[0013] Technical means for solving technical problems

[0014] This invention provides a method for efficiently manufacturing polysiloxane compounds, etc. The manufacturing method of this invention does not generate environmentally damaging byproducts such as acids, and does not require solvents, especially solvents that pose safety concerns.

[0015] This invention includes methods for manufacturing polysiloxanes as described below.

[0016] [1] A method for manufacturing a polysiloxane, wherein the polysiloxane has a siloxane structural unit represented by any one of the following formulas (1-1) to (1-4), the method comprising a polymerization step of polymerizing a silane compound selected from diaryloxysilane compounds, diekoxysilane compounds and silicon compounds with a dihydroxy compound containing an aromatic dihydroxy compound or an alicyclic dihydroxy compound, wherein in the polymerization step a transesterification catalyst containing a phosphorus compound is used, wherein the diaryloxysilane compound contains at least one of dialkyldiaryloxysilane, diaryldiaryloxysilane and monoalkylmonaryldiaryloxysilane, wherein the diekoxysilane compound contains at least one of dialkyldialkoxysilane, diaryldialkoxysilane and monoalkylmonaryldialkoxysilane, and wherein the silicon compound contains at least one of cyclic siloxane compounds and linear siloxane compounds.

[0017]

[0018] (In equations (1-1) to (1-4), R) 1 and R 2 Each can independently represent an alkyl group having a total of 1 to 20 carbon atoms that may have substituents, or an aryl group having a total of 6 to 30 carbon atoms that may have substituents.

[0019] R 3 ~R 10 and R 30 ~R 33 Each can independently represent hydrogen, halogen, alkoxy, alkyl (with a total of 1 to 20 carbon atoms that may have substituents), alkenyl (with a total of 2 to 20 carbon atoms that may have substituents), or aryl (with a total of 6 to 30 carbon atoms that may have substituents).

[0020] Z1 and Z2 independently represent alkylene groups with a total carbon number of 1 to 5 that may have substituents.

[0021] J1 independently represents integers above 0 and below 5.

[0022] K1 independently represents integers above 0 and below 5.

[0023] A1 and A2 independently represent either -O- or -CH-.

[0024] L1 and L2 independently represent integers above 0 and below 3.

[0025] X is a single bond, or any of the structural formulas shown in equation (2) below.

[0026]

[0027] In equation (2), R 11 and R 12 Each can independently represent hydrogen, halogen, alkyl groups with a total carbon number of 1 to 20 that may have substituents, or aryl groups with a total carbon number of 6 to 30 that may have substituents, or represent R. 11 and R 12 Carbon rings or heterocycles with 1 to 20 carbon atoms that are bonded together can have substituents.

[0028] The aforementioned substituents are each independently any one of halogen, cyano, alkenyl, alkynyl, or alkoxy.

[0029] a and b independently represent integers greater than 0 or 1 and less than 5000.

[0030] [2] The method for manufacturing polysiloxane as described in [1] above, wherein the phosphorus compound comprises a compound represented by the following general formula (I).

[0031] (PRe4) + (Xc) － ···(I)

[0032] In general formula (I), Re independently represents alkyl, aryl, or alkylaryl, and multiple Re can bond together to form a ring structure.

[0033] Xc represents a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl carbonyloxy group, an aryl carbonyloxy group, HCO3, or BRf4 (where Rf is independently a hydrogen atom, alkyl group, or aryl group).

[0034] [3] The method for manufacturing polysiloxane as described in [1] above, wherein the phosphorus compound comprises any one of biphenyltriphenylphosphonium hydroxide, biphenyltriphenyltetraphenylboronic acid, biphenyltriphenylphenoxyphosphonium, biphenyltriphenylphosphonium chloride, tetraphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide, tetraphenylphenoxyphosphonium, tetraphenyltetraphenylboronic acid, methoxyphenyltriphenyltetraphenylboronic acid, phenoxyphenyltriphenyltetraphenylboronic acid, naphthylphenyltriphenyltetraphenylboronic acid, tetraphenylphenoxyphosphonium, methoxyphenyltriphenylphenoxyphosphonium, phenoxyphenyltriphenylphenoxyphosphonium, naphthylphenyltriphenylphenoxyphosphonium, tetraphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride, and naphthylphenyltriphenylphosphonium chloride.

[0035] [4] The method for manufacturing polysiloxane as described in [3] above, wherein the phosphorus compound comprises at least one of tetraphenylphenoxyphosphonium and tetraphenyltetraphenylboratephosphonium.

[0036] [5] The method for manufacturing polysiloxane as described in any one of [1] to [4] above, wherein the transesterification catalyst further comprises an alkali metal catalyst.

[0037] [6] The method for manufacturing polysiloxane as described in [5] above, wherein the transesterification catalyst comprises at least a sodium-containing alkali metal transesterification catalyst.

[0038] [7] The method for manufacturing polysiloxane as described in any one of [1] to [6] above, wherein, in the polymerization step, the amount of the transesterification catalyst relative to the amount of the dihydroxy compound is 1.0 × 10⁻⁶ molar ratio. －7 ~1.0×10 －2 .

[0039] [8] The method for manufacturing polysiloxane as described in any one of [1] to [7] above, wherein the reaction temperature in the polymerization process is in the range of 150°C to 300°C.

[0040] [9] The method for manufacturing polysiloxane as described in any one of [1] to [8] above, wherein no solvent is used in the polymerization process described above.

[0041]

[10] The method for manufacturing polysiloxane as described in any one of [1] to [9] above, wherein the ratio of the molar number of the silane compound used in the polymerization step to the molar number of the dihydroxy compound is 0.9 or more and 1.2 or less.

[0042]

[11] The method for manufacturing polysiloxane as described in any one of [1] to

[10] above, wherein, in the polymerization step above, the carbonate compound is further polymerized with the silane compound and the dihydroxy compound.

[0043]

[12] The method for manufacturing polysiloxane as described in any one of [1] to

[11] above, wherein the polysiloxane further has a polycarbonate structural unit derived from the carbonate compound represented by any one of the following formulas (3-1) to (3-4).

[0044]

[0045] (In general formulas (3-1) to (3-4),

[0046] R 3 ~R 10 R 21 ~R 26 and R 31 ~R 36Each of the following can independently represent a hydrogen atom, a halogen atom, an alkoxy group with 1 to 5 carbon atoms that may have substituents, an alkyl group with 1 to 20 carbon atoms that may have substituents, an alkenyl group with 2 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents.

[0047] Z1 and Z2 are each independently an alkylene group having 1 to 5 carbon atoms that can have substituents.

[0048] The substituents mentioned above are any one of halogen, cyano, alkenyl, alkynyl, or alkoxy.

[0049] J1 independently represents integers from 0 to 5.

[0050] K1 independently represents integers from 0 to 5.

[0051] A1 and A2 independently represent either -O- or -CH2-.

[0052] L1 and L2 independently represent integers from 0 to 3.

[0053] X is a single bond, or any of the structural formulas shown in equations (1) to (7) below.

[0054]

[0055] (in general formulas (1) to (7),

[0056] R 11 and R 12 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, or an aryl group with 6 to 30 carbon atoms that may have substituents, or represent a group composed of R. 11 and R 12 Carbon rings or heterocycles with 1 to 20 carbon atoms that are bonded together can have substituents.

[0057] The substituents mentioned above are any one of halogen, cyano, alkenyl, alkynyl, or alkoxy.

[0058] r and s independently represent integers from 0 to 5000.

[0059]

[13] The method for manufacturing polysiloxane as described in

[12] above, wherein the molar ratio of the total of the siloxane structural units to the total of the polycarbonate structural units is 0.1:99.9 to 100:0.

[0060]

[14] The method for manufacturing polysiloxane as described in

[12] or

[13] above, wherein, in the polymerization step above, under molten conditions and reduced pressure, the alcohol from the carbonate compound is removed while the silane compound is polymerized with the dihydroxy compound.

[0061]

[15] The method for manufacturing polysiloxane as described in any one of [1] to

[10] above, wherein the polysiloxane is composed only of the aforementioned siloxane structural units.

[0062]

[16] The method for manufacturing polysiloxane as described in any one of [1] to

[15] above, wherein the weight-average molecular weight (Mw) of the polysiloxane converted to polystyrene is 10,000 to 300,000.

[0063]

[17] The method for manufacturing polysiloxane as described in any one of [1] to

[16] above, wherein, in the polysiloxane, the low molecular weight compound with a weight average molecular weight of 1,000 or less is 1% by weight or less.

[0064]

[18] The method for manufacturing polysiloxane as described in

[17] above, wherein the proportion of low molecular weight compounds with a weight average molecular weight of 1,000 or less calculated from the GPC area ratio in the polysiloxane is 1% by weight or less.

[0065]

[19] The method for manufacturing polysiloxane as described in any one of [1] to

[18] above, wherein the thermal decomposition temperature of the polysiloxane with a 1% mass reduction is above 300°C.

[0066]

[20] The method for manufacturing polysiloxane as described in any one of [1] to

[19] above, wherein the mass retention rate of the polysiloxane at 500°C is 40% or more.

[0067]

[21] A composition comprising a polysiloxane obtained by any one of the manufacturing methods described in [1] to

[20] above, and a polycarbonate resin.

[0068]

[22] The composition as described in

[21] above, wherein the total Si content in the composition is 0.1 to 20% by mass.

[0069]

[23] A molded body comprising a polysiloxane obtained by any one of the manufacturing methods described in [1] to

[20] above.

[0070]

[24] An optical lens comprising a polysiloxane obtained by any one of the manufacturing methods described in any one of [1] to

[20] above.

[0071]

[25] An optical lens obtained by molding the composition described in

[21] or

[22] above.

[0072] Invention Effects

[0073] The method for manufacturing polysiloxanes according to the present invention improves safety, reduces environmental impact, and efficiently manufactures polysiloxanes. According to the present invention, compositions and molded articles containing polysiloxanes can also be produced. Attached Figure Description

[0074] Figure 1 This is the calibration line used in the calculation of phenol conversion in each example and comparative example. This calibration line represents the relationship between the peak area of ​​phenol measured by GC / FID under the conditions described later and the concentration of phenol in the sample. Detailed Implementation

[0075] [I. Polysiloxane]

[0076] The method for manufacturing the polysiloxane of the present invention includes a polymerization step, as detailed below, in which at least one silane compound selected from a specified diaryloxysilane compound, a specified dialkoxysilane compound, and a specified silicon compound (siloxane compound) is polymerized with a dihydroxy compound such as an aromatic dihydroxy compound. In the polymerization step, as detailed below, a transesterification catalyst containing at least a phosphorus compound is used.

[0077] The above polymerization reaction is illustrated below. For example, when a diaryloxysilane compound having two methyl groups and a phenoxy group (Si(CH3)2(OPh)2), which is an example of a silane compound, is reacted with bisphenol A, which is an example of an aromatic dihydroxy compound, the following polysiloxane compound can be obtained.

[0078] That is, for example, a polysiloxane compound having a siloxane structural unit generated by a reaction of the following formula (A).

[0079] In this polymerization reaction, as described below, aryl alcohols derived from silane compounds, such as phenol (PhOH), are generated as byproducts. Therefore, in the polymerization step, it is preferable to carry out the polymerization reaction under reduced pressure while the mixture of the above-mentioned components is molten, removing the byproducts such as alcohols and aryl alcohols, such as phenol.

[0080]

[0081] Furthermore, carbonate compounds such as diphenyl carbonate (PhO-CO-OPh) can also be used together with the above-mentioned components in the polymerization reaction. Thus, when using carbonate compounds as addition components, polycarbonate structural units are formed by reacting carbonate compounds with dihydroxy compounds such as aromatic dihydroxy compounds, for example, as shown in formula (B).

[0082] Although the polysiloxane of the present invention is preferably composed of only siloxane structural units, when a carbonate compound is used as described above, a polysiloxane compound as a polycarbonate copolymer is generated that contains polycarbonate structural units in addition to siloxane structural units.

[0083]

[0084] The following provides a detailed description of the method for manufacturing the polysiloxane compound of the present invention.

[0085] <1. Manufacturing method of polysiloxane>

[0086] [(I) Silane compounds]

[0087] For example, as shown in equation (A) above, the silane-based compound used in the polymerization process is used to form the siloxane structural unit in the polysiloxane compound. Regarding the type of silane-based compound, as long as the main chain of the polysiloxane compound can form the structure containing -OSi(R) as detailed below... 1 R 2 The siloxane structural unit at the O- site is not particularly limited and can be selected from specified diaryloxysilane compounds, specified dialkoxysilane compounds, and specified silicon compounds (siloxane compounds).

[0088] That is, in the polymerization process, at least one silane compound selected from the diaryloxysilane compound, dialkoxysilane compound, and silicon compound described in detail below is used. As a silane compound, multiple diaryloxysilane compounds, multiple dialkoxysilane compounds, and multiple silicon compounds can be used in combination. Furthermore, mixtures of diaryloxysilane compounds and silicon compounds, mixtures of dialkoxysilane compounds and silicon compounds, and mixtures of diaryloxysilane compounds and dialkoxysilane compounds can also be used. The diaryloxysilane compounds will be described below.

[0089] (A-1) Diaryloxysilane compounds

[0090] Examples of diaryloxysilane compounds include dialkyldiaryloxysilanes, diaryldiaryloxysilanes, and monoalkylmonoaryldiaryloxysilanes. That is, any one or more of them can be used as silane compounds in the polymerization process.

[0091] In the general formula Si(R) a R b When )(OAr)2 represents a diaryloxysilane compound, R a and R b Each is independently selected from alkyl and aryl groups. R is preferred. a and R b Each can be an alkyl group having a total of 1 to 20 carbon atoms and an aryl group having a total of 6 to 30 carbon atoms, respectively, and may independently have substituents. More preferably, in R a and R b When the alkyl group can have substituents, it is preferred that the total number of carbon atoms is 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2.

[0092] Additionally, in R a and R b When the aryl group can have substituents, it is preferable that the total number of carbon atoms is 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0093] Examples of substituents mentioned above include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, epoxypropoxy, and mercapto.

[0094] As R in equation (1) a and R b Preferred specific examples may include methyl, phenyl, vinyl and propyl.

[0095] Furthermore, as can be seen from formula (A) above, the aryloxy group (OAr group) of the silane compound does not introduce into the polymer chain of the polysiloxane compound, but instead generates byproducts (ArOH) such as phenol. Therefore, there is no particular limitation on the type of aryloxy group. However, in order to remove byproducts from the reaction system as easily as possible during the polymerization process, the aryloxy group is preferably polar and has a low molecular weight, such as phenoxy.

[0096] Specific examples of dialkyl diaryloxysilanes include dimethyl diphenoxysilane, methyl ethyl diphenoxysilane, and diethyl diphenoxysilane. Specific examples of diaryl diaryloxysilanes include diphenyl diphenoxysilane. Furthermore, specific examples of monoalkyl monoaryl diaryloxysilanes include methyl phenyl phenoxysilane.

[0097] (A-2)dialkoxysilane compounds

[0098] Examples of dialkoxysilane compounds include dialkyl dialkoxysilanes, diaryl dialkoxysilanes, and monoalkyl monoaryl dialkoxysilanes. That is, any one or more of them can be used as silane compounds in the polymerization process.

[0099] In the general formula Si(R) a R b (OR) C When )2 represents a diekoxysilane compound, R a and R b Independently with the R described in the (A-1) diaryloxysilane compound category a and R b Similarly, they are selected from alkyl and aryl groups.

[0100] Furthermore, as can be seen from the above formula (A), the alkoxy group (OR) of silane compounds C The alkoxy group (OR) does not introduce into the polymer chain of the polysiloxane compound, but instead generates byproducts such as methanol (MeOH). Therefore, there is no particular limitation on the type of alkoxy group. However, in order to remove byproducts from the reaction system as easily as possible during the polymerization process, alkoxy groups (OR) are preferred. C (e.g., methoxy group).

[0101] Specific examples of dialkyldialkoxysilanes include dimethyldimethoxysilane, methylethyldimethoxysilane, and diethyldimethoxysilane. Specific examples of diaryldialkoxysilanes include diphenyldimethoxysilane. Furthermore, specific examples of monoalkylmonalyldialkoxysilanes include methylphenyldimethoxysilane.

[0102] (B) Silicon compounds (siloxane compounds)

[0103] The following describes silicon compounds. Examples of silicon compounds include cyclic siloxane compounds and linear siloxane compounds. That is, either type can be used as a silane compound in the polymerization process.

[0104] (B-1) Cyclic siloxane compounds

[0105] As siloxane compounds used in the polymerization process, cyclic siloxane compounds as shown in formula (5) can be listed.

[0106]

[0107] In equation (5), R c and R d Each can independently represent an alkyl, alkenyl, or aryl group that may have substituents. R in preferred formula (5) c and R d They are alkyl groups having a total of 1 to 20 carbon atoms or aryl groups having a total of 6 to 30 carbon atoms, respectively.

[0108] In R c and Rd When the alkyl group can have substituents, it is preferable that the total number of carbon atoms is 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2.

[0109] Additionally, in R c and R d When the aryl group can have substituents, it is preferable that the total number of carbon atoms is 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0110] Examples of substituents mentioned above include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, epoxypropoxy, and mercapto.

[0111] As R in equation (5) c and R d Preferred specific examples may include methyl, phenyl, vinyl and propyl.

[0112] Cyclic siloxane compounds have a siloxane structure. Examples of siloxane structures include those with the aforementioned R... c base and R d The base of -OSi(R) c R d The -OSi(R) structure. In the polymerization process, such cyclic siloxane compounds... c R d The O-site is introduced into the polysiloxane compound described in detail later.

[0113] In equation (5), n represents an integer of 3 to 30. The value of n in equation (5) is preferably 3 to 15, more preferably 3 to 10, even more preferably 3 to 8, and particularly preferably 3 to 5.

[0114] The molecular weight of the cyclic siloxane compound shown in Formula (5) is preferably 2,000 or less, more preferably 1,600 or less, further preferably 1,200 or less, and particularly preferably 1,000 or less. In addition, the molecular weight of the cyclic siloxane compound shown in Formula (5) is, for example, 100 or more, preferably 150 or more, and more preferably 200 or more.

[0115] (B-2) Straight-chain siloxane compounds

[0116] As siloxane compounds used in the polymerization process, linear siloxane compounds as shown in formula (6) can also be listed.

[0117]

[0118] In equation (6), R e and Rf Each can independently represent an alkyl or aryl group that may have substituents. R in preferred formula (6) e and R f They are alkyl groups having a total of 1 to 20 carbon atoms or aryl groups having a total of 6 to 30 carbon atoms, respectively.

[0119] In R e and R f When the alkyl group can have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 or 2.

[0120] Additionally, in R e and R f When the aryl group can have substituents, it is preferable that the total number of carbon atoms is 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0121] Examples of substituents mentioned above include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, epoxypropoxy, and mercapto.

[0122] As R in equation (6) e and R f Preferred specific examples may include methyl, phenyl, vinyl and propyl.

[0123] Furthermore, linear siloxane compounds also possess a siloxane structure. Examples of siloxane structures include those with the aforementioned R... e base and R f The base of -OSi(R) e R f The -OSi(R) structure of linear siloxane compounds is used in the polymerization process. e R f The O-site is introduced into the polysiloxane compound described in detail later.

[0124] In formula (6), m represents an integer of 2 to 10,000. The value of m in formula (6) is preferably 10 to 7,000, more preferably 100 to 2,000, and even more preferably 200 to 500.

[0125] In formula (6), X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group with a total carbon number of 1 to 10 that may have substituents, a hydrocarbon group with a total carbon number of 1 to 10 that may have substituents, oxygen atoms, or nitrogen atoms, or an amino group that may have substituents. Preferably, X is any one of a hydrogen atom, a hydroxyl group, an alkoxy group with a total carbon number of 1 to 10 that may have substituents, or an alkyl group with a total carbon number of 1 to 10 that may have substituents, more preferably a hydroxyl group or an alkyl group with a total carbon number of 1 to 10 that may have substituents, and even more preferably a hydroxyl group or an alkyl group with a total carbon number of 1 to 5.

[0126] Examples of substituents for X include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, epoxypropoxy, and mercapto.

[0127] The molecular weight of the linear siloxane compound shown in formula (6) is preferably 60,000 or less, more preferably 56,000 or less, further preferably 50,000 or less, and particularly preferably 45,000 or less. Additionally, the molecular weight of the linear siloxane compound shown in formula (6) is, for example, 1,000 or more, preferably 5,000 or more, and more preferably 10,000 or more.

[0128] In the cyclic siloxane compound of formula (5) above and the linear siloxane compound of formula (6) below, only a single siloxane compound may be used, or two or more siloxane compounds may be used in the form of a mixture. Furthermore, the siloxane compound of formula (5) or formula (6) may be used in combination with the above-mentioned (A) diaryloxysilane compound.

[0129] The aforementioned silane compounds can be synthesized using known methods or commercially available products.

[0130] [(II) Dihydroxy compounds]

[0131] As mentioned above, dihydroxy compounds are used in conjunction with silane-based compounds during the polymerization process. Examples of dihydroxy compounds include the following substances.

[0132] [(II-1) Aromatic dihydroxy compounds]

[0133] As shown in formulas (A) and (B) above regarding the overview of the polymerization reaction, the aromatic dihydroxy compounds used in the polymerization process are used to form the main chain of the polysiloxane compound.

[0134] As an aromatic dihydroxy compound used in the polymerization process, preferably a monomer that can become a material for polycarbonate resin, examples include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and 2,2-bis(4-hydroxy-3-methylphenyl)propane. 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3-methoxyphenyl)propane, 4,4′-dihydroxydiphenyl ether, 4,4′- Dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxyphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3′-dimethylphenyl sulfone 5-Trimethylcyclohexane, 4,4′-dihydroxybiphenyl, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 4,4′-sulfonyldiphenol, 2,2′-diphenyl-4,4′-sulfonyldiphenol, 2,2′-dimethyl-4,4′-sulfonyldiphenol, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1].[02,6] Decane, 4,4′-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(4-(2-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9- Bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene Fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthyl (BNE), 9,9-bis(6-(2-hydroxyethoxy)naphthyl-2-yl)fluorene (BNEF), 2,2′-bis(2-hydroxyethoxy)-6,6′-diphenyl-1,1′-binaphthyl, 2,2′-bis(2-hydroxyethoxy)-6,6′-bis(phenanthrene-9-yl)-1,1′-binaphthyl, etc. Preferably, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), and 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene (BPMEF) are preferred, and more preferably 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF).

[0135] [(II-2) Alicyclic dihydroxy compounds]

[0136] The following substances can be listed as alicyclic dihydroxy compounds used in the polymerization process.

[0137] That is, examples can be given of isosorbide (compounds in formulas (1-3) where L1 and L2 are 1, A1 and A2 are oxygen atoms, and J1, K1, J2, and K2 are 0):

[0138]

[0139] Spirocyclopentanediol (SPG) is shown in the following formula:

[0140]

[0141] Examples include decahydro-1,4:5,8-dimethylbridged naphthalene glycol (D-NDM, where R is a hydrogen compound in the following formula):

[0142]

[0143] (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; in preferred materials, R is hydrogen).

[0144] Cyclohexanediethanol as shown in the following formula:

[0145]

[0146] The following formula represents pentacyclic pentadecanediethanol (PCPMD):

[0147]

[0148] Tricyclic decanediethanol (TCDDM) is shown in the following formula:

[0149]

[0150] The following formula represents 1,3-adamantanediethanol and other adamantanediethanols:

[0151] wait.

[0152] The preferred polysiloxane compounds contain structural units derived from these alicyclic diols in their main chain.

[0153] The aforementioned polysiloxane compounds have high fluidity and are suitable for forming molded bodies, as well as for molding thin sheets, films, etc.

[0154] [(III) Carbonate compounds (optional)]

[0155] As shown in formula (B) above regarding the overview of the polymerization reaction, the carbonate compound is used to introduce the carbonyl (-CO-) group of the polycarbonate structural unit into the polysiloxane compound. That is, the two -OR groups of the carbonate compound represented by the general formula RO-CO-OR (R is independently selected from aryl, alkyl, and aralkyl), and for example, the two aryloxy groups (ArO-) when the carbonate compound is a diaryl carbonate represented by the general formula ArO-CO-OAr, are not introduced into the polymer chain of the polysiloxane compound. These -OR groups generate alcohols from the carbonate compound as byproducts, such as aryl alcohols (ArOH) such as phenol, which are generated as byproducts from carbonate compounds having aryloxy groups (ArO-).

[0156] Therefore, there is no particular limitation on the type of aryl, alkyl, and aralkyl groups in the carbonate compound. However, in order to facilitate the removal of byproducts from the reaction system during the polymerization process, it is preferable that the -OR group of the above general formula is an aryloxy group (or that the -R group of the above general formula RO-CO-OR is an aryl group) in the carbonate compound, and it is even more preferable that the carbonate compound has low polarity and low molecular weight, and that the -OR group of the above general formula is, for example, a phenoxy group.

[0157] As described above, in carbonate compounds, it is preferable that any one or two of the aforementioned Ar groups are aryl groups with a total carbon number of 10 or less, such as phenyl, benzyl, etc. That is, as preferred specific examples of carbonate compounds, diaryl carbonates such as diphenyl carbonate, dibenzyl carbonate, xylene carbonate, bis(chlorophenyl) carbonate, and m-toluene carbonate can be listed, but dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate, or monoaryl monoalkyl carbonates can also be used.

[0158] The aforementioned carbonate compounds can be synthesized using known methods or commercially available products can be used.

[0159] [(IV) Transesterification Catalyst]

[0160] The following substances can be used as transesterification catalysts in the polymerization process.

[0161] (IV-1) Phosphorus-based transesterification catalysts

[0162] As a transesterification catalyst in the polymerization process, a catalyst containing at least a phosphorus compound can be used.

[0163] Phosphorus-based transesterification catalysts preferably contain at least a compound represented by the following general formula (8): (PRe4) + (Xc) － ···(8)

[0164] In general formula (8), Re independently represents alkyl, aryl or alkylaryl, and multiple Re can be bonded to each other to form a ring structure, preferably an aryl with 6 to 16 carbon atoms.

[0165] In general formula (8), Xc is a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl carbonyloxy group, an aryl carbonyloxy group, HCO3, or BRf4 (Rf is independently a hydrogen atom, an alkyl group, or an aryl group), preferably an aryloxy group containing 6 to 16 carbon atoms, or BRf4 containing 6 to 16 carbon atoms as Rf4. Among these, the aryl groups containing 6 to 16 carbon atoms are preferably 6 to 12 carbon atoms, and more preferably 6 to 8 carbon atoms.

[0166] Specific examples of phosphorus-based transesterification catalysts include biphenyltriphenylphosphonium hydroxide, biphenyltriphenyltetraphenylboronic acid, biphenyltriphenylphenoxyphosphonium, biphenyltriphenylphosphonium chloride, tetraphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide, tetraphenyltetraphenylboronic acid, methoxyphenyltriphenyltetraphenylboronic acid, phenoxyphenyltriphenyltetraphenylboronic acid, naphthylphenyltriphenyltetraphenylboronic acid, tetraphenylphenoxyphosphonium, methoxyphenyltriphenylphenoxyphosphonium, phenoxyphenyltriphenylphenoxyphosphonium, naphthylphenyltriphenylphenoxyphosphonium, tetraphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride, naphthylphenyltriphenylphosphonium chloride, etc.

[0167] Among these, tetraphenylphenoxyphosphonium and tetraphenyltetraphenylborate phosphonium are particularly preferred. (IV-2) Alkali metal transesterification catalysts (catalysts containing basic compounds)

[0168] In the polymerization process, in addition to the phosphorus compound catalysts mentioned above, other transesterification catalysts can also be used. Among the transesterification catalysts that can be used besides phosphorus compound catalysts, catalysts containing basic compounds are preferred. Examples of basic compound catalysts include catalysts containing alkali metal compounds, alkaline earth metal compounds, etc., and examples of such compounds include inorganic salts, oxides, hydroxides, hydrides, or alkoxides of organic acid salts, carbonates, etc., of alkali metals and alkaline earth metal compounds. Alternatively, quaternary ammonium hydroxides or their salts, amines, etc., can be used as basic compound catalysts. Furthermore, these compounds can be used alone or in combination.

[0169] As a secondary transesterification catalyst used in conjunction with a phosphorus compound catalyst, the aforementioned basic compound catalysts preferably contain an alkali metal catalyst, namely an alkali metal carbonate, an alkali metal organoacid salt, or an alkali metal hydroxide. Specific examples of alkali metal catalysts include those containing cesium carbonate, potassium carbonate, sodium carbonate, sodium bicarbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, sodium acetate, sodium benzoate, etc. Therefore, sodium and other alkali metals are preferably included as components in the basic compound catalyst. That is, as a secondary transesterification catalyst, alkali metal-based catalysts containing at least sodium are preferred. By using alkali metal organoacid salts such as sodium acetate and sodium benzoate in conjunction with a phosphorus compound catalyst, the thermal stability of the polysiloxane compound can be improved.

[0170] The aforementioned secondary transesterification catalyst can be prepared according to known methods or commercially available products can be used.

[0171] [(V) Polymerization process]

[0172] In the polymerization process, at least the aforementioned (I) silane compound and (II) dihydroxy compound, together with (III) carbonate compound (optional), are polymerized in the presence of (IV) a transesterification catalyst. During this polymerization reaction, the mixture of the above components is melted into a molten state, and alcohols, such as aryl alcohols, which are byproducts from the silane compound and dihydroxy compound, are removed under reduced pressure. By setting the reaction conditions in this way, the polymerization reaction can be carried out efficiently.

[0173] In the polymerization process, the polymerization reaction is preferably carried out at a pressure of 400 Pa or less. That is, the pressure in the polymerization reaction is preferably in the range of 400 Pa or less.

[0174] In the polymerization process, it is preferable to maintain atmospheric pressure or a state with minimal pressure reduction for a certain period of time, and then reduce the pressure within the system to further carry out the polymerization reaction. For example, in the polymerization process, it is preferable to gradually reduce the reaction pressure from an initial atmospheric pressure to below 400 Pa in stages: 27,000 Pa, 24,000 Pa, 20,000 Pa, 16,000 Pa, 8,000 Pa, 4,000 Pa, 2,000 Pa, 400 Pa, and below 400 Pa. This stepwise pressure reduction within the reaction system, with the pressure reduction increasing midway through, suppresses the distillation of the feedstock and efficiently removes alcohols as byproducts, and is therefore preferred.

[0175] The polymerization time is appropriately determined based on factors such as the type of target polysiloxane compound, pressure, and temperature. For example, the total polymerization time is within 5 to 10 hours. More specifically, the reaction time before depressurization in the reaction system is 0.5 to 3 hours, preferably 1 to 2 hours, and the reaction time after depressurization is 1 to 5 hours, preferably 2 to 4 hours.

[0176] In the polymerization process, the temperature of the polymerization reaction is preferably in the range of 150 to 300°C. More preferably, the polymerization temperature is 180 to 290°C, and even more preferably, 200 to 280°C.

[0177] Furthermore, the components of the aforementioned silane compounds, aromatic dihydroxy compounds, and carbonate compounds such as diaryl carbonates (optional components) exhibit good compatibility with each other, enabling the production of polysiloxanes without the use of solvents during the polymerization process. Therefore, the polymerization process can be simplified.

[0178] In the polymerization process, the molar ratio of the transesterification catalyst to the dihydroxy compound (molar ratio, i.e., the molar amount of transesterification catalyst / the molar amount of dihydroxy compound) is preferably 1.0 × 10⁻⁶. －7~1.0×10 －2 (mol / mol: 0.1~10000μmol / mol or 1.0×10) －4 ~10 mmol / mol). A more preferred molar ratio is 1.0 × 10⁻⁶. －7 ~2.0×10 －5 mol / mol (or 0.1–20 μmol / mol).

[0179] In the polymerization process, the molar ratio of the dihydroxy compound to the silane compound (i.e., the molar number of the silane compound / the molar number of the dihydroxy compound) is, for example, 0.8 to 1.3, preferably 0.9 or more and 1.2 or less, more preferably 0.9 or more and 1.25 or less, and even more preferably 0.95 or more and 1.2 or less.

[0180] Furthermore, in the polymerization process, when using carbonate compounds such as diaryl carbonate, the molar ratio of the dihydroxy compound to the total number of moles of the carbonate compound and the silane compound (i.e., the value of (total number of moles of carbonate compound and silane compound) / moles of the dihydroxy compound) is preferably 0.9 to 1.2 or less, more preferably 0.95 to 1.15 or less.

[0181] The polysiloxane of the present invention will now be described in detail.

[0182] <2. Polysiloxane>

[0183] [(I) Structural Units]

[0184] The polysiloxanes manufactured by the method of the present invention are polymers having siloxane structural units as described above, and the following polymers can be specifically listed.

[0185] That is, polysiloxane is a polymer having at least one of the siloxane structural units shown in any of the following formulas (1-1) to (1-4).

[0186]

[0187] Equations (1-1) to (1-4) contain R 1 and R 2 The siloxane structure is introduced by the above-mentioned diaryloxysilane compound, dialkyldialkoxysilane, or silicon compound (siloxane compound).

[0188] In equations (1-1) to (1-4), R 1 and R 2 Each can be independently represented as an alkyl group having a total of 1 to 20 carbon atoms that may have substituents, or an aryl group having a total of 6 to 30 carbon atoms that may have substituents.

[0189] In R 1 and R 2 When the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2.

[0190] Additionally, in R 1 and R 2 When the aryl group can have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0191] In equations (1-1) and (1-2), R 3 ~R 10 and R 30 ~R 33 Each can be independently represented as hydrogen, halogen, alkoxy, alkyl with a total number of carbon atoms of 1 to 20 that may have substituents, alkenyl with a total number of carbon atoms of 2 to 20 that may have substituents, or aryl with a total number of carbon atoms of 6 to 30 that may have substituents.

[0192] In R 3 ~R 10 and R 30 ~R 33 When the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2.

[0193] In R 3 ~R 10 and R 30 ~R 33 When the alkenyl group can have substituents, the total number of carbon atoms is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

[0194] Additionally, in R 3 ~R 10 and R 30 ~R 33 When the aryl group can have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0195] In formulas (1-1) to (1-3), Z1 and Z2 are independently alkylene groups having a total number of carbon atoms of 1 to 5, preferably alkylene groups having a total number of carbon atoms of 1 to 3, and more preferably alkylene groups having a total number of carbon atoms of 1 or 2.

[0196] In equations (1-1) to (1-3), J1 and K1 independently represent integers of 0 to 5, preferably integers of 0 to 3, more preferably integers of 0 to 2, for example, 1 or 2.

[0197] In equation (1-3), A1 and A2 independently represent either -O- or -CH-.

[0198] L1 and L2 independently represent integers above 0 and below 3, and L1 and L2 are preferably 1 or 2.

[0199] In equations (1-1) and (1-2), X is independently a single bond or any of the structural formulas shown in equation (2).

[0200]

[0201] In equation (2), R 11 and R 12 Each can independently represent hydrogen, halogen, alkyl groups with a total carbon number of 1 to 20 that may have substituents, or aryl groups with a total carbon number of 6 to 30 that may have substituents, or represent R. 11 and R 12 Carbon rings or heterocycles with 1 to 20 carbon atoms that are bonded together can have substituents.

[0202] a and b independently represent integers above 0 or 1 and below 5000.

[0203] R 11 and R 12 Preferably, each is hydrogen, an alkyl group having a total carbon number of 1 to 10 that may have substituents, or an aryl group having a total carbon number of 6 to 16 that may have substituents.

[0204] In equation (2), a and b are independently integers of 0 or 1 to 5000, and a and b are preferably integers of 1000 or less, more preferably integers of 500 or less, and even more preferably integers of 100 or less.

[0205] Furthermore, in the siloxane structural unit, X is preferably composed of R. 11 and R 12 Fluorene rings are formed by bonding together.

[0206] The optional substituents mentioned above in formulas (1-1) to (1-4), (2), etc., are independently selected from halogen, cyano, alkenyl, alkynyl, and alkoxy groups.

[0207] In addition, the siloxane structural unit preferably includes at least the structure shown in formula (1).

[0208]

[0209] Equation (1) contains R 1 and R 2 The siloxane structure is introduced by the above-mentioned diaryloxysilane compound, diekoxysilane compound or silicon compound (siloxane compound).

[0210] In equation (1), R 1 and R 2 Each can independently represent an alkyl, alkenyl, or aryl group that may have substituents. R in formula (1) 1 and R 2 They are alkyl groups having a total of 1 to 20 carbon atoms or aryl groups having a total of 6 to 30 carbon atoms, respectively.

[0211] Regarding R 1 and R 2 The preferred option is R in equations (1-1) to (1-4) above. 1 and R 2 same.

[0212] As mentioned above, R 1 and R 2 Substituents can include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, epoxypropoxy, mercapto, etc.

[0213] As R in equation (1) 1 and R 2 Preferred specific examples may include methyl, phenyl, vinyl and propyl.

[0214] In equation (1), regarding R 3 ~R 10 The preferred option is R in equations (1-1) to (1-4) above. 3 ~R 10 same.

[0215] As mentioned above, R 3 ~R 10 Substituents can include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, epoxypropoxy, mercapto, etc.

[0216] In formula (1), X is the same as X in formulas (1-1) and (1-2) above. In addition, the optional substituents mentioned above in formula (1) are preferably selected independently from halogen, cyano, alkenyl, alkynyl, and alkoxy groups, respectively.

[0217] The polysiloxane compound is preferably a polymer having a siloxane structural unit shown in any of the following formulas (1-1′) to (1-4′).

[0218]

[0219] R in equations (1-1′)~(1-4′) 1 ~R 10 The symbols Z1, Z2, J1, K1, A1, A2L1, L2, X, etc., which are shared with equations (1-1) to (1-4), have the same meanings as those in equations (1-1) to (1-4).

[0220] In addition, the siloxane structural unit preferably includes at least the structural unit shown in the following formula (1′).

[0221]

[0222] R in equation (1′) 1 ~R 10 The symbols shared with Equation (1) have the same meaning as those in Equation (1).

[0223] Furthermore, in equations (1-1') to (1-4') above, m1 to m4, and in equation (1'), m, each independently represents an integer of 10 to 1,000. The values ​​of m1 to m4 and m are preferably 20 to 800 and more preferably 30 to 500.

[0224] In addition, the optional polycarbonate structural unit in the polysiloxane is preferably represented by any of the following formulas (3-1) to (3-4).

[0225]

[0226] In (3-1) to (3-2), R 13 ~R 20 and R 40 ~R 51 Each can be independently represented as hydrogen, halogen, alkoxy, alkyl with a total number of carbon atoms of 1 to 20 that may have substituents, alkenyl with a total number of carbon atoms of 2 to 20 that may have substituents, or aryl with a total number of carbon atoms of 6 to 30 that may have substituents.

[0227] In R 13 ~R 20 and R 40 ~R 51 When the alkyl group may have substituents, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2.

[0228] In R 13 ~R 20 and R 40 ~R 51When the alkenyl group can have substituents, the total number of carbon atoms is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

[0229] Additionally, in R 13 ~R 20 and R 40 ~R 51 When the aryl group can have substituents, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

[0230] In formulas (3-1) to (3-3), Z3 and Z4 are independently alkylene groups having 1 to 5 carbon atoms, preferably alkylene groups having 1 to 3 carbon atoms, and more preferably alkylene groups having 1 or 2 carbon atoms.

[0231] In equations (3-1) to (3-3), J2 and K2 independently represent integers of 0 to 5, preferably integers of 0 to 3, and more preferably 1 or 2.

[0232] In equation (3-3), A1 and A2 independently represent either -O- or -CH-.

[0233] L1 and L2 represent integers above 0 and below 3 independently, and L1 and L2 are preferably above 0 and below 2.

[0234] In addition, the optional substituents of formulas (3-1) to (3-4) are preferably selected independently from halogen, cyano, alkenyl, alkynyl, and alkoxy.

[0235] In equations (3-1) to (3-2), Y is either a single bond or any of the structural formulas shown in equation (4).

[0236]

[0237] (where R is in the formula) 21 and R 22 Each can independently represent hydrogen, halogen, alkyl groups with 1 to 20 carbon atoms that may have substituents, or aryl groups with 6 to 30 carbon atoms that may have substituents, or represent R... 21 and R 22 A carbon ring or heterocycle with 1 to 20 carbon atoms that can have substituents, formed by bonding together, where c and d independently represent 0 or an integer greater than 1 and less than 5000.

[0238] R 21 and R 22Preferably, each is independently hydrogen, an alkyl group having 1 to 10 carbon atoms that may have substituents, or an aryl group having 6 to 16 carbon atoms that may have substituents.

[0239] In equation (4), c and d are each independently an integer of 0 or 1 to 5000, and c and d are preferably integers of 1000 or less, more preferably integers of 500 or less, and even more preferably integers of 100 or less.

[0240] Furthermore, in the polycarbonate structural unit, Y is preferably composed of R. 11 and R 12 Fluorene rings are formed by bonding together.

[0241] The polycarbonate structural unit preferably includes at least the structural unit shown in formula (3).

[0242]

[0243] In equation (3), regarding R 13 ~R 20 The preferred option is R in equations (3-1) to (3-2) above. 3 ~R 10 same.

[0244] As mentioned above, R 13 ~R 20 Substituents can include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth)acryloyloxy, epoxypropoxy, mercapto, etc.

[0245] In equation (3), Y is the same as Y in equations (3-1) to (3-2) above.

[0246] [(II) Properties of Polysiloxanes]

[0247] The weight-average molecular weight of the polysiloxane is preferably 10,000 to 300,000, more preferably 10,000 to 200,000, even more preferably 10,000 to 100,000, for example, more preferably 20,000 to 80,000, even more preferably 30,000 to 70,000, and particularly preferably 40,000 to 65,000.

[0248] In polysiloxanes, the molar number of siloxane structural units is preferably 1 to 1000. Furthermore, when polycarbonate structural units are included, the molar number is preferably 1 to 1000. These molar numbers refer to the number of structural units contained in one polysiloxane compound molecule, more preferably 10 to 800, and even more preferably 100 to 600.

[0249] In polysiloxanes, the proportion of siloxane structural units in the total molar number of siloxane structural units and polycarbonate structural units is preferably 2.0% or more and 90% or less. More preferably, the proportion of siloxane structural units is 3.0% or more, for example, greater than 3.1% and 90% or less, even more preferably 5% or more and 90% or less, and particularly preferably 8% or more and 90% or less.

[0250] Furthermore, when polysiloxanes are not used directly alone but are mixed with other resins to form a composition, it is sometimes preferable to significantly increase the proportion of the aforementioned siloxane structural units. For example, by mixing polysiloxanes with high Si content with polymers that do not contain Si or siloxane structural units, as detailed later, with a proportion of 30% or more, 50% or more, or 70% or more of the aforementioned siloxane structural units, it is possible to achieve a resin with excellent properties, such as high impact resistance and flowability. Additionally, when the proportion of siloxane structural units is preferably increased as described above, the upper limit of the proportion of the aforementioned siloxane structural units is not limited to 90%, and may also be, for example, 92%, 95%, 98%, etc.

[0251] In polysiloxane compounds, the molar ratio of siloxane structural units to polycarbonate structural units (i.e., the ratio of the number of moles of siloxane structural units to the number of moles of polycarbonate structural units) is preferably 0.01:99.99 to 99.99:0.01. More preferably, the molar ratio is 0.1:99.9 to 99.9:0.1, and even more preferably, 30:70 to 99.9:0.01, but other ranges are also possible, such as 1:99 to 99:1, 10:90 to 90:10, etc.

[0252] In polysiloxanes, the Q value (the melt flow volume per unit time measured at 280°C and a load of 160 kg, × 10) is... －2 cm 3 s －1 The preferred value is 8 (×10) －2 cm 3 s －1 The Q value is more preferably 20 (×10) or higher. －2 cm 3 s －1 ) or more, and more preferably 40 (×10) －2 cm 3 s －1 ) or more, especially preferably 60 (×10) －2 cm 3 s －1 )above.

[0253] In polysiloxanes, the glass transition temperature (Tg) based on JIS K7121 is, for example, 40–200°C, preferably 45–180°C, and more preferably 50–160°C.

[0254] In the aforementioned polysiloxanes, i.e., polysiloxanes having at least one siloxane structural unit as shown in any of formulas (1-1) to (1-4), the low molecular weight compound with a weight average molecular weight of 1,000 or less is preferably 30% by weight or less, more preferably 20% by weight or less, further preferably 10% by weight or less, further more preferably 5.0% by weight or less, particularly preferably 1.5% by weight or less, and further preferably less than 1.0% by weight. Polysiloxanes containing a large amount of low molecular weight compounds with a weight average molecular weight of 1,000 or less tend to have the mold (mold) contaminated with trace amounts of deposits (mold deposits) in the early stages of continuous injection molding for manufacturing optical discs or complex, thin-walled products. Regarding this, if the amount of low molecular weight compounds with a weight average molecular weight of 1,000 or less is less than 1.5% by weight in the polysiloxane, mold contamination can be effectively prevented.

[0255] Furthermore, the lower limit for the content of low molecular weight compounds with a weight average molecular weight of 1,000 or less in polysiloxanes is not particularly important and can be around 0.7% by weight. However, even if the polysiloxane contains approximately 0.001%, 0.01%, or 0.1% by weight or more of the aforementioned low molecular weight compounds, the properties of the polysiloxane, especially when used in optical applications, are not problematic, and the effect of improved flowability can also be confirmed. Therefore, the lower limit for the content of low molecular weight compounds with a weight average molecular weight of 1,000 or less in polysiloxanes can be 0.001%, 0.01%, or 0.1% by weight.

[0256] The content of the aforementioned low molecular weight compounds in the polysiloxane is calculated by summing the contents of several low molecular weight compounds as impurities, based on the ratio of the peak areas of each component obtained by GPC analysis. That is, as explained in detail below, the proportion of low molecular weight compounds with a molecular weight of 1,000 or less in the polysiloxane is calculated based on the ratio of the area of ​​the retention time of 20.5 min to 21.5 min under specified GPC analysis conditions to the area of ​​the retention time of 0 min to 21.5 min.

[0257] In the above-mentioned polysiloxane, that is, polysiloxane having at least one of the siloxane structural units shown in formulas (1-1) to (1-4), the total content of the cyclic bodies shown in formulas (5-1) to (5-3) is preferably 4.0% by weight or less, more preferably 3.0% by weight or less, further preferably 2.0% by weight or less, and particularly preferably 1.0% by weight or less, based on the total weight of the polysiloxane.

[0258] When the content of these cyclic dimers is within the above range, the properties of polysiloxanes, especially when used in optical applications, are generally acceptable.

[0259]

[0260] In equations (5-1) to (5-3), m and n represent the total number of structural units containing the (-OSi(R1R2)O-) portion and the total number of structural units containing the (-OC(=O)O-) portion in each annulus. That is, when the annulus in equation (5-1) contains structural units other than those containing the (-OSi(R1R2)O-) portion, and when the annulus in equation (5-2) contains structural units other than those containing the (-OC(=O)O-) portion, m and n respectively represent the total number of the structural units shown in the equation in the annulus. In particular, in equation (5-3), structural units containing the (-OSi(R1R2)O-) portion and structural units containing the (-OC(=O)O-) portion are mixed, including annulus where they are arranged alternately, m and n also respectively represent the total number of the structural units shown in the equation in the annulus.

[0261] In formula (5-1), m represents an integer from 2 to 10, preferably 2 to 5, more preferably 2 or 3, and even more preferably 2.

[0262] In formula (5-2), n represents an integer from 2 to 10, preferably 2 to 5, more preferably 2 or 3, and even more preferably 2.

[0263] In equation (5-3), the total value of m is 1 to 10, and the total value of n is 1 to 10. Furthermore, m and n are preferably 1 to 5, more preferably 1 or 2, and even more preferably 1.

[0264] Furthermore, in Equation (5-3), as described above, the configuration of structural units containing the (-OSi(R1R2)O-) portion and structural units containing the (-OC(=O)O-) portion in the annular body of Equation (5-3) is arbitrary.

[0265] In formulas (5-1) to (5-3), X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms that may have substituents, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms.

[0266] i and ii independently represent integers above 0 and below 5, preferably integers above 0 and below 3, more preferably 1 or 2.

[0267] Furthermore, in equations (5-1) to (5-3), R1 R 2 R 3 ~R 10 R 13 ~R 20 And X are respectively related to R in equations (1-1) and (1-2) 1 R 2 R 3 ~R 10 R 13 ~R 20 Same as X.

[0268] In addition, as specific examples of compounds of formulas (5-1) to (5-3), the following cyclic forms of formulas (5-1′) to (5-3′) can be listed.

[0269]

[0270] In formula (5-1'), m = 2 or 3, preferably m = 2; in formula (5-2'), n = 2 or 3, preferably n = 2; in formula (5-3'), m = any one of 1 to 3 and n = any one of 1 to 3, preferably both 1 or 2, more preferably both 1.

[0271] Furthermore, the polysiloxane may contain a total amount of the cyclic bodies shown in formulas (6-1) and (6-2). These cyclic bodies can be considered as cyclic dimers generated by the side reactions of the polymerization reaction used to manufacture the polysiloxane. Regarding the total amount of these cyclic dimers in the polysiloxane, based on the total weight of the polysiloxane, it is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, further preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less.

[0272]

[0273] In equations (6-1) and (6-2), R 1 R 2 R 3 ~R 10 R 30 ~R 33 The meanings of X and X are the same as those in equations (1-1) and (1-2).

[0274] In equations (6-1) and (6-2),

[0275] X1 and X2 are each independently an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms.

[0276] i and ii independently represent integers greater than or equal to 0 and less than 5, preferably integers greater than or equal to 0 and less than 3, and more preferably 1 or 2.

[0277] n represents an integer from 2 to 10, preferably an integer from 2 to 5, more preferably 2 or 3, for example 2.

[0278] Furthermore, there is no particular limitation on the lower limit of the total content of the cyclic dimers shown in formulas (6-1) and (6-2) contained in the polysiloxane, for example, it can be 0.001 wt%, 0.01 wt%, or 0.1 wt%. The presence of a small amount of cyclic dimers helps to improve the flowability of the polysiloxane during molding.

[0279] In addition, as specific examples of compounds of formulas (6-1) and (6-2), the following cyclic forms of formulas (6-1′) and (6-2′) can be listed.

[0280]

[0281] In equations (6-1′) and (6-2′), R 1 and R 2 R 3 ~R 10 and R 30 ~R 33 Z1 and Z2, J1, K1 and X are as described above.

[0282] In polysiloxanes, a 1% mass reduction in thermal decomposition temperature of 300°C or higher is preferred, a 1% mass reduction in thermal decomposition temperature of 320°C or higher is more preferred, a 1% mass reduction in thermal decomposition temperature of 330°C or higher is even more preferred, and a 1% mass reduction in thermal decomposition temperature of 350°C or higher is particularly preferred.

[0283] In polysiloxanes, the mass reduction ratio at 500°C, measured according to the method described in detail below, is preferably 40% or less, more preferably 30% or less, further preferably 25% or less, even more preferably 20% or less, and particularly preferably 17% or less.

[0284] That is, the mass retention rate (%) of the polysiloxane at 500°C is 100 minus the value of "mass reduction rate (%) at 500°C", and this mass retention rate (%) is preferably 40% or more, more preferably 50% or more or 60% or more, further preferably 70% or more, further more preferably 75% or more, further more preferably 80% or more, and particularly preferably 83% or more.

[0285] Details regarding the mass reduction percentage (%) at 500°C will be provided in the examples below.

[0286] In polysiloxanes, the proportion of the total weight of silicon atoms (total Si content) based on the total weight of the polysiloxane is preferably 0.1 to 20% by mass, more preferably 1.0 to 15% by mass, further preferably 2.0 to 12% by mass, and particularly preferably 3.0 to 10% by mass (e.g., more than 3.1% by mass, or more than 3.1% by mass but less than 9.8% by mass).

[0287] The compositions involved in this invention, namely compositions containing the above-mentioned polysiloxanes, will now be described in detail.

[0288] <3. Composition>

[0289] The compositions of the present invention contain the aforementioned polysiloxane and polycarbonate resin. Examples of polycarbonate resins that are completely free of, or substantially free of, siloxane structures can be cited.

[0290] In the compositions of the present invention, for example, based on the total weight of the composition, polysiloxane is contained in proportions of 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, or 95% by weight or more.

[0291] Regarding the types of polycarbonate resins mentioned above, there are no particular limitations as long as they contain a -[O-R-OCO]- unit with a carbonate bond in the main molecular chain (R being an aliphatic group, an aromatic group, or a group containing both aliphatic and aromatic groups, or a group having a straight-chain structure or a branched structure). Furthermore, polycarbonate resins may contain polyester carbonates. Similarly, polyester carbonates are not particularly limited as long as they contain a -[O-R-OC]- unit with a carbonate bond in the main molecular chain (R as described above).

[0292] The weight-average molecular weight of the polycarbonate resin is preferably 10,000 to 100,000, more preferably 13,000 to 80,000, and even more preferably 15,000 to 60,000.

[0293] The compositions of the present invention may contain resins other than polycarbonate resins, preferably thermoplastic resins. There is no particular limitation on the type of thermoplastic resin; in addition to polycarbonate resins and polyester carbonate resins, examples include acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide (PI), cyclic olefin copolymers (COC), resins containing norbornene, polyethersulfone, cellulol, aromatic polyamides, and various other resins.

[0294] In the composition, the proportion of the total weight of silicon atoms (total Si content) based on the total weight of the composition is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and particularly preferably 0.3 to 10% by mass. The proportion of total Si content in the composition can be adjusted by the proportion of siloxane structural units in the polysiloxane in all structural units, or by the amount of resin mixed with polycarbonate resin or the amount of Si.

[0295] The Q value (Q1) of the composition containing polysiloxane, measured at 280°C and 160 kgf, is preferably 120% or more (20% or more higher) than the Q value (Q2) of the polycarbonate resin contained in the composition alone, measured under the same conditions. The Q1 value of the entire composition is more preferably 130% or more, further preferably 140% or more, particularly preferably 150% or more, and for example 160% or more, compared with the Q2 value of polycarbonate alone.

[0296] Furthermore, for example, in the case of a composition containing 5% by mass of polysiloxane, the Q value, i.e., Q1, measured at 280°C and 160 kgf, is preferably 140% or more (40% or more higher) than the Q value, i.e., Q2, measured under the same conditions for only the polycarbonate resin contained in the composition. The Q1 value of the entire composition is more preferably 150% or more, further preferably 160% or more, particularly preferably 170% or more, and for example, 180% or more, compared with the Q2 value of polycarbonate alone.

[0297] Using polysiloxanes with high Si content, compositions with excellent properties can be manufactured. By mixing polysiloxanes with a Si content of, for example, 0.1% by mass or more with a resin that is substantially free of siloxane structural units, preferably a polycarbonate resin, the resulting composition can possess both excellent impact resistance and flowability.

[0298] Furthermore, compositions containing polysiloxanes may contain phenolic compounds generated as byproducts of the polymerization reaction, or unreacted silane compounds, carbonate compounds, and dihydroxy compounds. Phenolic compounds and DPC (diphenyl carbonate), as impurities, may cause a decrease in strength or the generation of odor when the molded body is formed; therefore, their content is preferably as low as possible. Thus, the content of phenolic compounds, silane compounds, carbonate compounds, and dihydroxy compounds is preferably so low as to be undetectable, but from a productivity point of view, they may be included in the composition within a range that does not impair the effect. Additionally, based on the total weight of the composition, by containing a specified amount of residual monomer, for example, 1 to 1000 ppm by weight, preferably 10 to 900 ppm, more preferably 20 to 800 ppm, the effect of improved flowability during molding and good plasticity of the resin during melting can be obtained.

[0299] The molded articles of the present invention containing polysiloxane will now be described.

[0300] <4. Molded Body>

[0301] The molded articles involved in this invention are obtained by molding the aforementioned polysiloxane or a composition containing polysiloxane. There are no particular limitations on the molding method of the molded articles; examples of molded articles include injection molded articles, compression molded articles, blow molded articles, extrusion molded articles, vacuum molded articles, and air-molded articles.

[0302] Furthermore, the optical lenses and molded bodies according to the present invention are obtained by molding the polysiloxane of the present invention, or a composition containing polysiloxane. The polysiloxane of the present invention is suitable for optical applications, and the optical lenses of the present invention have refractive index, Abbe number, etc., suitable for use as lenses.

[0303] <5. Regarding secondary components>

[0304] Deactivating agent

[0305] To maintain the thermal and hydrolytic stability of the polysiloxane of the present invention after polymerization, the catalyst can be removed or deactivated. A method of deactivating the catalyst by adding a known acidic substance can be appropriately implemented. Specifically suitable acidic substances include: esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonates such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphite esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; and phosphite esters such as triphenyl phosphate, diphenyl phosphate, and phosphoric acid. Phosphate esters such as monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonates such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonate esters such as diethyl phenylphosphonate; phosphine derivatives such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboronic acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organohalides such as stearoyl chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfuric acids such as dimethyl sulfuric acid; and organohalides such as benzyl chloride. The amount of these deactivating agents used is, for example, 0.001 to 50 moles, preferably 0.01 to 30 moles, relative to the amount of catalyst.

[0306] additive

[0307] <Stabilizer>

[0308] The polysiloxane of the present invention can be supplemented with a stabilizer. Examples of stabilizers include heat stabilizers and antioxidants. Regarding the proportion of stabilizer added, in the case of a compound, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.02 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1.4 parts by mass or less, and further preferably 1.0 parts by mass or less, relative to 100 parts by mass of the polysiloxane compound. The stabilizer may contain only one type or two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0309] <<Heat Stabilizer>>

[0310] As heat stabilizers, phenolic, phosphorus-based, and sulfur-based heat stabilizers can be listed. Specifically, examples include: oxyacids of phosphorus such as phosphoric acid, phosphonic acid, phosphorous acid, hypophosphonic acid, and polyphosphoric acid; acidic metal pyrophosphates such as sodium pyrophosphate, potassium pyrophosphate, and calcium pyrophosphate; phosphates of Group 1 or Group 10 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organophosphate esters, organophosphites, and organophosphonates. Furthermore, at least one of the following can be listed: phosphites (a), phosphorous acid (b), and tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenyl-diphosphonate (c), which are esterified by phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms. Specific examples of phosphite compounds (a) include trioctyl phosphite, tri-octadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tri(mononylphenyl) phosphite, tri(mononyl / dinonyl-phenyl) phosphite, trinonylphenyl phosphite, tri(octylphenyl) phosphite, tri(2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, and bis(2,4-di-tert-butylphenyl) phosphite. (Butylphenyl) pentaerythritol phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, monooctyl diphenyl phosphite, distearate pentaerythritol diphosphite, tricyclohexyl phosphite, diphenyl pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis(4,6-di-tert-butylphenyl) octyl phosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, etc. These can be used alone or in combination of two or more.

[0311] Examples of organophosphite compounds include "ADK STAB1178" (trade name, hereinafter the same), "ADK STAB 2112" and "ADK STAB HP-10" produced by ADEKA CORPORATION, "JP-351", "JP-360" and "JP-3CP" produced by Jōhoku Chemical Industry Co., Ltd., and "Irgafos 168" produced by BASF.

[0312] In addition, examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tri(nonylphenyl) phosphate, and 2-ethylphenyl diphenyl phosphate.

[0313] Regarding the proportion of heat stabilizer added, in the case of compounding, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.03 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.7 parts by mass or less, and even more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the polysiloxane compound.

[0314] The heat stabilizer may contain only one type or two or more types. When it contains two or more types, the total amount is preferably within the range mentioned above.

[0315] <<Antioxidants>>

[0316] As antioxidants, examples include phenolic antioxidants, hindered phenolic antioxidants, bisphenol antioxidants, and polyphenol antioxidants. Specific examples include 2,6-di-tert-butyl-4-methylphenol, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate, tetra[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 4,4′-butylenebis-(3-methyl-6-tert-butylphenol), and triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methyl-6-methyl-6-methylphenol]. [3,9-Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N′-hexane-1,6-dimethyl Bis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(trimethylbenzene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)o-cresol, ethylidene bis( Examples of such products include oxoethylene bis[3-(5-tert-butyl-4-hydroxym-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol.

[0317] Examples of phenolic antioxidants include BASF's "Irganox 1010" (registered trademark, hereinafter the same) and "Irganox 1076", and ADEKA CORPORATION's "ADK STAB AO-50" and "ADK STAB AO-60".

[0318] Regarding the proportion of antioxidants added, in the case of compounding, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and more preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, relative to 100 parts by mass of the polysiloxane compound.

[0319] The antioxidant may contain only one type or two or more types. When containing two or more types, the total amount is preferably within the range mentioned above.

[0320] In the polysiloxane compounds of the present invention, various additives may be incorporated without departing from the spirit of the invention. Examples of additives include at least one selected from flame retardants, flame retardant auxiliaries, ultraviolet absorbers, release agents, and colorants, preferably containing at least one of flame retardants and release agents.

[0321] In addition, as long as the desired physical properties are not significantly impaired, antistatic agents, fluorescent whitening agents, antifogging agents, flow improvers, plasticizers, dispersants, antibacterial agents, etc., can also be added.

[0322] <Flame retardant>

[0323] In the polysiloxane compounds of the present invention, various additives may be incorporated without departing from the spirit of the invention. As flame retardants, organometallic salt flame retardants, phosphorus-based flame retardants, organosilicon-based flame retardants, etc., may be incorporated. Examples of flame retardants (flame retardant compositions) that can be used in the present invention include those described in paragraphs 0085 to 0093 of Japanese Patent Application Publication No. 2016-183422, the contents of which are incorporated herein by reference.

[0324] <Ultraviolet Absorber>

[0325] In addition to inorganic UV absorbers such as cerium oxide and zinc oxide, organic UV absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxaloyl aniline compounds, malonic acid ester compounds, hindered amine compounds, and phenyl salicylate compounds can also be listed as UV absorbers. Among these, benzotriazole-based or benzophenone-based organic UV absorbers are preferred. Specific examples of benzotriazole compounds include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-[2′-hydroxy-3′,5′-bis(α,α-dimethylphenylmethyl)phenyl]-benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butyl-phenyl)-benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butyl-phenyl)-benzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-butyl-phenyl)-5-chlorobenzotriazole, and 2-(2′-hydroxy-3′,5′-di-tert-butyl-phenyl)-benzotriazole. 2-(2′-hydroxy-3′,5′-ditert-pentyl)-benzotriazole, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazole-2-yl)phenol], 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4,6-bis(2,4-dimethylphenyl)-1 [3,5-triazine-2-yl]-5-(octyloxy)phenol, 2,2′-(1,4-phenylene)bis[4H-3,1-benzoxazine-4-one], [(4-methoxyphenyl)-methylene]-propanediol-dimethyl ester, 2-(2H-benzotriazine-2-yl)p-cresol, 2-(2H-benzotriazine-2-yl)-4,6-bis(1-methyl-1-phenylmethyl)phenol, 2-[5-chloro(2H)-benzotriazine-2-yl]-4-methyl-6 -(tert-butyl)phenol, 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetrabutyl)phenol], [methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol] condensate, etc. Among the above, 2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole and 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol] are preferred.Specific examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and 2,2′,4,4′-tetrahydroxybenzophenone. Specific examples of phenyl salicylate-based ultraviolet absorbers include phenyl salicylate and 4-tert-butyl-phenyl salicylate. Furthermore, specific examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol and 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol. Additionally, specific examples of hindered amine-based ultraviolet absorbers include bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

[0326] Regarding the proportion of the ultraviolet absorber added, in the case of compounding, it is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 3 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the polysiloxane compound.

[0327] One type of ultraviolet absorber may be used, or two or more types may be used. When using two or more types, it is preferable that the total amount is within the range mentioned above.

[0328] <Mold Release Agent>

[0329] Release agents can include carboxylic acid esters, polysiloxane compounds, paraffin (polyolefin-based), etc. Specifically, at least one compound selected from aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils can be included. As aliphatic carboxylic acids, saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids can be included. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids with 6 to 36 carbon atoms, more preferably saturated aliphatic mono-carboxylic acids with 6 to 36 carbon atoms. Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, hexanoic acid, decanoic acid, lauric acid, arachidic acid, benzyl acid, ceramide, beeswax acid, tetracosanoic acid, linaloic acid, glutaric acid, adipic acid, azelaic acid, etc. As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and alcohol, the same carboxylic acid as the aforementioned aliphatic carboxylic acids can be used. On the other hand, examples of alcohols include saturated or unsaturated mono- or poly-hydric alcohols. These alcohols may have substituents such as fluorine atoms or aryl groups. Among these, mono- or poly-hydric saturated alcohols with 30 or fewer carbon atoms are preferred, and aliphatic saturated mono- or poly-hydric alcohols with 30 or fewer carbon atoms are more preferred. Aliphatic compounds also include alicyclic compounds. Specific examples of alcohols include octanol, decanol, dodecanol, stearyl alcohol, betaine alcohol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentyl glycol, bis(trimethylolpropane), dipentaerythritol, etc. Furthermore, the above-mentioned ester compounds may contain aliphatic carboxylic acids and / or alcohols as impurities, or they may be mixtures of various compounds. Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture mainly composed of beeswax palmitate), stearate stearate, benzyl benzyl acid, stearate benzyl acid, glyceryl monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate. Examples of aliphatic hydrocarbons with a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch synthetic wax, and α-olefin oligomers with 3 to 12 carbon atoms. Aliphatic hydrocarbons also include alicyclic hydrocarbons. Furthermore, these hydrocarbon compounds can be partially oxidized. Among these, paraffin wax, polyethylene wax, or partial oxides of polyethylene wax are preferred, and paraffin wax and polyethylene wax are more preferred. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons can be single substances or mixtures of aliphatic hydrocarbons with different constituent components or molecular weights, as long as the main component is within the above-mentioned range. Examples of polysiloxane-based silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl organosilicones. Two or more of these can be used in combination.

[0330] Regarding the addition ratio of the release agent, in the case of compounding, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and more preferably 2 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the polysiloxane compound.

[0331] One type of release agent may be used, or two or more types may be used. When using two or more types, it is preferable that the total amount is within the range mentioned above.

[0332] <Coloring agent>

[0333] Coloring agents can be either dyes or pigments, such as inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include: sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; oxide pigments such as titanium dioxide, zinc white, iron oxide red, chromium oxide, iron black, titanium yellow, zinc-iron brown, titanium-cobalt green, cobalt green, cobalt blue, copper-chromium black, and copper-iron black; chromic acid pigments such as lead yellow and molybdenum orange; and ferrocyanide pigments such as Prussian blue. In addition, examples of organic pigments and dyes used as coloring agents include phthalocyanine pigments such as copper phthalocyanine blue and copper phthalocyanine green (the term "pigment" is used to refer to dyes or pigments, hereinafter the same); azo pigments such as nickel azo yellow; fused polycyclic pigments such as thioindole, pyrene, perylene, quinacridone, dioxazine, isoindolinone, and quinoline; and quinoline, anthraquinone, heterocyclic, and methyl pigments. Furthermore, from the viewpoint of thermal stability, titanium dioxide, carbon black, phthalocyanine, quinoline, anthraquinone, and phthalocyanine pigments are preferred.

[0334] In addition, for the purpose of improving operability during extrusion and improving dispersibility in resin compositions, colorants may also be substances obtained by mastering polystyrene resins, polycarbonate resins, or acrylic resins.

[0335] Regarding the proportion of colorant added, in the case of a compound, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, and at least 0.1 parts by mass, relative to 100 parts by mass of the polysiloxane compound. Only one type of colorant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above-mentioned range.

[0336] <6. Shaped bodies other than lenses>

[0337] There are no restrictions on the shape, style, color, or size of molded bodies obtained using polysiloxane compounds; they can be arbitrarily set according to their intended use. Specific examples of molded bodies include electrical and electronic equipment, OA (Office Automation) equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building components, various containers, leisure goods / miscellaneous items, lighting equipment, components of various household electrical products, housings, containers, covers, storage sections, boxes, and covers or boxes for lighting fixtures. Examples of electrical and electronic equipment include displays for personal computers, game consoles, television receivers, LCD or plasma display devices, printers, copiers, scanners, fax machines, electronic notebooks or portable information terminals (PDAs), electronic desktop computers, electronic dictionaries, cameras, camcorders, portable telephones, battery packs, drives or reading devices for storage media, mice, numeric keypads, CD (Compact Disc) players, MD (Mini Disc) players, and portable broadcast / audio players. In addition, as molded products, examples include illuminated billboards, LCD backlights, lighting displays, traffic signs, signs, screens, reflectors or instrument components, automotive parts (vehicle-mounted parts), toys, decorations, etc.

[0338] The polysiloxane compound of the present invention can produce molded articles with excellent impact resistance, high melt flowability, and a fine structure, making it suitable for use as automotive electrical and electronic components, mechanical components, and vehicle components. Examples of such components include automotive interior panels, automotive lamp lenses, automotive interior lenses, automotive lens covers, and automotive light guides.

[0339] <7. Molding Method of Molded Components>

[0340] The manufacturing method of the molded article of the present invention is not particularly limited, and any molding method commonly used for resins can be employed. Examples include injection molding, high-speed injection molding, injection compression molding, two-color molding, gas-assisted hollow molding, molding using insulated molds, molding using rapidly heated molds, foam molding (including supercritical fluid molding), insert molding, IMC (in-mold coating) molding, extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, and compression molding. Additionally, molding methods employing hot runner systems can also be used.

[0341] <8. Other Resins>

[0342] In the polysiloxane compounds of the present invention, components other than the polysiloxane compounds of the present invention may be included as needed, provided that the intended physical properties are not significantly impaired. For example, resins other than the polysiloxane compounds of the present invention may be included.

[0343] Other examples of such resins include, for instance, thermoplastic polyester resins such as polycarbonate resins other than the polysiloxane compounds of the present invention, polyethylene terephthalate resin (PET resin), polypropylene terephthalate resin (PTT resin), and polybutylene terephthalate resin (PBT resin); styrene-based resins such as polystyrene resin (PS resin), high-impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and methyl methacrylate-styrene copolymer (MS resin); methyl methacrylate- Core / shell elastomers such as acrylic rubber-styrene copolymer (MAS), polyester elastomers, and other elastomers; polyolefin resins such as cyclic olefin resin (COP resin) and cyclic olefin copolymer (COP) resin; polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resin (PEI resin); polyurethane resin (PU resin); polyphenylene ether resin (PPE resin); polyphenylene sulfide resin (PPS resin); polysulfone resin (PSU resin); polymethyl methacrylate resin (PMMA resin); polycaprolactone, etc.

[0344] For example, based on the total weight of the polysiloxane compound, the components other than polysiloxane in the polysiloxane compound of the present invention are contained in proportions of less than 10% by weight, less than 5% by weight, more than 3% by weight, less than 2% by weight, or less than 1% by weight.

[0345] Example

[0346] The following illustrative embodiments illustrate the present invention in more detail. However, the present invention is not limited to the following embodiments, and can be implemented in any way without departing from the spirit of the invention.

[0347] Example 1

[0348] 112.00 g (0.49 mol) of 2,2-bis(4-hydroxyphenyl)propane, 134.25 g (0.55 mol) of dimethyldiphenoxysilane, and 10.0 μmol / mol of tetraphenyltetraphenylboronic acid phosphonium as a catalyst (catalyst amount is relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 500 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The reactants were heated to 180 °C to melt them. After the reactants were completely melted, the reaction solution was collected after 10 minutes, 20 minutes, and 30 minutes.

[0349] The obtained reaction solution was dissolved in chloroform to prepare a 1,000 μg / mL solution, which was then analyzed and quantified using GC / FID. The phenol conversion rate was 34% after 10 minutes, 50% after 20 minutes, and 54% after 30 minutes.

[0350] Example 2

[0351] 112.00 g (0.49 mol) of 2,2-bis(4-hydroxyphenyl)propane, 134.25 g (0.55 mol) of dimethyldiphenoxysilane, and 10.0 μmol / mol of tetraphenylphenoxyphosphonium as a catalyst (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 500 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The reactants were heated to 180 °C to melt them. After the reactants were completely melted, the reaction solution was collected after 10 minutes, 20 minutes, and 30 minutes.

[0352] The obtained reaction solution was dissolved in chloroform to prepare a 1,000 μg / mL solution, which was then analyzed and quantified using GC / FID. The phenol conversion rate was 30% after 10 minutes, 46% after 20 minutes, and 52% after 30 minutes.

[0353] Example 3

[0354] 112.00 g (0.49 mol) of 2,2-bis(4-hydroxyphenyl)propane, 134.25 g (0.55 mol) of dimethyldiphenoxysilane, and 3.0 μmol / mol of tetraphenyltetraphenylboronic acid phosphonium (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 500 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The reactants were heated to 180 °C to melt them. After the reactants were completely melted, the reaction solution was collected after 10 minutes, 20 minutes, and 30 minutes.

[0355] The obtained reaction solution was dissolved in chloroform to prepare a 1,000 μg / mL solution, which was then analyzed and quantified using GC / FID. The phenol conversion rate was 23% after 10 minutes, 40% after 20 minutes, and 52% after 30 minutes.

[0356] Example 4

[0357] 112.00 g (0.49 mol) of 2,2-bis(4-hydroxyphenyl)propane, 134.25 g (0.55 mol) of dimethyldiphenoxysilane, and 1.0 μmol / mol of tetraphenylphenoxyphosphonium as a catalyst (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 500 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The reactants were heated to 180 °C to melt them. After the reactants were completely melted, the reaction solution was collected after 10 minutes, 20 minutes, and 30 minutes.

[0358] The obtained reaction solution was dissolved in chloroform to prepare a 1,000 μg / mL solution, which was then analyzed and quantified using GC / FID. The phenol conversion rate was 11% after 10 minutes, 23% after 20 minutes, and 31% after 30 minutes.

[0359] Example 5

[0360] 112.00 g (0.49 mol) of 2,2-bis(4-hydroxyphenyl)propane, 134.25 g (0.55 mol) of dimethyldiphenoxysilane, and 0.5 μmol / mol of tetraphenylphenoxyphosphonium as a catalyst (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 500 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The reactants were heated to 180 °C to melt them. After the reactants were completely melted, the reaction solution was collected after 10 minutes, 20 minutes, and 30 minutes.

[0361] The obtained reaction solution was dissolved in chloroform to prepare a 1,000 μg / mL solution, which was then analyzed and quantified using GC / FID. The phenol conversion rate was 7% after 10 minutes, 14% after 20 minutes, and 20% after 30 minutes.

[0362] Comparative Example 1

[0363] 112.00 g (0.49 mol) of 2,2-bis(4-hydroxyphenyl)propane, 134.25 g (0.55 mol) of dimethyldiphenoxysilane, and 3.0 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 500 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The reactants were heated to 180 °C to melt, and after the reactants were completely melted, the reaction solution was collected after 10 minutes, 20 minutes, and 30 minutes.

[0364] The obtained reaction solution was dissolved in chloroform to prepare a 1,000 μg / mL solution, which was then analyzed and quantified using GC / FID. The phenol conversion rate was 2% after 10 minutes, 5% after 20 minutes, and 8% after 30 minutes.

[0365] The results of the above embodiments and Comparative Example 1 are shown in Table 1 below.

[0366] [Table 1]

[0367]

[0368] Example 6

[0369] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 64.30 g (0.26 mol) of dimethyldiphenoxysilane, 25.98 g (0.12 mol) of diphenyl carbonate, and 10.0 μmol / mol of tetraphenyltetraphenylborate as a catalyst (catalyst amount is relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0370] Subsequently, the transesterification reaction was carried out for 2 hours while condensing and removing the phenol distilled from the reaction system using a cooling pipe. This brought the system to 260°C and a pressure reduction below 2 hPa, which was then maintained for another hour, resulting in a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0371] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 38,352.

[0372] Regarding the thermal decomposition temperature, the mass retention rate is 65% when the weight is reduced by 1% to 363℃ and 500℃.

[0373] Example 7

[0374] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 60.40 g (0.25 mol) of dimethyldiphenoxysilane, 25.98 g (0.12 mol) of diphenyl carbonate, and 10.0 μmol / mol of tetraphenyltetraphenylborate as a catalyst (catalyst amount is relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0375] Then, for 1 hour and 30 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, and then maintained for another 2 hours, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0376] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 44,030.

[0377] Regarding the thermal decomposition temperature, the mass retention rate is 61% when the weight is reduced by 1% to 361℃ and 500℃.

[0378] Example 8

[0379] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 60.40 g (0.25 mol) of dimethyldiphenoxysilane, 25.98 g (0.12 mol) of diphenyl carbonate, and 10.0 μmol / mol of tetraphenylphenoxyphosphonium as a catalyst (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0380] Then, for 1 hour and 30 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, and then maintained for another 2 hours, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0381] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 46,356.

[0382] Regarding the thermal decomposition temperature, the mass retention rate is 52% when 1% weight is reduced to 361℃ or 500℃.

[0383] Example 9

[0384] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 63.00 g (0.26 mol) of dimethyldiphenoxysilane, 25.98 g (0.12 mol) of diphenyl carbonate, and 3.0 μmol / mol of tetraphenylphenoxyphosphonium as a catalyst (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged under a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0385] Then, for 1 hour and 45 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, and then maintained for another 2 hours, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0386] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 43,719.

[0387] Regarding the thermal decomposition temperature, the mass retention rate is 66% when the weight is reduced by 1% to 359℃ and 500℃.

[0388] Example 10

[0389] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 64.30 g (0.26 mol) of dimethyldiphenoxysilane, 25.98 g (0.12 mol) of diphenyl carbonate, and 1.0 μmol / mol (relative molar amount of tetraphenylphenoxyphosphonium) and 1.0 μmol / mol (relative molar amount of sodium bicarbonate) of tetraphenylphenoxyphosphonium as catalysts were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0390] Then, for 2 hours and 15 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, which was then maintained for another 1 hour and 45 minutes, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0391] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 44,081.

[0392] Regarding the thermal decomposition temperature, the mass retention rate is 54% when the weight is reduced by 1% to 349℃ and 500℃.

[0393] Example 11

[0394] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 64.30 g (0.26 mol) of dimethyldiphenoxysilane, 25.98 g (0.12 mol) of diphenyl carbonate, and 0.5 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) and 1.0 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) as catalysts were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0395] Then, for 2 hours and 45 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, which was then maintained for another 2 hours and 40 minutes, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0396] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 47,535.

[0397] Regarding the thermal decomposition temperature, the mass retention rate is 58% when the weight is reduced by 1% to 347℃ and 500℃.

[0398] Example 12

[0399] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 63.41 g (0.26 mol) of dimethyldiphenoxysilane, 25.62 g (0.12 mol) of diphenyl carbonate, and 6.0 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) and 1.5 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) as catalysts were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0400] Then, for 1 hour and 30 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, and then maintained for another 2 hours, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0401] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 44,949.

[0402] Regarding the thermal decomposition temperature, the mass retention rate is 47% when the weight is reduced by 1% to 359℃ and 500℃.

[0403] Example 13

[0404] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 61.66 g (0.25 mol) of dimethyldiphenoxysilane, 24.90 g (0.12 mol) of diphenyl carbonate, and 10.0 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) and 14 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) of sodium acetate as catalysts were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0405] Then, for 1 hour and 48 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, which was then maintained for 2 hours, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0406] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 63,619.

[0407] Regarding the thermal decomposition temperature, the mass retention rate is 60% when the weight is reduced by 1% to 353℃ and 500℃.

[0408] Example 14

[0409] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 61.66 g (0.25 mol) of dimethyldiphenoxysilane, 24.90 g (0.12 mol) of diphenyl carbonate, and 10.0 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) and 26 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) as catalysts were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0410] Then, for 1 hour and 43 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, which was then maintained for 2 hours, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0411] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 63,619.

[0412] Regarding the thermal decomposition temperature, the mass retention rate is 59% when the weight is reduced by 1% to 349℃ and 500℃.

[0413] Example 15

[0414] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 63.41 g (0.26 mol) of dimethyldiphenoxysilane, 25.62 g (0.12 mol) of diphenyl carbonate, and 3.0 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) and 6 μmol / mol (catalyst amount relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) as catalysts were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged with a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0415] Then, for 1 hour and 52 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, which was then maintained for 2 hours, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0416] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 63,619.

[0417] Regarding the thermal decomposition temperature, the mass retention rate is 66% when the weight is reduced by 1% to 351℃ and 500℃.

[0418] Comparative Example 2

[0419] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 67.30 g (0.28 mol) of dimethyldiphenoxysilane, 25.98 g (0.12 mol) of diphenyl carbonate, and 3.0 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount is relative to the molar amount of 2,2-bis(4-hydroxyphenyl)propane) were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged under a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0420] Then, for 2 hours and 40 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa. This was maintained for another 2 hours and 30 minutes, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0421] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 56,695.

[0422] Regarding the thermal decomposition temperature, the mass retention rate is 66% when the weight is reduced by 1% to 359℃ and 500℃.

[0423] Comparative Example 3

[0424] 80.13 g (0.35 mol) of 2,2-bis(4-hydroxyphenyl)propane, 64.30 g (0.28 mol) of dimethyldiphenoxysilane, 25.98 g (0.12 mol) of diphenyl carbonate, and 1.5 μmol / mol of sodium bicarbonate as a catalyst (catalyst amount relative to the molar ratio of 2,2-bis(4-hydroxyphenyl)propane) were added to a 300 mL four-necked flask equipped with a stirrer, and the system was purged under a nitrogen atmosphere. The raw materials were heated to 190 °C to melt, and stirred for 20 minutes.

[0425] Then, for 3 hours and 20 minutes, while condensing and removing the phenol distilled from the reaction system using a cooling pipe, a transesterification reaction was carried out to bring the system to 260°C and a pressure reduction below 2 hPa, which was then maintained for another 2 hours, thereby obtaining a colorless and transparent polycarbonate copolymer with an arylene siloxane structure. During the pressure reduction, the pressure was adjusted in stages from atmospheric pressure to below 27,000 Pa, 24,000 Pa, 20,000 Pa, 17,000 Pa, 14,000 Pa, 10,000 Pa, 8,000 Pa, 6,000 Pa, 4,000 Pa, 2,000 Pa, 1,000 Pa, and 200 Pa.

[0426] The Mw of the polycarbonate copolymer containing siloxane was determined using GPC, and the result was 37,590.

[0427] Regarding the thermal decomposition temperature, the mass retention rate is 62% when 1% weight is reduced to 365℃ and 500℃.

[0428] The results of the above embodiments and comparative examples 2 and 3 are shown in Table 2 below.

[0429] [Table 2]

[0430]

[0431] Analytical methods

[0432] <Determination of Phenol Conversion Rate>

[0433] The methods for determining the phenol conversion rate in each example and comparative example are as follows.

[0434] The samples from the examples or comparative examples were dissolved in chloroform to prepare a solution of 1,000 μg / mL, which was then analyzed and quantified using GC / FID.

[0435] The quantitative value is based on a pre-made Figure 1 The calibration line for phenol shown indicates the conversion value of phenol.

[0436] The amount of phenol produced in the reaction solution is calculated based on the phenol conversion value.

[0437] (Calculation formula (A))

[0438] (Phenol production (g) / Theoretical phenol production (g)) × 100 = Phenol conversion rate (%) ... (A)

[0439] The phenol conversion rate (%) can be calculated using the above formula (A).

[0440] [GC / FID Measurement Conditions]

[0441] The conditions for GC / FID determination in each embodiment and comparative example are as follows.

[0442] ·Device: GC2025 manufactured by Shimadzu Corporation

[0443] • Column: Capillary column DB-35, 30mm × 0.25mm × 0.25μm

[0444] • Heating conditions: 40℃―300℃ (5min hold), 10℃ / min

[0445] Injection port temperature: 300℃; Dosage: 1.0 μL (split ratio 1:20)

[0446] Carrier gas: He

[0447] • Air flow rate: 400 mL / min

[0448] H2 flow rate: 40 mL / min

[0449] • Supplemental gas: 30 mL / min

[0450] • Standard substance: phenol

[0451] <Thermal Decomposition Temperature>

[0452] 1% – The percentage of mass reduction at the onset temperature and at 500°C.

[0453] In aluminum containers (Al open-type sample containers) Accurately weigh 10 mg of the test sample within a 2.5 mm (H2.5 mm) space. The determination is performed under atmospheric conditions. 0.00519 g of α-alumina is used as the reference material. The sample temperature is adjusted to 30 °C and increased to 500 °C at a rate of 10 °C / min. The temperature at which 1% mass decreases is defined as the "1% - thermal mass decrease start temperature". Furthermore, the percentage of mass reduction of the sample at 500 °C, i.e., the percentage based on the mass of the sample before heating, is defined as the "500 °C mass reduction percentage (%)". The table below shows the "mass retention rate at 500 °C (%)", which is 100 minus the "500 °C mass reduction percentage (%)".

[0454] Measurement Apparatus: Thermogravimetric Analysis (TG / DTA) Apparatus (manufactured by Hitachi High Technology Co., Ltd., TG / DTA7300)

[0455] <Determination of converted weight-average molecular weight (Mw) of polystyrene>

[0456] Using GPC (gel permeation chromatography), chloroform was used as the developing solvent, and a calibration line was constructed using a standard polystyrene (Shodex STANDARD, SM-105) with a known molecular weight (molecular weight distribution = 1). The dissolution time and molecular weight values ​​of each peak were labeled based on the measured standard polystyrene values, and an approximation was made using a cubic equation to construct the calibration line.

[0457] Then, using the obtained calibration line as a reference, the weight-average molecular weight (Mw) is calculated from the polystyrene conversion value using the following formula.

[0458] [Calculation formula]

[0459] Mw=Σ(Wi×Mi) / Σ(Wi)

[0460] (In the above formula, i represents the i-th segmentation point when dividing molecular weight M, Wi represents the weight of the i-th segment, and Mi represents the molecular weight of the i-th segment. The molecular weight M represents the molecular weight converted from polystyrene at the same dissolution time as the calibration line.)

[0461] [Measurement Conditions]

[0462] ·Device: Labsolutions manufactured by Shimadzu Corporation;

[0463] • Chromatographic columns: 1 guard column (Shodex GPC K-G 4A), 2 analytical columns (Shodex GPC K-805L);

[0464] Solvent: Chloroform (HPLC grade);

[0465] Injection volume: 10 μL;

[0466] • Sample concentration: 2000 ppm;

[0467] Solvent flow rate: 1 mL / min;

[0468] • Measurement temperature: 40℃;

[0469] • Detector: RI.

Claims

1. A method for manufacturing a polysiloxane, said polysiloxane having a siloxane structural unit represented by any one of the following formulas (1-1) to (1-4), characterized in that, The polymerization process includes polymerizing a silane compound selected from the following diaryloxysilane compounds with a dihydroxy compound containing an aromatic dihydroxy compound or an alicyclic dihydroxy compound. In the polymerization step of polymerizing the silane compound with the dihydroxy compound, an transesterification catalyst containing a phosphorus compound is used. In the polymerization process, the silane compound and the dihydroxy compound are polymerized in a molten state. The polysiloxane has a weight-average molecular weight (Mw) of 20,000 to 80,000 when converted to polystyrene. The diaryloxysilane compound comprises at least one of dialkyldiaryloxysilane, diaryldiaryloxysilane, and monoalkylmonoaryldiaryloxysilane, and the diaryloxysilane compound comprises at least dialkyldiaryloxysilane, wherein the dialkyldiaryloxysilane comprises at least dimethyldiphenoxysilane. In equations (1-1) to (1-4), R 1 and R 2 Each can be independently represented as an alkyl group with or without substituents and a total carbon number of 1 to 20, or an aryl group with or without substituents and a total carbon number of 6 to 30. R 3 ~R 10 and R 30 ~R 33 Each of the following can be independently represented: hydrogen, halogen, alkoxy, alkyl with or without substituents having a total of 1 to 20 carbon atoms, alkenyl with or without substituents having a total of 2 to 20 carbon atoms, or aryl with or without substituents having a total of 6 to 30 carbon atoms. Z1 and Z2 independently represent alkylene groups with or without substituents, having a total number of carbon atoms of 1 to 5. J1 independently represents integers above 0 and below 5. K1 independently represents integers above 0 and below 5. A1 and A2 independently represent either -O- or -CH-. L1 and L2 independently represent integers above 0 and below 3. X is a single bond, or any of the structural formulas shown in equation (2) below. In equation (2), R 11 and R 12 Each can independently represent hydrogen, halogen, alkyl group with or without substituents having a total of 1 to 20 carbon atoms, or aryl group with or without substituents having a total of 6 to 30 carbon atoms, or R. 11 and R 12 Carbon rings or heterocycles with 1 to 20 carbon atoms, formed by bonding together, with or without substituents. The substituents are each independently one of halogen, cyano, alkenyl, alkynyl, or alkoxy. a and b represent integers above 0 or 1 and below 5000, respectively.

2. The method for manufacturing polysiloxane as described in claim 1, characterized in that, The phosphorus compound comprises a compound represented by the following general formula (I). (PRe4) + (Xc) － ···(I) In general formula (I), Re independently represents alkyl, aryl, or alkylaryl groups. Multiple Re groups may bond together to form a ring structure or not bond together to form a ring structure. Xc represents a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl carbonyloxy group, an aryl carbonyloxy group, HCO3, or BRf4, wherein Rf is independently a hydrogen atom, an alkyl group, or an aryl group.

3. The method for manufacturing polysiloxane as described in claim 1, characterized in that, The phosphorus compound comprises any one of biphenyltriphenylphosphonium hydroxide, biphenyltriphenyltetraphenylboronic acid, biphenyltriphenylphenoxyphosphonium, biphenyltriphenylphosphonium chloride, tetraphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide, tetraphenylphenoxyphosphonium, tetraphenyltetraphenylboronic acid, methoxyphenyltriphenyltetraphenylboronic acid, phenoxyphenyltriphenyltetraphenylboronic acid, naphthylphenyltriphenyltetraphenylboronic acid, methoxyphenyltriphenylphenoxyphosphonium, phenoxyphenyltriphenylphenoxyphosphonium, naphthylphenyltriphenylphenoxyphosphonium, tetraphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride, and naphthylphenyltriphenylphosphonium chloride.

4. The method for manufacturing polysiloxane as described in claim 3, characterized in that, The phosphorus compound comprises at least one of tetraphenylphenoxyphosphonium and tetraphenyltetraphenylboratephosphonium.

5. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, The transesterification catalyst also includes an alkali metal catalyst.

6. The method for manufacturing polysiloxane as described in claim 5, characterized in that, The transesterification catalyst comprises at least a sodium-containing alkali metal transesterification catalyst.

7. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, In the polymerization process, the amount of the transesterification catalyst relative to the amount of the dihydroxy compound is 1.0 × 10⁻⁶ molar ratio. －7 ~1.0×10 －2 .

8. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, The reaction temperature in the polymerization process is in the range of 150°C to 300°C.

9. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, No solvent is used in the polymerization process.

10. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, The ratio of the molar number of the silane compound to the molar number of the dihydroxy compound used in the polymerization process is more than 0.9 and less than 1.

2.

11. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, In the polymerization process, the carbonate compound is further polymerized with the silane compound and the dihydroxy compound.

12. The method for manufacturing polysiloxane as described in claim 11, characterized in that, The polysiloxane also has a polycarbonate structural unit derived from any of the following formulas (3-1) to (3-4) of the carbonate compound. In general formulas (3-1) to (3-4), R 3 ~R 10 R 21 ~R 26 and R 31 ~R 36 Each of the following can be independently represented: a hydrogen atom, a halogen atom, an alkoxy group with or without a substituent (1 to 5 carbon atoms), an alkyl group with or without a substituent (1 to 20 carbon atoms), an alkenyl group with or without a substituent (2 to 20 carbon atoms), or an aryl group with or without a substituent (6 to 30 carbon atoms). Z1 and Z2 are each independently an alkylene group having 1 to 5 carbon atoms, with or without substituents. The substituent is any one of halogen, cyano, alkenyl, alkynyl, or alkoxy. J1 independently represents integers from 0 to 5. K1 independently represents integers from 0 to 5. A1 and A2 independently represent either -O- or -CH2-. L1 and L2 independently represent integers from 0 to 3. X is a single bond, or any of the structural formulas shown in equations (1) to (7) below. In general formulas (1) to (7), R 11 and R 12 Each of the following can be independently represented: a hydrogen atom, a halogen atom, an alkyl group with or without substituents and having 1 to 20 carbon atoms, or an aryl group with or without substituents and having 6 to 30 carbon atoms, or a group composed of R. 11 and R 12 Carbon rings or heterocycles with 1 to 20 carbon atoms, formed by bonding together, with or without substituents. The substituent is any one of halogen, cyano, alkenyl, alkynyl, or alkoxy. r and s represent integers from 0 to 5000 independently.

13. The method for manufacturing polysiloxane as described in claim 12, characterized in that, The molar ratio of the total number of siloxane structural units to the total number of polycarbonate structural units is 0.1:99.9 to 100:

0.

14. The method for manufacturing polysiloxane as described in claim 12 or 13, characterized in that, In the polymerization process, under reduced pressure, the alcohol from the carbonate compound is removed while the silane compound is polymerized with the dihydroxy compound.

15. A method for manufacturing a polysiloxane, said polysiloxane having a siloxane structural unit represented by any one of the formulas (1-1) to (1-4), characterized in that, The polymerization process includes polymerizing a silane compound selected from the following diaryloxysilane compounds with a dihydroxy compound containing an aromatic dihydroxy compound or an alicyclic dihydroxy compound. In the polymerization step of polymerizing the silane compound with the dihydroxy compound, an transesterification catalyst containing a phosphorus compound is used. In the polymerization process, the silane compound and the dihydroxy compound are polymerized in a molten state. The polysiloxane has a weight-average molecular weight (Mw) of 20,000 to 80,000 when converted to polystyrene. The diaryloxysilane compound comprises at least one of dialkyldiaryloxysilane, diaryldiaryloxysilane, and monoalkylmonoaryldiaryloxysilane, and the diaryloxysilane compound comprises at least dialkyldiaryloxysilane, wherein the dialkyldiaryloxysilane comprises at least dimethyldiphenoxysilane. In equations (1-1) to (1-4), R 1 and R 2 Each can be independently represented as an alkyl group with or without substituents and a total carbon number of 1 to 20, or an aryl group with or without substituents and a total carbon number of 6 to 30. R 3 ~R 10 and R 30 ~R 33 Each of the following can be independently represented: hydrogen, halogen, alkoxy, alkyl with or without substituents having a total of 1 to 20 carbon atoms, alkenyl with or without substituents having a total of 2 to 20 carbon atoms, or aryl with or without substituents having a total of 6 to 30 carbon atoms. Z1 and Z2 independently represent alkylene groups with or without substituents, having a total number of carbon atoms of 1 to 5. J1 independently represents integers above 0 and below 5. K1 independently represents integers above 0 and below 5. A1 and A2 independently represent either -O- or -CH-. L1 and L2 independently represent integers above 0 and below 3. X is a single bond, or any of the structural formulas shown in equation (2) below. In equation (2), R 11 and R 12 Each can independently represent hydrogen, halogen, alkyl group with or without substituents having a total of 1 to 20 carbon atoms, or aryl group with or without substituents having a total of 6 to 30 carbon atoms, or R. 11 and R 12 Carbon rings or heterocycles with 1 to 20 carbon atoms, formed by bonding together, with or without substituents. The substituents are each independently one of halogen, cyano, alkenyl, alkynyl, or alkoxy. a and b independently represent integers greater than 0 or 1 and less than 5000. The polysiloxane is composed solely of the siloxane structural units.

16. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, The polysiloxane has a weight-average molecular weight (Mw) of 30,000 to 70,000 when converted to polystyrene.

17. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, In the polysiloxane, the low molecular weight compound with a weight average molecular weight of less than 1,000 is less than 1% by weight.

18. The method for manufacturing polysiloxane as described in claim 17, characterized in that, In the polysiloxane, the proportion of low molecular weight compounds with a weight average molecular weight of less than 1,000 calculated from the GPC area ratio is less than 1% by weight.

19. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, The polysiloxane has a thermal decomposition temperature above 300°C when its mass is reduced by 1%.

20. The method for manufacturing polysiloxane according to any one of claims 1 to 4, characterized in that, In the polysiloxane, the mass retention rate at 500°C is above 40%.

21. A composition, characterized in that, It contains a polysiloxane, consisting solely of the siloxane structural units, obtained by the manufacturing method of claim 15, and a polycarbonate resin.

22. The composition according to claim 21, characterized in that, The total Si content in the composition is 0.1-20% by mass.

23. A molded body, characterized in that, It includes polysiloxanes obtained by the manufacturing method of claim 15, which are composed solely of the siloxane structural units.

24. An optical lens, characterized in that, It includes polysiloxanes obtained by the manufacturing method of claim 15, which are composed solely of the siloxane structural units.

25. An optical lens obtained by molding the composition of claim 21 or 22.

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