JP2002239357A - Gas separation membrane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas separation membrane excellent in carbon dioxide selective separation capacity. SOLUTION: In the gas separation membrane, a polycarbonate resin, which is a polycarbonate obtained by the reaction of 9,9-bis(4-hydroxy-3-methylphenyl) fluorene and a compound of formula A (X expresses homopolymers or a copolymer of -SiO(R8)(R9) and/or -SiO(R10)(R11)-) or a compound of formula A and formula B Y is -[C(R14)(R15)]a-, -S-, -SO2-, -O-, -CO-, or -SO-} with a carbonate forming compound, serves as a base material. The compound of the formula A is 20-60 wt.% of the total monomer components [9,9-bis(4- hydroxy-3-methylphenyl fluorene and the compounds of the formulas A and B], and the intrinsic viscosity [η] of the polycarbonate is 0.2-2.0 dl/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an exhaust gas separation process,
The present invention relates to a gas separation membrane useful for gas separation for industrial gas.

[0002]

2. Description of the Related Art At the Global Warming Prevention Council in 1997, targets for reducing greenhouse gas emissions in developed countries have been set. Therefore, it is necessary to reduce the emission of carbon dioxide, which emits the largest amount of greenhouse gases into the atmosphere. Have been.

[0003] On the other hand, gas separation membranes for selectively separating a target gas from a gas mixture are known. Particularly, polymer gas separation membranes are excellent in permeability and processability, and are used in large quantities in thermal power plants and factories. It is expected to separate carbon dioxide gas discharged into the country.

[0004] As the polymer gas separation membrane, various polymers can be cited as a base material. In consideration of the separation of exhaust gas, a polymer having a certain degree of heat resistance is desired. For this reason, a polycarbonate-based gas separation membrane having a relatively high gas permeability and heat resistance has been studied (JP-A-48-641).
99, JP-A-10-99666). Although these polycarbonate-based gas separation membranes use a unique modified polycarbonate having a fluorene structure as a base material, there is still room for improvement when attention is paid to carbon dioxide gas separation selectivity.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a gas separation membrane having an excellent ability to selectively separate carbon dioxide gas as compared with a conventional polymer gas separation membrane.

[0006]

The present inventors have conducted intensive studies to solve the conventional problems, and as a result, have found that 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and a specific polysiloxane A gas separation membrane based on a copolymerized polycarbonate resin derived from a class, found to be a good quality gas separation membrane having an excellent ability to selectively separate carbon dioxide, and completed the present invention. .

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS That is, the present invention relates to 9,9-bis (4
-Hydroxy-3-methylphenyl) fluorene and general formula (A) or 9,9-bis (4-hydroxy-3-
Methylphenyl) fluorene is a polycarbonate obtained by reacting a compound represented by the general formula (A) and a compound represented by the general formula (B) with a carbonate-forming compound, wherein the general formula (A) has all the monomer components [9, 9-bis (4-hydroxy-3-methylphenyl) fluorene + general formula (A) +
The present invention provides a gas separation membrane based on a polycarbonate resin having a basic viscosity [η] of 0.2 to 2.0 [dl / g] based on the general formula (B)]. is there.

[0008]

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(Where R₁~ R_TwoAre each independently water
Element, alkyl group having 1 to 5 carbon atoms, ant having 6 to 12 carbon atoms
Alkenyl group having 2 to 5 carbon atoms, 1 to 5 carbon atoms
An alkoxy group or an aralkyl group having 7 to 17 carbon atoms
And when these groups have a carbon atom,
To form an alkyl group having 1 to 5 carbon atoms and an alkyl group having 2 to 5 carbon atoms.
Having a kenyl group or an alkoxy group having 1 to 5 carbon atoms
You can also. R_Three~ R₆Is hydrogen, an alkyl group having 1 to 5 carbon atoms.
Alkyl group, aryl group having 6 to 12 carbon atoms, 2 to 5 carbon atoms
An alkenyl group, an alkoxy group having 1 to 5 carbon atoms, or
Aralkyl groups having 7 to 17 carbon atoms;
When it has an elemental atom, it has 1 to 5 carbon atoms as a substituent.
Alkyl group, alkenyl group having 2 to 5 carbon atoms, or carbon
It may also have an alkoxy group of the formulas 1 to 5. R₇Is
It represents an aliphatic group having 1 to 6 carbon atoms or simply represents a bond. X
Is -SiO (R₈) (R₉)-And / or -SiO
(R_Ten) (R ₁₁)-Homopolymer or random copolymer
And the degree of polymerization is from 1 to 200;₈~ R₁₁Is each
Each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, 6 carbon atoms
Aryl group, alkenyl group having 2 to 5 carbon atoms, carbon
An alkoxy group having a prime number of 1 to 5, or an alkoxy group having a carbon number of 7 to 17
When it is an aralkyl group and these groups have a carbon atom
Represents an alkyl group having 1 to 5 carbon atoms as a substituent,
An alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms
It can also have a di group. Where R₈~ R₁₁Medium, small
At least one containing an aryl group having 6 to 12 carbon atoms
It is. )

[0010]

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(R _{12 to} R ₁₃ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and 1 to 5 carbon atoms. Or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or It may have an alkoxy group having 1 to 5 carbon atoms.

[0012]

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Wherein R ₁₄ and R ₁₅ are each hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 carbon atoms.
Represents an aryl group of 12 to 12 or a group in which R ₁₄ and R ₁₅ are bonded together to form a carbon ring or a heterocyclic ring having 3 to 6 carbon atoms, and when these groups have a carbon atom, As a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms can be used. a represents an integer of 0 to 20. )

The polycarbonate resin used as the base material of the gas separation membrane of the present invention comprises the aforementioned 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as BCFL) and the general formula (A) or It can be produced by reacting BCFL with a compound of the general formula (A) and a compound of the general formula (B) with a carbonate-forming compound, and is used for producing a polycarbonate derived from bisphenol A. Known methods such as direct reaction of bisphenols with phosgene (phosgene method),
Alternatively, a method such as a transesterification reaction between a bisphenol and a bisaryl carbonate (a transesterification method) can be employed.

In the phosgene method and the transesterification method, the phosgene method is preferred in consideration of the reactivity of BCFL and the compound of the formula (A).

In the former phosgene method, the BCFL and the compound of the general formula (A), or the BCFL and the compound of the general formula (A), and the compound of the general formula (B) are generally used in the presence of an acid binder and a solvent. Is reacted with phosgene. Examples of the acid binder include pyridine and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. Examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene. Further, a catalyst such as a tertiary amine catalyst such as triethylamine is used to promote the condensation polymerization reaction.
To control the degree of polymerization, a monofunctional compound such as phenol, pt-butylphenol, p-cumylphenol, alkyl-substituted phenols, alkyl hydroxybenzoates and alkyloxyphenols is added as a molecular weight regulator. Further, if desired, an antioxidant such as sodium sulfite and hydrosulfite, phloroglucin,
Reduce the use of branching agents such as isatin bisphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene. The reaction is usually carried out at a temperature in the range of usually 0 to 150 ° C., preferably 5 to 40 ° C. The reaction time depends on the reaction temperature, but is usually 0.5 min.
10 hours, preferably 1 minute to 2 hours. During the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

On the other hand, in the latter transesterification method, BCFL and a compound of the general formula (A) or a compound of the general formula (A) and a compound of the general formula (B) in the present invention are mixed with a bisaryl carbonate. The reaction is carried out at elevated temperature under reduced pressure. At this time, a monofunctional compound such as phenol, pt-butylphenol, p-cumylphenol, alkyl-substituted phenols, alkyl hydroxybenzoates and alkyloxyphenols may be added as a molecular weight regulator. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of reduced pressure is finally preferably 1 mmHg or less, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the degree of pressure reduction.
About 10 hours. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon, and if desired, the reaction may be performed by adding an antioxidant or a branching agent.

Specific examples of the compound represented by formula (A) used in the present invention include the following.

[0019]

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These can be used in combination of two or more. Particularly, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethyldiphenyl random copolymerized siloxane is preferable.

Specific examples of the compound of the formula (B) in the present invention include 4,4′-biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether and bis (4hydroxyphenyl) ether. -Hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1- Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2,2
-Bis (4-hydroxy-3-methylphenyl) propane (dimethylbisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane (bisphenol AP; BPAP), bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-allylphenyl) propane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane and the like are exemplified. These may be used in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.

Examples of the carbonic acid ester-forming compound in the present invention include phosgene and bisphenyls such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Allyl carbonate is mentioned. These compounds can be used in combination of two or more.

When the phosgene method is employed in the present invention, the tertiary amine polymerization catalyst used may be, for example, triethylamine, tri-n-propylamine, tri-n-
Butylamine, N, N'-dimethylcyclohexylamine,
There are N, N'-diethylaniline, diethylaminopyridine and the like, and triethylamine is preferred from the viewpoint of catalytic activity and washing and removal. In general, the amount of the polymerization catalyst to be used is preferably 0.001 to 5 mol% based on all bisphenols used.

Further, when the phosgene method is employed, a small amount of a quaternary ammonium salt may be added in order to carry out the reaction efficiently. Specifically, tetramethylammonium chloride, trimethylbenzylammonium chloride,
Examples thereof include triethylbenzylammonium chloride, tetraethylammonium bromide, and tetra-n-butylammonium iodide. Of these, trimethylbenzylammonium chloride and triethylbenzylammonium chloride are preferred. The quaternary ammonium salt is generally preferably used in an amount of 0.0005 to 5 mol% based on all bisphenols used.

Further, when a molecular weight regulator is used in the present invention, monohydric phenol is particularly preferred. Specifically, phenol, butyl phenol, octyl phenol, nonyl phenol, decanyl phenol, tetradecanyl phenol, heptadecanyl phenol, octadecane Alkyl-substituted phenols such as nilphenol; alkyl benzoates such as butyl hydroxybenzoate, octyl hydroxybenzoate, nonyl hydroxybenzoate, decanyl hydroxybenzoate, heptadecanyl hydroxybenzoate; butoxyphenol, octyloxyphenol, nonyloxyphenol , Decanyloxyphenol, tetradecanyloxyphenol, heptadecanyloxyphenol, alkyl such as octadecanyloxyphenol Alkoxy phenols are exemplified. The amount of the molecular weight modifier to be added is 0.05 to 50 mol% based on all bisphenols. Preferably, 0.5 to 10
mol%.

The polycarbonate resin of the present invention synthesized by these reactions can be molded as a gas separation membrane by a known molding method such as wet molding, extrusion molding, injection molding, and compression molding. In order to be molded as, it is desirable that wet molding can be easily performed, and the intrinsic viscosity is preferably in the range of 0.2 to 2.0 dl / g.
More preferably, it is in the range of 0.3 to 1.5 dl / g.

In consideration of the flexibility of the gas separation membrane and the selectivity of permeation of carbon dioxide, the amount of the general formula (A) is calculated based on the total amount of the BCFL and the general formulas (A) and (B). On the other hand, 20 to 60% by weight is preferable. When the general formula (A) is less than 20% by weight, the flexibility required for the film is insufficient, and when it exceeds 60% by weight, the ratio of carbon dioxide gas permeability coefficient / nitrogen gas permeability coefficient becomes small.

The use of the general formula (B) can be used to improve various performances and reduce costs, but in consideration of the selectivity of carbon dioxide permeation of the gas separation membrane, the general formula (B) can be used.
Is preferably less than 50% by weight based on the total amount of the BCFL and the general formula (B). When the general formula (B) is 50% by weight or more with respect to the total amount of the BCFL and the general formula (B), the ratio of the carbon dioxide gas permeability coefficient / nitrogen gas permeability coefficient becomes small.

When the gas separation membrane based on the polycarbonate resin of the present invention is formed by wet molding, the polycarbonate resin of the present invention is dissolved in an appropriate solvent, and the solution is subjected to casting, coating, hollow fiber nozzle extrusion and the like. After the wet molding step, the solvent is removed to obtain a molded product such as a flat membrane or a hollow fiber membrane.

Solvents for dissolving the polycarbonate of the present invention include halogenated hydrocarbons such as chloroform and dichloromethane, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, and cyclohexanone. And cyclic ketones such as cyclopentanone, amides such as N, N-dimethylacetamide and dimethylformamide, and acrylates such as methyl acrylate and methyl methacrylate. A plurality of these solvents can be used, and a small amount of a poor solvent may be added for controlling film-forming properties and solvent solubility.

The polycarbonate resin of the present invention is preferably highly refined similarly to the conventional refined polycarbonate for optical disks and the like. Specifically, the diameter is 50 μm
The above dust is practically not detected, and has a diameter of 0.5 to 50 μm.
m is 3 × 10 ⁴ or less, inorganic and organic residual chlorine is 2 ppm or less, residual alkali metal is 2 ppm or less, residual hydroxyl group is 200 ppm or less, residual nitrogen amount is 5 ppm or less,
Purification is performed so as to satisfy as much as possible the criteria such as residual monomer of 20 ppm or less. In some cases, post-treatment such as extraction is performed to remove low molecular weight substances or remove solvents. It is also preferable to use a material in which impurities, isomers and the like are reduced as much as possible for the raw material BCFL, the compounds of the general formulas (A) and (B), the carbonate-forming compound and the like.

The polycarbonate resin of the present invention may be a hindered phenol-based or phosphite-based antioxidant; silicone-based, fatty acid ester, if necessary, in order to secure the stability and releasability required for molding a gas separation membrane. Lubricants and release agents such as natural oils, fatty acids, fatty acid glycerides, beeswax and other natural fats and oils; benzotriazoles, benzophenones,
Light stabilizers such as dibenzoylmethane and salicylate;
Antistatic agents such as polyalkylene glycols and fatty acid glycerides, and inorganic solutions such as lithium chloride may be used in combination.

The gas separation membrane based on the polycarbonate resin of the present invention has a carbon dioxide gas permeability coefficient of at least 16.
(10 ^-10 cm ³ (STP) · cm / (s · cm ² · cmHg)) or more with good carbon dioxide permeability and a ratio of carbon dioxide permeability coefficient / nitrogen gas permeability coefficient of 30 or more Is preferred.

[0034]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

Example 1 9,9-Water was added to 550 ml of an 8.8% (w / v) aqueous sodium hydroxide solution.
113.4 g of bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as BCFL) and hydrosulfite
0.1 g was added and dissolved. 500 ml of methylene chloride
While stirring at 15 ° C., adding 0.1 g of benzyltriethylammonium chloride, and then adding 51 g of phosgene.
Over 50 minutes. After completion of the blowing, stirring was stopped, and 0.9 g of pt-butylphenol (hereinafter abbreviated as PTBP) and 113.4 g of the following polysiloxane compound (hereinafter abbreviated as Si1) were added.
Further, 100 ml of an 8.8% (w / v) aqueous sodium hydroxide solution was added, and the stirring was resumed.

[0036]

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After 10 minutes, 0.2 ml of triethylamine (TE
A) was added and stirring was continued for about an additional hour to complete the polymerization. The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the water washing was repeated until the conductivity of the washing liquid became 10 μS / cm or less. The obtained polymer resin liquid was dropped into warm water maintained at 60 ° C., and the polymer was granulated while the solvent was removed by evaporation. After filtering the obtained white powdery polymer, 105
C. for 8 hours to obtain a powdered polycarbonate resin. This polymer has a concentration of 0.5 g using methylene chloride as a solvent.
The intrinsic viscosity [η] obtained as a Huggins constant of 0.45 at a temperature of 20 ° C. for a / dl solution was 0.75 dl / g. The obtained polycarbonate resin was adjusted to a 15 w / w% tetrahydrofuran solution, and a casting film was formed on a glass plane. After air drying, dry at 100 ℃ for 24 hours, average 55μm
A thick film was obtained. When the obtained film was measured gas permeability coefficient of carbon dioxide and nitrogen gas 0 ℃ with GTR-10 gas permeability coefficient measuring apparatus manufactured by Yanagimoto Seisakusho Co., carbon dioxide gas permeability coefficient 17.3 (10 ^{-10 cm 3 (STP) · cm /} (s · cm 2
・ CmHg)), nitrogen gas permeability coefficient is 0.50 (10 ^-10 cm ³ (STP) ・
cm / (s · cm ² · cmHg)).

Example 2 A polymerization reaction was carried out in the same manner as in Example 1 except that 75.6 g of the following polysiloxane compound (hereinafter abbreviated as Si 2) was used instead of Si 1, and PTBP was changed to 1.0 g.

[0039]

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The intrinsic viscosity [η] of the obtained polymer is 0.49 dl.
/ g. The obtained polycarbonate resin was obtained in Example 1.
After wet molding in the same manner as described above, gas separation membrane evaluation was performed. As a result, the carbon dioxide permeability coefficient was 18.5 (10 ^-10 cm ³ (STP) cm / (s
· Cm ² · cmHg)), the nitrogen gas permeability coefficient is 0.52 (10 ^-10 cm ³
(STP) · cm was ^{/ (s · cm 2 · cmHg} )).

Example 3 Example 3 was repeated except that BCFL was changed to 94.5 g and Si1 to 75.6 g, and 18.9 g of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as BPA) was simultaneously charged with BCFL. A polymerization reaction was carried out in the same manner as in Example 1. The intrinsic viscosity [η] of the obtained polymer was 0.70 dl / g. The obtained polycarbonate resin was subjected to wet molding in the same manner as in Example 1 and then subjected to gas separation membrane evaluation. As a result, the carbon dioxide gas transmission coefficient was 17.0 (10 ^-10 cm ³
(STP) · cm / (s · cm 2 · cmHg)), nitrogen gas permeability coefficient
0.55 (10 ⁻¹⁰ cm ³ (STP) · cm / (s · cm ² · cmHg)).

Comparative Example 1 A commercial BPA type was used instead of the polycarbonate of Example 1.
Polycarbonate resin (Eupiro manufactured by Mitsubishi Gas Chemical Co., Ltd.)
E-2000) as a 15% w / w dichloromethane solution
A gas separation membrane similar to that of Example 1 was formed except that the molding was performed.
And evaluated. The resulting gas separation membrane is
The excess coefficient is 4.8 (10^-Tencm^Three(STP) cm / (scm ^Two・ CmHg)),
The nitrogen gas permeability coefficient is 0.24 (10^-Tencm^Three(STP) ・ cm / (s ・ c
m^Two・ CmHg)).

Comparative Example 2 Reactive polymerization was carried out in the same manner as in Example 1 except that 113.4 g of 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter abbreviated as BFL) was used instead of BCFL, and Si1 was not used. Was. The intrinsic viscosity [η] of the obtained polymer was 0.60 dl / g. The obtained polycarbonate resin was subjected to wet molding in the same manner as in Example 1 and then subjected to gas separation membrane evaluation. As a result, the carbon dioxide gas transmission coefficient is 15.0 (10 ^-10 cm ³ (STP) · cm / (s · cm ² · cmHg))
, The nitrogen gas permeability coefficient is 0.55 (10 ^-10 cm ³ (STP) cm / (s
Cm ² · cmHg)).

Comparative Example 3 Example 1 was repeated except that 113.4 g of BFL and 113.4 g of the following polysiloxane compound (hereinafter abbreviated as Si3) were used instead of BCFL.
Reaction polymerization was carried out in the same manner as described above. The intrinsic viscosity [η] of the obtained polymer was 0.62 dl / g.

[0045]

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The obtained polycarbonate resin was prepared in Example 1.
After wet molding in the same manner as described above, gas separation membrane evaluation was performed. As a result, the carbon dioxide gas permeability coefficient was 14.3 (10 ^-10 cm ³ (STP) · cm / (s
・ Cm ²・ cmHg)), and the nitrogen gas permeability coefficient is 0.72 (10 ^-10 cm ³ (S
TP) · cm was ^{/ (s · cm 2 · cmHg} )).

Table 1 shows the evaluation results of the gas separation membranes of Examples 1 to 3 and Comparative Examples 1 to 3.

[0048]

[Table 1]

(Explanation of Table) Permeability coefficient: Gas permeability coefficient in terms of 0 ° C. and 1 atom. The unit is 1 (10 ^-10 cm ³ (STP) · cm / (s · cm ² · cmHg)) = 1B
arrer.

[0050]

According to the present invention, it is possible to provide a gas separation membrane having an excellent ability to selectively separate carbon dioxide gas as compared with a conventional polymer gas separation membrane. In particular, it is suitable as a membrane for separating carbon dioxide from exhaust gas discharged in large quantities from thermal power plants and factories.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 69:00 C08L 69:00 F term (Reference) 4D006 GA41 HA41 KD29 MA03 MB04 MC49 MC49X NA05 NA10 NA64 PA02 PB19 PB64 PC80 4F071 AA50 AA50X AA81 AA81X AA88 AA88X AF08 AH02 BA02 BB02 BC01 4J029 AA09 AB01 AB07 AC01 AC02 AD01 AE03 BB18 BF23 BH04 HC01 HC05A JC712 JF352

Claims (7)

[Claims] 1. A method for preparing 9,9-bis (4-hydroxy-3-methine).
Tylphenyl) fluorene and the general formula (A) or 9,
9-bis (4-hydroxy-3-methylphenyl) fur
Olen and compounds represented by general formulas (A) and (B)
Is reacted with a carbonate-forming compound to obtain
A carbonate wherein the general formula (A) is a total monomer component
[9,9-bis (4-hydroxy-3-methylphenyl)
F) Fluorene + general formula (A) + general formula (B)]
And the intrinsic viscosity [η] is 0.2 to 60% by weight.
2.0 [dl / g] polycarbonate resin
Body separation membrane. Embedded image(Where R₁~ R_TwoAre each independently hydrogen and carbon number 1 to
5 alkyl groups, aryl groups having 6 to 12 carbon atoms, carbon number
2-5 alkenyl groups, C1-C5 alkoxy groups,
Or an aralkyl group having 7 to 17 carbon atoms;
When the group has a carbon atom, it has 1 carbon atom as a substituent.
To 5 alkyl groups, alkenyl groups having 2 to 5 carbon atoms,
May have an alkoxy group having 1 to 5 carbon atoms.
R_Three~ R₆Is hydrogen, an alkyl group having 1 to 5 carbon atoms,
Aryl group having 6 to 12 carbon atoms, alkenyl having 2 to 5 carbon atoms
Group, an alkoxy group having 1 to 5 carbon atoms, or 7 to 1 carbon atoms
7 aralkyl groups having carbon atoms in these groups
In some cases, as a substituent, an alkyl group having 1 to 5 carbon atoms,
An alkenyl group having 2 to 5 carbon atoms, or an alkenyl group having 1 to 5 carbon atoms
It can also have a lucoxy group. R₇Has 1 to 6 carbon atoms
Represents an aliphatic group or simply represents a bond. X is -SiO
(R₈) (R₉)-And / or -SiO (R_Ten) (R ₁₁)
-Represents a homopolymer or a random copolymer, and has a degree of polymerization.
Is 1 to 200, and R₈~ R₁₁Are each independently water
Element, alkyl group having 1 to 5 carbon atoms, ant having 6 to 12 carbon atoms
Alkenyl group having 2 to 5 carbon atoms, 1 to 5 carbon atoms
An alkoxy group or an aralkyl group having 7 to 17 carbon atoms
And when these groups have a carbon atom,
To form an alkyl group having 1 to 5 carbon atoms and an alkyl group having 2 to 5 carbon atoms.
Having a kenyl group or an alkoxy group having 1 to 5 carbon atoms
You can also. Where R₈~ R₁₁Medium, at least one
Is a group containing an aryl group having 6 to 12 carbon atoms. )(R₁₂~ R₁₃Are each independently hydrogen, carbon number 1 to 10
An alkyl group, an aryl group having 6 to 12 carbon atoms, and 2 carbon atoms
To 5 alkenyl groups, C1 to C5 alkoxy groups, and
Or an aralkyl group having 7 to 17 carbon atoms.
Has a carbon atom as a substituent,
5 alkyl groups, alkenyl groups having 2 to 5 carbon atoms, or
It may have an alkoxy group having 1 to 5 carbon atoms. Y
IsWhere R₁₄, R₁₅Are hydrogen and carbon number 1 respectively
Alkyl group of 10 to 10, alkenyl group of 2 to 5 carbon atoms, carbon
An alkoxy group having a prime number of 1 to 5, or an ant having a carbon number of 6 to 12
Or a group represented by R₁₄, R₁₅Are bonded together to form a carbon
Represents a group forming 3 to 6 carbon rings or heterocyclic rings,
When any of these groups has a carbon atom,
An alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms,
Or it may have an alkoxy group having 1 to 5 carbon atoms.
You. a represents an integer of 0 to 20. ) 2. The gas separation membrane according to claim 1, wherein the carbonate-forming compound is phosgene. 3. The gas separation membrane according to claim 1, wherein R _{3 to} R _{6 in} the general formula (A) are at least one selected from a methyl group and a phenyl group. 4. The gas separation membrane according to claim 1, wherein the general formula (A) is a random copolymer of dimethylsiloxane and diphenylsiloxane having a 3- (o-hydroxyphenyl) propyl group at α, ω positions. 5. The gas separation membrane according to claim 1, wherein the general formula (B) is 2,2-bis (4-hydroxyphenyl) propane. 6. The ratio of the general formula (B) is:
2. The gas separation membrane according to claim 1, wherein [9,9-bis (4-hydroxy-3-methylphenyl) fluorene + general formula (B)] <0.5 (weight ratio). 7. A carbon dioxide gas transmission coefficient of 16 (10 ^-10 cm ³ (ST
P) ・ cm / (s ・ cm ²・ cmHg))
The gas separation membrane according to claim 1, wherein a ratio of a nitrogen gas permeability coefficient is 30 or more.