JPS59213403A - Organic high molecular membrane - Google Patents

Abstract

PURPOSE:To manufacture an organic high molecular membrane, capable of controlling characteristically the permeability of the membrane to gaseous or other substances of every kind, by incorporating a nematic liquid crystal into a specified organic high molecular compd., and controlling the orientation of the liquid crystal. CONSTITUTION:The high molecular mebrane contains >=1 kinds among the following high molecular compds: polyethylene terephthalate polymer, polymer contg. an aliphatic tertially amino group, polyvinyl alcohol made into acetal with aliphatic aldehyde, cellulosic derivatives esterified with >=1 kinds among aliphatic carbonic acids having 5-16 carbon atoms, copolymer of poly (4-methylpentene-)organopolysiloxane polycarbonate, silicone rubber, and polyalkylsulfone. 5-95pts.wt. nematic liquid crystalline substance is used to 100pts.wt. high melecular compd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic polymer membrane capable of controlling substance selection function.

In recent years, membrane technologies that utilize permeability or selective permeability have been developed in a wide range of fields such as engineering, medicine, and agriculture, and are now being implemented in reality, such as moisture-proof membranes, desalination membranes, artificial fK visceral dialysis membranes, and ion-exchange membranes. It is being done. Furthermore, recently, as an energy-saving technology, the development of specific and highly functional membranes such as oxygen enrichment membranes, resource separation membranes, and charge separation membranes has become increasingly important.

For example, regarding oxygen enrichment membranes, their materials include porous polymer membranes (Japanese Patent Laid-Open No. 55-8803), fluorine-containing silicone rubber-porous polytetrafluoroethylene (Japanese Patent Laid-Open No. 56-5121), Cross-linked polyorganosiloxane-linear polyorganosiloxane copolymer (JP-A-5
6-26508), cellulose monocarboxylic acid ester ('% JP-A-56-26526), styrene siloxane polymer-α, ω-2 functional polysiloxane cross-linked polymer (JP-A-56-28604, etc.), etc. proposals have been made. However, each material has an insufficient balance in gas permeability coefficient, separation coefficient, or film thickness that can be manufactured.

The present inventors have completed research on well-balanced membrane materials for many years and have completed the present invention.

That is, the organic polymer membrane capable of controlling the substance selection function according to the present invention is a polyethylene terephthalate-based polymer,
Aromatic polyesters, aliphatic tertiary amino group-containing polymers, polyvinyl alcohol acetalized with aliphatic aldehydes, cellulose derivatives esterified with at least ] aliphatic monocarboxylic acids having 5 to 16 carbon atoms. , poly(4-methylpentene-1), organoborisiloxane-polycarbonate copolymer, silicone rubber, polyphenylene ether, and at least one organic polymer compound selected from the group consisting of polyalkyl sulfone. and an i-Matic liquid crystal material.

The polyethylene terephthalate polymer used in the present invention is polyethylene terephthalate or a polyester containing 85% or more, preferably 90% or more of ethylene terephthalate units, or a mixture thereof with a small amount of other polymer added. be. Examples of other ester constituents that can be copolymerized with ethylene terephthalate include dibasic acids or oxyacids such as isophthalic acid, inphthalic acid sulfonic acid, zincenyldicarboxylic acid, and sebacic acid, or diethylene glycol, propylene glycol, and tribasic acid. Examples include dihydric alcohols such as methylene glycol, tetramethylene glycol, hexamethylene glycol, and J,4-dihydroxymethylcyclohexane.

The aromatic polyester used in the present invention includes terephthalic acid, inctalic acid, a mixture of terephthalic acid and isophthalic acid (functional derivatives thereof), and bisphenols represented by the general formula % or functional derivatives thereof (however, , -X- is -0-1-so2-1-co-.

-S-, an alkylene group and an alkylidene group, R1, R2, R3, R4, R1, R'2.
R'3 and R'4 are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. or an aromatic polyester obtained from a mixture thereof. Examples of bisphenols used here include 4,4'-dihydroxy-diphenyl ether, 4,4. '-dihydrox'/-
2,2'-dimethyl-diphenyl ether, 4,4'-
Dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-diphenyl sulfide,
4,4. '-dihydroquine-dinenyl sulfone, /1
．． 4'-dihydroxy-diphenylketone, bis(4-
hydroxyphenyl)methane, 1,1-bis(4-hydroquinophenyl)cyclohexane, 2,2-bis(4-
hydroxyphenyl)furopane, 2,2-bis(4-hydroxy-3,5-dibromphenyl)furopane, 21
2-bis(4-hydroxy-3,s-,>chlorphenyl)propane, 2,2-his(4-hydroxy-3
,5-dinotylphenyl)propane, 9,9-bis(4
-Hydroquine pheninolifluorene, 2,2-bis(4
-Hydroxy/phenyl)lupornan, 2,2-bis(4-hydroquine).

Examples of the bisphenol derivatives include bisphenol acetate derivatives. These bisphenols can be used singly or as a mixture of two or more. Further, as the acid component of the aromatic polyester used in the present invention, there may be mentioned buterphthalic acid, inketalic acid, a mixture of terephthalic acid and inphthalic acid, or a functional derivative thereof. Specific examples of the functional derivatives include terephthalic acid chloride, inphthalic acid chloride, terephthalic acid phenyl ester, inctalic acid phenyl ester, and the like.

The aliphatic tertiary amino group-containing polymer in the present invention is
It can be obtained by polymerizing a monomer containing an aliphatic tertiary amino group alone or using two or more components, or by condensation polymerization together with other suitable monomers. For example, an aliphatic tertiary amine group-containing polyether can be obtained by polymerizing an aliphatic tertiary amine group-containing glycol. Specifically, the aliphatic tertiary amino group-containing glycol includes 2-methyl-2-(N,N-dimethylamino)methyl-1,3-
Propanediol, 2-methyl-2-(N,N-diethylamino)methyl-1,3-propanediol, '2-
Methyl-2-(N,N-di-n-propylamino)methyl-1,3-propanediol, 2-methyl-2-(N
, N-di-n-butylamino)ethyl-1,3-propanediol, 2-ethyl-2-(N.

N-dibenzylamino)methyl-1,3-propanediol, 2,2-bis(N,N-dimethylaminomethyl)
-1,3-furopanediol, 2-ethyl-2-piperidylmethyl-1,3-propanediol, 2-1-propyl-2-(N,N-dimethylamino)-n-propyl-1,3- Propanediol, N,N-bis(2-hydroxyethyl)-ethylamine, N,N-bis(2-hydroxypropyl)-methylamine, N,N'-bis(2-hydroxyethyl)-2,3-dimethyl Examples include piperazine, N,N'-bis(2-hydroxypropyl)-piperazine, and the like. Such glycols form polyethers by homopolymerization, as well as ethylene glycol,
It may be copolymerized with one or more commonly used glycols such as propylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Polyurethane and polyether urethane can be obtained by condensation polymerization with diyne/anate using the aliphatic tertiary amine group-containing glycol as described above.

The diisocyanates used at this time include tetramethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate), 1,4-phenylene diisocyanate, -t, diphenylmethane-4,4'
-diisophi; -1-, etc. can be exemplified. If necessary, the obtained polyurethane and/or polyether urethane can be chain-extended with a diamine such as ethylene diamine, m-xylylene diamine, 1,4-butylene diamine, etc. by a conventional method to increase the polymer molecular weight. be. Furthermore, the above-mentioned tertiary amine group-containing glycols can be made into polyesters by condensation polymerization with dicarboxylic acids, and polyesters obtained by synthesis of ordinary glycols and aliphatic tertiary amino group-containing dicarboxylic acids are also effective. It is. Furthermore, it can be made into a hazy polymer by reacting with a chain extender such as diyne/anate or carbonate ester.

The polyvinyl alcohol diacetalized with an aliphatic aldehyde used in the present invention includes polyvinyl alcohol acetalized with an aliphatic aldehyde having 4 to 30 carbon atoms. Aliphatic aldehydes are
A linear and/or branched and/or cyclic aliphatic aldehyde having 4 to 30 carbon atoms, preferably 6 to 28 carbon atoms, and more preferably 8 to 26 carbon atoms, and containing an unsaturated bond in the molecular chain. Alternatively, hydrogen in the molecular chain may be substituted with a functional group such as nitrogen or nitro group. Specific examples of aliphatic aldehydes include n-butyraldehyde,
n-hexaldehyde, tert-butylacetaldehyde, cyclohexanaldehyde, n-octaaldehyde, nonanal, decanal, hexadecanal, octadecaltal, eicosanal, triacontanal,
Examples include hexenal, nonenal, 9-chlorononaldehyde, 5-hydroxypentanal, and the like.

According to the invention, at least one
Cellulose derivatives diesterified with certain aliphatic monocarboxylic acids are also usefully used.

The aliphatic monocarboxylic acid is a linear and/or branched aliphatic monocarboxylic acid having 5 to 16 carbon atoms,
A portion of the hydrogen atoms in the molecular chain may be substituted with a substituent such as a nitrogen nitro group, an alkoxyl group, or an amine group.

Specific examples include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, methyloctanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, and ω-nitrodecanoic acid. acid, ω-methquine tetradecanoic acid '4. Cellulose as a raw material is available in the form of pulp, powder, etc., but cellulose is 10%-,
, may be regenerated cellulose obtained by saponifying with an alkali. Esterification of cellulose with a nuclear carboxylic acid is preferably carried out using the carboxylic acid esterification method, which yields highly esterified cellulose esters with approximately the same degree of polymerization. Te is recommended.

In the present invention, poly(4-methylpentene-1), organoboria xane-polycarbonate copolymer, /recon rubber, polyphenylene ether, and polyalkyl sulfone are also effectively used.Poly(4-methylpentene-1)
1) is a two-dimensional or more copolymer of 4-methylpentene-1 and other monomers such as ethylene, styrene, or butadiene within a range that does not impair the properties of poly(4-medium/l//<ntene-1). Consolidation can also be used.

The organic polymer compound used in the present invention is selected depending on the intended use of the film and the usage situation, as long as it has compatibility with the nematic liquid crystal material. For example, when used as an oxygen-enriched membrane, an organic polymer compound having an appropriate solvent is selected.

Examples of the imatic liquid crystal materials used in the present invention include methoxybenzylidene-pn-butylaniline, ethoxybenzylidine-pn-butylaniline, and n-propyroquinebenzylidene-pn-butylaniline. , n-butquinbenzylidene-pn-butylaniline, methoxy7benzylidene-pn-amylaniline/, ethoxy/benzylidene-pn-amylaniline,
n-probyloxybenzylidene-p-n-amylaniline, n-butylidene-pn-amylaniline, n-amyloxybenzylidene-pn-alkylaniline, methoxybenzylitine-p -n-hexylani+)7. p-7 dicylidene-p-aζnophenyl acetate, p-ani/redene-p-a(nobenzonitrile, p-azoki7-anineol, p-ethyl-7-p'-
Hexanonyloxyazobenzene, p-n-hegifulve/
Zoicqua/Nodo-p/n-hekifluoroxyphenyl ester, phthyl/1. -(4'-Ethoxyphenoxycarbonyl)-phenyl carboy;-(BEPC
, PC), N-4-be/thyroxycarbonyloxypensyritene-4'-aninodine (PCBA), 4-n-heptinobenzoic acid (HBA), N,N'-
Bis-p-methquinbenzylidene-3,3'-cyclopendiazine (MT3DB) and the like can be mentioned.

The amount of nematic liquid crystal material used depends on the intended use of the membrane.
The amount can be appropriately selected from the range of 5 to 95 parts by weight based on 100 parts by weight of the organic polymer compound.

In the present invention, the effect is further enhanced when a substance selectivity improver is used in combination. The substance selectivity enhancer is selected from a wide range of substances depending on the intended use of the membrane. For example, when the organic polymer membrane according to the present invention is used as an oxygen-enriching membrane, a substance with a high oxygen uptake capacity is advantageously selected as the substance selectivity improver. Examples include perfluorotributylamine, perfluorodecalin, perfluoromethyldeca\hacillin, perfluorotetrahydrofuran, perfluorobutyltetrahydrofuran, and the like.

Furthermore, when a crown ether is used as a material selectivity improver, an organic polymer membrane that selectively transmits metal ions can be obtained. Furthermore, when azo crown ether is used, it is possible to obtain, for example, an organic polymer M-gold whose transport of K+ ions can be accelerated by light. The amount of addition of the material selectivity improver is appropriately determined by taking into account the type of organic polymer compound used in the organic polymer film, the type of nematic liquid crystal material, the amount used, and the like. Furthermore, a surfactant or the like may be added to improve the dispersion of the substance-selective agent.

The organic polymer membrane according to the present invention can be used in stacked forms such as a flat membrane, a spiral membrane, and a hollow fiber membrane. When used as a flat film, it is often used as an extremely thin film, but the organic polymer film according to the present invention can fully exhibit its performance when used as a thin film. As a method for producing the film, any of the dry-wet film forming method, polymer solution coating method, mainland spreading method, etc. can be used.

The organic polymer membrane according to the present invention can specifically control the selection function of various substances, and has a wide range of applications including oxygen enrichment membranes, resource separation membranes, charge separation membranes, and the like. Furthermore, since it contains a nematic liquid crystal material, the liquid crystal alignment can be controlled by applying an electric field, thereby making it possible to specifically control the membrane permeability of gases and other substances.

Hereinafter, the present invention will be specifically explained using examples.

Example 1 2.2-bis(4-hydroxyphenyl)propane 50
By interfacial polycondensation, 50 mol% of 2,2-bis(4-hydroxy3.5-dimethylphenyl)furopane was used as a bisphenol component, 50 mol% of terephthalic acid chloride and 50 mol% of inphthalic acid chloride were used as acid components. Obtain aromatic polyester. and a polymer of
N,N'-bis-p-methquinbenzilitine-3,3'
- A chloroform solution of dichloropendiazine (MBDB) was cast onto a glass plate using an applicator.

After drying in air at room temperature, the glass plate was immersed in ice water, and the film came off after about 1 hour. The thickness of the obtained film was 20 μm.

The transmission of 02/N2 was measured for this film.

The oxygen permeability is 5. lX10'''8cm3 (STP)
/cmsee-cm H5', separation factor (PO2/P
N,,) was 3.5.

Example 2 The aromatic polyester used was a polymer obtained by interfacial polycondensation from a mixture of isophthaloyl chloride and isophthaloyl chloride with isoelectric st in 1,1-bis(4-hydroxyphenyl)cyclohexene.
A film was formed in the same manner as in Example 1. Similar results were obtained for oxygen permeability and separation coefficient. ' Example 3 2-methyl-2-(N,N-dimethylamino)methyl-
1,3-furopanediol 14.1 f Dissolved in dimethylformamide 100F, and added diphenylmethane diincyanate 25? dimethylpolamide 502
was gradually added to the mixture and reacted at 5° C. for 2 hours to complete the polymerization.

N-4-Benzyloxycarbonyloxybenzylidene-4'-anisidine (PCBA') was added to the obtained polymer solution, 10 mA of the obtained polymer solution was poured onto a glass plate, and the solvent was heated at 70°C for 5 hours. was removed.

The transmission of 02/N2 was measured on the thus obtained film (thickness: 201%), and the same results as in Example 1 were obtained.

Example 4 N-ethyljetanolamine 13.5 F, bexamethylene diyne cyanur) J, 8. ! M, 0.2 f of diptyltin diwhale urate and 2 oor of methylformamide were polymerized at 70° C. for 4 hours in a nitrogen stream. A film was obtained from this polymer by kneading in the same manner as in Example 3, and the transmission of 02/N2 was measured, and the same results as in Example 3 were obtained.

Example 5 Cyclohexenol was added to cyclohexene, and 5
It was prepared in a manner similar to the concentration of % by weight. Poly4-methylpentene-1 was dissolved in this to a concentration of 5% by weight, and 4-n-hebutyroxy was dissolved in zoic acid (NB).
A) was added dropwise to water to prepare a thin film.

As a result of measuring the transmission of 02/N2 for this film, the same results as in Example 1 were obtained.

Example 6 When the permeation of 02/N2 was measured for a film obtained from a mixture of polysiloxane-polycarbonate copolymer and ethoxybenzyrib 7-p-n-amylanilide, it was almost the same as in Example 1. Similar results were obtained.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] Polyethylene terephthalate-based polymers, aromatic polyesters, aliphatic tertiary amino group-containing polymers, sitapolyvinyl alcohol diacetalized with aliphatic aldehydes, at least one aliphatic monocarboxylic acid having 5 to 16 carbon atoms Diesterified cellulose derivative, poly(4-methylpentene-1), organopolysiloxane-polycarbonate copolymer, silicone comb,
An organic polymer membrane capable of controlling a substance selection function, characterized by containing at least one organic polymer compound selected from the group consisting of polyphenylene ether and polyalkyl sulfone, and an imatic liquid crystal substance.