JPS61250012A - Copolymer having electron accepting group - Google Patents

Abstract

PURPOSE:To provide the titled copolymer composed of a recurring unit having a specific substituted aromatic group, etc., at the side chain, a recurring unit having hydroxyl group, carboxyl group, etc., at the side chain, etc., having high selective permeability and useful as a raw material of separation membrane for a liquid mixture containing aromatic compounds. CONSTITUTION:The objective copolymer having a molecular weight of >=10,000 and composed of the recurring unit of formula III (R<2> and R<3> are same as R<1>; Y is S, O, ester group, amide group, etc.; Z is aromatic group or quinonyl group substituted with NO2, CN, halogen, etc.; m is 0 or 1; n is 0 or positive integer) and the recurring unit of formula IV can be produced by homopolymerizing the monomer of formula I (R<1> is H, halogen or 1-4C hydrocarbon group; X is O, S, ester group, amide group, etc.; l is 0 or 1; E is CH2CH2 OH, COOH, etc.) or copolymerizing the above monomer with the monomer of formula II (R<4> is same as R<1>; A is H, cyano, OH, COOH, etc.), and reacting the obtained homopolymer or copolymer with a carboxylic acid derivative having aromatic group or aromatic quinonyl group group nucleus-substituted with an electron accepting group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel copolymer having an electron-accepting group that is useful as a membrane material for a separation membrane for liquid mixtures containing aromatic compounds.

[Prior art]

The copolymer of the present invention is a new compound that has not been described in any literature, and can be used as a separation membrane for liquid mixtures containing aromatic compounds, which is more efficient than membrane formation.

Pervaporation is known as a typical method for separating liquid mixtures using a non-porous, uniform polymer membrane. This membrane separation method involves organic liquid mixtures that cannot be separated by ordinary distillation methods, such as azeotropic mixtures, near-boiling point mixtures, structural isomers, and thermally denatured organic liquid mixtures, which contain a large amount of J*.

For example, xylene isomers and ethylbenzene obtained as the 08 fraction of petroleum refining can be separated by a series of methods that combine highly precise distillation, fractional crystallization, and chemical reactions, or by extracting and separating the target substances by specifically complexing them. Since it is necessary to repeat extremely complicated operations, there is a strong desire to develop an efficient separation method. Attempts have also been made to apply the above-mentioned pervaporation method to this separation, and as separation membranes, crystalline polyethylene membranes, cellulose s-conductor g, and cyclodetrines-containing polymer membranes are known, or the former two are selective. In addition, the latter has extremely poor membrane permeability, making it difficult to put it into practical use. Recently, a method has been proposed in which a Werner complex that specifically forms an clathrate compound for these nuclear substitution isomers is supported in a membrane to improve the separation ability, but the conditions when creating the membrane, It is complicated to operate, and its transparency is low, making it unsuitable for practical use.

As described above, to date, there are no known polymer membranes that can efficiently separate liquid mixtures containing aromatic compounds.

[Problem that the invention seeks to solve]

Provides a polymeric separation membrane material that can efficiently separate liquid mixtures containing aromatic compounds, and liquid mixtures containing aromatic compounds that are unsubstituted or have electron-donating nuclear substituents. However, it is possible to overcome the drawbacks of the above-mentioned polymer membranes.

[Detailed description of the invention]

Generally, it is known that charge transfer complexes are formed between electron-donating compounds, electron-accepting compounds, and 0, but even though they differ in their ability to form complexes (Organic Char
ge-Transfer Complexes.

Academic Press, 1969) The present invention has focused on this point, and has a novel electron-accepting group that can be used as a separation membrane material that realizes efficient membrane separation by cleverly utilizing the formation of intermolecular charge transfer complexes. The present invention provides a copolymer.

That is, the present invention relates to a copolymer of 10,000 or more molecules in molecule-1 consisting of a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula A (in the formula, a', 6nF and R4 is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 4 carbon atoms; methylene chain of 4, Y represents a sulfur atom, an oxygen atom, an ester bond, an amide bond, a urethane bond, an imine bond, an iminoether bond, a sulfide bond, or a bond represented by the structural formula. Both represent an aromatic group or quinonyl group substituted with one nitro group, cyano group, carbonyl group, sulfonyl group, or halogen atom (however, cases in which the nucleus is substituted with only a nitro group are excluded).Hydrogen atom , a cyano group, a hydroxyl group, a carboxyl group, or a group represented by the formula (wherein g is a hydrocarbon group having 1 to 15 carbon atoms, or the structural formula and I each independently represent a carbon A hydrocarbon group having 1 to 4 carbon atoms;
is the same as above, gFi-OH2C)I20f(.

-CH2CH2C1, -CH2CH2Br, -(?
H2CH2I, -COOH, -α℃1, -N■, -
qsu, -〇H1-NH2, -CH2C(OH,)280
3H, -8H, -0H2CH7H.

Indicates υ 1. However, if necessary, it may be protected with an acetyl group or the like during polymerization. W and H are the same as above.) The resulting polymer has electron-accepting properties such as one or more nitro groups, cyano groups, carbonyl groups, sulfonyl groups, etc. Amino≠conductor, alcohol derivative, having an aromatic group substituted with a group or an aromatic quinonyl group as a substituent;
It can be obtained by reacting carboxylic acid derivatives or thiol derivatives (however, derivatives whose nucleus is substituted only with nitro groups are excluded).

Things expressed by the general formula (to)! - as 2-hydroxyethyl acrylate, d2-hydrodiethyl methacrylate, 2-hydro-dipropyl methacrylate, glycidyl methacrylate, p-nitrophenyl acrylate, p-nitrophenyl methacrylate x=sp, 7/skW12 -chloroether, N-(2-chloroether)acrylamide, 2-hydroxyethyl vinyl ether, acrylic acid 2
-bromoether, 2-'M-doether methacrylate, allylamine, allyl alcohol, N-(2-hydroxyethyl)acrylamide, thioglycidyl acrylate,
Acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid chloride, vinyl isocyanate, acrolein, vinyl alcohol, N-(2-methyl-2-sulfopropyl)acrylamide, 2-mercaptoethyl methacrylate, acrylic acid 2.3-? ) Human cI-? Dipropyl, pentachlorophenyl acrylate, vinylthioic anate, acrylic acid hydrazide, acrylic hydro+tA11', 7/! Examples include 2-chlorosulfonyl ethyl acid.

In addition, monomers represented by the general formula include ethylene, pro, pyrene, acrylonitrile, vinyl alcohol (protected with an acetyl group during polymerization), acrylic acid, methacrylic acid, acrylamide, methacrylamide, methyl acrylate, acrylic Ethyl acid, methyl methacrylate, propyl methacrylate, #t-butyl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, ethyl acrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2 Examples include -hydroxypropyl, N,N-dimethylacrylamide, N,N-diethylmethacrylamide, ethyl vinyl ether, n-silvinyl ether, and vinyl acetate.

For these monomer ○ copolymerization reactions, known methods such as radical copolymerization, ionic polymerization, redox polymerization, and photopolymerization can be used. During the radical copolymerization reaction,
Bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used, but it is preferable to carry out the copolymerization in a solvent because it allows copolymerization in a homogeneous reaction and obtains a high molecular weight product. As a radical initiator used for the reaction, Examples include organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, and lauroyl peroxide, and azo compounds such as azoisobutyronitrile and azobiscyclohenotenitrile, but are not particularly limited to these. It's not something you can do. The solvent used in the reaction is suitable as long as it can uniformly dissolve each of the seven molecules (for example, N, N-
Examples include dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfonate, dihydrofuran, ethyl acetate, butyl acetate, chloroform, acetone, methanol, ethanol, dioxane, and the like.

It is desirable to carry out the polymerization reaction at a temperature in the range of 40°C to 200°C in order to proceed with the reaction efficiently.

In the case of anionic polymerization or spherical polymerization, a base, an anionic catalyst, or a Lewis acid is used as a catalyst, and the reaction is generally carried out at a temperature in the range of -110°C to 60°C. At this time, it is preferable to carry out the reaction in a solvent, and examples of the solvent that can be used include dihydrofuran, dimethoxyethane, diodPsan, acetonitrile, N,N-dimethylformamide, and aromatic hydrocarbons.

As bases, butyllitecum, lithium diisopropylamide, lithium, bis(trimethylsilyl)amide,
Examples include phenyllithium, phenylmagnecum bromide, chalicum tert-butoxide, and sodium tert-amilium chloride.

Examples of the anionic catalyst include potassium heptafluoride, cesium heptafluoride, tetrabutylammonium fluoride, potassium potassium heptafluoride, trialkylsuldinium heptafluoride, potassium cyanide, and sodium azide.

Examples of Lewis acids include zinc bromide, zinc chloride, zinc iodide, and -dimethylaluminum chloride. When using this catalyst, aromatic hydrocarbons or halogenated acids such as dichloroethane and dichloroethane can be used as solvents. Preference is given to using hydrocarbons.

The molecular weight of the copolymer of the present invention is 10,000 or more, particularly 50,000 or more.
When using the copolymer as a separation membrane, it is desirable for the copolymer to have a molecular weight of 10,000 or more. Further, the composition of the repeating unit having an electron-accepting group represented by general formula (1) in the copolymer is in the range of 1 to 95 mol, more preferably 5 to 60 mol.
It is desirable to be in the 〇 range. If the content of the repeating unit of general formula (I) is more than 95 molty, the mechanical strength when used as a separation membrane will be poor, and if the content is less than 1 molty, the selectivity will be reduced.

〔Effect of the invention〕

The copolymer of the present invention can be formed into a film by, for example, a casting method after being dissolved in a solvent. The resulting polymer membrane has sufficient mechanical strength as a separation membrane. In addition, it exhibits selectivity and permeability that are superior to the prior art in the separation of isomers, for example, and can be useful as a separation membrane for liquid mixtures containing aromatic compounds. More detailed explanation〇Example 1 7/IJ 2-hydrodiethyl acid (HEA) 15.8
g was charged into a glass polymerization tube, and N was added as a diluent.

97m of N-dimethylformamide (DMF) and 0.1Og of 2,2-azobisisopteronitol (IBN) as a polymerization initiator were added, and after degassing in the usual manner, under high vacuum (
The tube was sealed with 1 g (10 mrnl or less). This was shaken and polymerized at 60° C. for 2 hours.

18. Pour the reaction mixture into a large amount of diethyl ether.
A homopolymer of HEA (PHEA) was obtained with a yield of 6-.

The average weight molecular weight of this polymer was determined by GPC measurement in DMF to be 4. It was rare with 1X10'.

After dissolving 1.1 g of PHEA in 50% DMF and thoroughly purging with argon, a DMF solution of 201 containing 1.5g of pentafluorobenzoic acid chloride was added dropwise at 0°C, and the mixture was stirred overnight under an argon stream. did. Then increase the temperature to 50
The temperature was raised to 0.degree. C. and stirring was continued for an additional 1.5 hours.

The reaction mixture was poured into a large amount of diethyl ether to precipitate the polymer. This was purified by filtering it, redissolving it in DMF, and precipitating it in diethyl ether, yielding 1
．． 8 g of a polymer was obtained with a yield of 69.2%. IR,NM
After elemental analysis, it was confirmed that the polymer contained 1 c27.1 mole of pentafluoro 2 enyl groups in side chains, and as a result of GPC measurement, the molecular weight was 4, OXI O' (polystyrene equivalent).

IR (cs+): 3400(-α(), 2800(
-CH2-).

1730 (C==0), 1650 (hexasubstituted benzene ring)
, 1140 (-C-F) Elemental analysis (CH): C, 46,9; H, 4,9 Synthesis of Example 2 Acrylonitrile (AN) 3.7 g and p-nitrophenyl acrylate (PNP) 5.8 g into a glass polymerization tube, DMF40- and AIB No. 034
g, and after degassing in the usual manner, under high vacuum (10 mmHg
Good to seal with (below). This was shaken and polymerized at 60° C. for 4 hours. The reaction mixture was poured into a large amount of water-methanol mixture (1:9 volume ratio) to obtain a 14.2-sized AN-PNPA copolymer. PNPs in copolymers
The A content was 9,9-w- as determined by elemental analysis, and the molecular weight was 1,6X]0' (GPC).

1 (3): 3100 (disubstituted pen-try@).

2250 (C!!!N), 1760 (C=0), 153
0 (N-0) Elemental analysis (%): C, 59,2; H, 4,3; N, 13
．． 0.61 g of the obtained par-PNP copolymer was DM
A DMF solution containing 1.28 g of 2-pentachlorophenylthioetheramine (POP) dissolved therein was added dropwise at room temperature, and after stirring overnight, the temperature was reduced to 60° and the reaction was continued for a further 4 hours. The reaction mixture was poured into a large amount of methanol to precipitate a polymer, which was filtered and dried under vacuum to obtain 60 g of fiO polymer. As a result of the I-N measurement, PCP was quantitatively introduced into the polymer through ester-amide exchange with the PNP human site, resulting in AN-N.
It was confirmed that -(2-pentachlorophenylthioethyl)acrylamide (PeAm) copolymer was produced.

The composition of PCAm in the AN-PCAm copolymer was determined to be 39.5 mol-1 and the molecular weight was 1.6×10'.

IR (cm'): 2800 (-〇)Iz)
, 2200 (C thought N).

1760 (C==O), 1440 (-8-), 105L
)~x1oo (C-CI), 87u (hexasubstituted benzene ring) Elemental analysis (%): C, 40,1; H, 2,7; N, 7,
6;8.7,0;C1,37,4 Example 3 4.8g of AN and 5.2gt of VAc in acetic acid
DMF 40 and AIBN 0.03 in a gas 2 gas tube.
After adding 4 g and degassing by a conventional method, the tube was sealed under high vacuum (10 mmHg or less). A polymerization reaction was carried out by shaking the mixture 9 times at 60° C. for 17 hours. The reaction mixture was poured into a large amount of methanol, yielding 3.61 g and 36.3 g.
c copolymer. The structure of the copolymer was double-checked, and the VAc composition calculated from elemental analysis was 16.0 mol. Also, molecular weight i2. I met it with lXIO3.

IR(es): 2800 (-C)12-),
2200 (C3iN).

1740 (C=0) Elemental analysis (chi): C, 63,9; f (, 5, 9; N, 2
0.12 g (F) AN-vAc copolymer to D
MF-water mixture (2:1 volume ratio) was dissolved, 15 ml of an aqueous solution containing 0.36 g of sodium hydroxide was added thereto, and the mixture was stirred at room temperature for 5 hours. The reaction mixture was poured into a large amount of methanol to precipitate the polymer. The yield was 1.6 g, yield 80 g.

As a result of the IR measurement of this polymer, the absorption at C=0 of 1740α observed in the AN-VAc copolymer completely disappeared, and a new absorption derived from the 10H group appeared around 3400 cm. It was confirmed that this was an AN-VA copolymer having a polyvinyl alcohol (MA) structure in which all VAc sites were saponified.

Elemental analysis (%): C, 66,1; H, 6,2; N, 23
．． 0.0 g of the obtained AN-V human copolymer was added to Dtvi
After dissolving in F and thoroughly purging with argon, a 20d DMF' solution containing pentafluorobenzoic acid chloride], Og was added dropwise at 0°C, and the mixture was stirred overnight under an argon stream.

The temperature was then raised to 50°C and stirring continued for an additional 1.5 hours. The reaction mixture was poured into a large amount of methanol to precipitate the polymer. The yield was 1.4 g and the yield was 77.8.

IR measurement results of the polymer showed that AN-VA copolymerized reed AN-vinyl pentafluorobenzoate (PFBV) has a structure in which a certain acid group is substituted with pentafluorobenzoate ester.
It was confirmed that it was a copolymer.

As a result of elemental analysis, the composition of the PFBV site in the copolymer is 1
It was 5.8 inches.

IR (CI+): 2800 (CH2),
2200 (C:iN).

1730 (e:0), 1650 (hexasubstituted benzene fi)
, 1140 (C-F) Elemental analysis (chi): C, 57, 6;) I, 1, 3;
N, 14.2 molecular weight: l, 7X105 (GPC) Example 4 AN 4.25 g and glycidyl methacrylate (GM
A) Pour 1.42g into a glass polymerization tube and add THF43
, 8 id and AIB No. 034 g were added, and after degassing in a conventional manner, the tube was sealed under high vacuum (10 mmHg or less). This was stirred at 60°C for 24 hours to carry out a polymerization reaction. The reaction mixture was poured into a large amount of methanol, II, 8q
A l-ω French copolymer was obtained with a yield of 6. In copolymers.

The GMA content was 26.37% based on elemental analysis, and the molecular weight was 4.1×10.

IR (m): 2B00~29'UO (-CH2+,
-(J(,).

2250 (CEN), 1735 (C=0), 1260°910.760 (Epo ring) Elemental analysis (chi): e, 63.4; H, 6, 4; N, 13
．． 0.6 g of 4λN-GMA copolymer was dissolved in 15-dimethyl sulfoxide (DJK), and 0.2 g of 2.4
A DM80 solution of 401 containing -dicyanophenol and 0.07 g of sodium hydroxide were added and stirred at 60°C overnight. After the reaction, DM80 was distilled off in vacuo and D
MF15- was added to make a homogeneous solution again. This was poured into a large amount of methanol to precipitate the polymer.

When the precipitate was filtered, dried, and subjected to IR measurement, the absorption of 1260 cm, 91 Uac, and 760 am derived from the epoxy ring disappeared, and a new absorption of 3400 cm was observed.
Absorption derived from the hydroxyl group at , and the trisubstituted benzene ring appeared near 1600α and 8501. From this, it was confirmed that it was a dipropyl (DCPM) in 3-(2,4-dicyano-7-enyl)-methacrylic acid and 2-hydro-in-bar methacrylic acid copolymer in which 2,4-dicyanophenol reacted with the epoxy group. . The DCPM content in the copolymer is 25.9%/→, the molecular weight is 3.2X] 0' (GPC) Tero'
:) &.

I 几(α): 3400(-α(), 2800~290
0(-CH2-,-CH,), 2200-2250(
C-N).

1735 (C=O), 16oO and 85G (, Efl
(benzene ring) Elemental analysis (%): C, 64, 7; 1 (, 5, 16;
N, 15.5 Example 5 0.88 of the AN-PNPA copolymer obtained in Example 2 was DM
2,3-dicyano-5-
DMF solution 201 containing 0.6 g of chloro-6-(2-aminoether)thio-1.4-benzonone (DCQ) was added and stirred overnight at room temperature. Mix the reaction mixture with a large amount of meth/
- to acetonitrile mixture (3:1 volume ratio) to precipitate the polymer, which was then dried in a vacuum to obtain a polymer of F) IJJg. As a result of I liter measurement, DC
Q was quantitatively introduced into the polymer through ester-amide exchange with the PNP human moiety, i.e., AN-N-(2-(2,3
-dicyano-5-chloro-1,4-benzo-nonylthio)ethylcoacrylamide (DCAm) copolymer. AN-D DC in CAm copolymer
Ati1 composition is 38.44/n, molecular weight is 1. IXI
O' (GPC) Terror 2 f5゜I几(C1l
): 2900(-C)Iz-), 2250(c
=N).

1740 (C===0), 10513-1100 (C-
CI) Elemental analysis (%): C, 52,6; H, 3,1
; Ns 15,9 ; 8.7,87; C1,8,7 Reference Example 1 1 g of the Hg-PPP copolymer obtained in Example 1 was added to 1 liter.

g of DMF, this was cast on a Teflon plate with 50 scratches, and DMP was distilled off at 40°C. Further under vacuum, 60
Uniform and transparent nickname 6 by vacuum drying overnight at ℃
A five-layer membrane was obtained. This membrane was inserted into a stainless steel cell for pervaporation (pervaporation cell), and the permeation side was reduced in pressure to 0.5 mmHg to permeate the benzene (Bz)-cyclohexane (ah) mixture. The composition of the mixed liquid that passed through the membrane was detected by TCD-gas chromatography, and the permeation rate P (g - m/m' - h) and selectivity α were determined by the following formula.

As a result, the feed liquid composition z/Ch=33.08766.9
2, P=1,58X10 g-m/m'-h,
A value of a=4.83 was obtained.

Reference Examples 2 to 9 0.5 g of the copolymer obtained in Examples 2 to 5 was added to DMF5
m and cast the solution on a glass plate at 50°C.
The solvent was distilled off for an hour. Next, this glass plate was immersed in water, and the film was peeled off. All the films obtained were uniform and transparent. Using these membranes, permeation measurements of liquid mixtures were carried out in the same manner as in Reference Example. The results are shown in Table IK.

Claims (1)

[Claims] (1) Molecular weight consisting of the repeating unit represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ - (I) and the repeating unit represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ - (II) 10,000 or more copolymers [wherein R^1, R^2, R^3 and R^4 are hydrogen atoms, halogen atoms, or hydrocarbon groups having 1 to 4 carbon atoms, X is oxygen atom, sulfur] atom, ester bond, amide bond, urethane bond, imine bond, iminoether bond, disulfide bond, sulfonyl bond or methylene chain having 1 to 4 carbon atoms, Y is a sulfur atom, oxygen atom, ester bond, amide bond, urethane bond, Represents an imine bond, iminoether bond, disulfide bond, or a bond represented by the structural formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ . Z represents an aromatic group or a quinonyl group whose nucleus is substituted with at least one nitro group, cyano group, carbonyl group, sulfonyl group, or halogen atom of the same or different types (however, this excludes cases where the substitution is only with a nitro group). ). A represents a hydrogen atom, a cyano group, a hydroxyl group, a carboxyl group, an amide group, or a group represented by the general formula -COOR^5, ▲numerical formula, chemical formula, table, etc.▼, -OR^8 or -OCOR^9 (In the formula, R^5 is a carbon number of 1 to 1
5 hydrocarbon group or structural formula -CH_2CH_2OH, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, groups indicated by , R^
6 and R^7 are hydrocarbon groups having 1 to 4 carbon atoms, R^8
and R^9 represents a hydrocarbon group having 1 to 6 carbon atoms. ). n represents 0 or a positive integer, and l and m represent 0 or 1. However, at least l, m, and n cannot be 0 at the same time. ] (2) In the copolymer, the general formula (
The copolymer according to claim 1, which contains 1 to 95 mol% of repeating units of I).