JPS6356531A - Novel graft copolymer and gas separation membrane - Google Patents

Abstract

PURPOSE:To obtain a copolymer capable of giving separation membranes for effectively separating gaseous oxygen from nitrogen followed by concentration, by reaction between a specific poly-disubstituted acetylene and strong base followed by with a cyclosiloxane compound and then stopping the reaction with a halogenosilane compound. CONSTITUTION:The objective poly-disubstituted acetylene/polyorganosiloxane graft copolymer of a molecular weight >=10,000 constituted of the recurring units of formula I (A is alkyl or phenyl; X is H or of formula II; Y is oxygen atom or divalent organic group; Z is polyorganosiloxane chain of formula III; R<1>-R<7> are each H, alkyl, alkenyl or phenyl) with the molar ratio for the recurring units: 99/1-5/95 (pref. 60/40-10/90) of the poly-disubstituted acetylene in the main chain to the polyorganosiloxane in the side chain.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention relates to a novel borini-substituted acetylene/polyorganosiloxane graft copolymer whose main chain is a polydisubstituted acetylene and whose side chain is a polyorganosiloxane, and to the copolymer. It relates to membranes for separating gas mixtures formed from coalescence.

In particular, the present invention relates to a selective gas separation membrane that has a large oxygen permeation rate capable of concentrating oxygen gas in the air, and has excellent permselectivity and membrane strength.

Gas separation methods using membranes are rapidly becoming increasingly popular due to their energy saving, high safety, and ease of operation. Among them, technology to separate oxygen from mixed gases,
In particular, technology that separates and concentrates oxygen from air is useful.

If oxygen-rich air can be easily and economically produced, it is expected to make a significant contribution to fields such as various combustion engines, medical equipment, the food industry, and waste treatment.

[Prior art and its problems] The desired characteristics of the membrane used for the above purpose are a large ratio of the permeability coefficients of oxygen gas to nitrogen gas and a large permeation amount of oxygen gas. In particular, the latter is extremely important in downsizing the separation device and increasing the amount of gas that can be processed. In order to obtain a large amount of oxygen gas permeation, it is necessary to select a membrane material with a large oxygen gas permeability coefficient Po2 and to make the membrane thickness as thin as possible. Therefore, it is important that the membrane material has sufficient membrane strength to withstand thinning.

Among the polymer membranes known so far, the large gas permeability coefficient P (hereinafter, unless otherwise specified, the unit of permeability coefficient is m2 (STP) 6 cm / am2@° formula・
cInHg. ) is polydimethylsiloxane.

The permeability coefficient Po2 of oxygen gas is 6X10-8, which is high permeability, but the separation coefficient α between oxygen gas and nitrogen gas (permeability coefficient Po2 of oxygen gas/permeability coefficient PN2 of nitrogen gas) is 2
．． As low as 0. Furthermore, since polydimethylsiloxane has a low mechanical strength, it is impossible to form a film that can withstand actual use at a thickness of several tens of μm or less. For this reason, it is difficult to obtain a membrane having a sufficient amount of gas permeation. US Patent No. 39
No. 80456, No. 3874986, JP-A-56-26
Copolymers of polydimethylsiloxane and polymers with high mechanical strength such as polycarbonate and polyα-methylstyrene have been developed for the purpose of improving the film-forming properties of polydimethylsiloxane, such as in Publication No. 504. The results were not necessarily satisfactory, as the permeability coefficient Po2 was decreased and the separation coefficient α was insufficient.

On the other hand, polydisubstituted acetylenes represented by pri(1-trimethylsilylzolopine) are known as materials with higher gas permeability coefficients than polydimethylsiloxane (
Ja Ama Chem, Soc, 5105.7
473 (1983) or J. Appl. Poly.
rri.

Set, 30.1605 (1985)). This poly(
1-trimethylsilylzorobin) has an oxygen permeability coefficient Po2 of 4 to 7×10.

It has a separation coefficient α of 1.7 to 2.0, and has excellent film strength, so it can be formed into a thin film.

However, when used as an oxygen separation membrane as it is, the separation coefficient α is small, so a sufficient oxygen concentration cannot be obtained, and furthermore, the oxygen permeability coefficient decreases when used for a long time.

(Polyrn fan Praprints * Jap
an a 35 e 424 (19ss)) polydisubstituted acetylenes other than (1-trimethylsilylpropyne), such as pri(2-octene), poly(2-decyne), poly(1-7enylpropyne), All films formed from materials such as poly(1-chloro-2-phenylacetylene) have sufficient film strength, but the oxygen permeability coefficient Po2 is 4×10 or less (F) (Polym@r
Bull@tin, 10 e 114 (1983)
) It cannot be used as a practical oxygen separation membrane.

[Problems to be Solved by the Invention] The present invention solves the drawbacks of the conventional gas separation membranes mentioned above, especially d
In order to solve the drawbacks of liny-substituted acetylene, there are nine new innovations that provide excellent gas permeability and selectivity and a stable gas permeability coefficient while maintaining the sufficient membrane strength of liny-substituted acetylene. It provides membrane materials for

[Means for Solving the Problems] The present inventors have made efforts to obtain a new membrane material that provides a high gas separation coefficient and a stable gas permeation coefficient while taking advantage of the excellent membrane strength of I-liny substituted acetylene. investigated. As a result, a membrane made of a polydisubstituted acetylene/polyorganosiloxane graft copolymer obtained by introducing a polysiloxane chain into a terini-substituted acetylene has a good gas separation coefficient and membrane strength, and has a significantly lower polydisubstituted acetylene. The present inventors have discovered that the present invention has a gas permeability coefficient higher than 1, and provides a stable gas permeation coefficient, and has completed the present invention.

That is, in the present invention, the repeating unit is represented by the general formula (1)% formula%
(1) (In the formula, A represents an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group. is an oxygen atom or a divalent organic group, 2 is the general formula (
The polyorganosiloxane chain represented by sl-o)-(II), R-R, and R and R may be the same or different (hydrogen atom, alkyl group).

Indicates a substituted alkyl group, alkenyl group, substituted alkenyl group, phenyl group or substituted phenyl group.

The molar ratio of the polyvinyl-substituted acetylene repeating unit in the main chain to the nosiloxane repeating unit in the side chain is in the range of 99/1 to 5/95, and the molecular weight is at least 10,000 or more. The present invention relates to a substituted acetylene/I-liorganosiloxane glatt copolymer and a separation membrane for a gas mixture comprising the copolymer. In addition, the branched chain A represented by general formula (1) includes a propyl group,
Alkyl groups with straight or branched chains such as isoglopy/l/ groups, pentyl groups, and hezotel groups, substituted alkyl groups in which these hydrogen atoms are substituted with other atoms, phenyl groups, and further hydrogen atoms of phenyl groups. Examples include substituted phenyl groups substituted with fluorine atoms and the like.

In the general formula (I), X represents a hydrogen atom, a substituent, or a divalent organic group, for example, a substitution). -CH20H2CH2-, etc. can be exemplified. Further, 2 is a polyorganosiloxane sedation represented by (Si-0)-. R-R is a hydrogen atom, a C1 to C1° linear or branched chain or cyclic alkyl group, and some of the hydrogen atoms of these alkyl groups are halodane atoms, trimethylsilyl group, phenyl group, hexafluoro Phenyl ts, -00F(CF,)2, -C00CH2(C
F2) Substituted alkyl groups and phenyl groups substituted with 3CF, -COOCH2C6H5, etc., and alkenyl groups such as substituted phenyl groups and vinyl groups in which some of the hydrogen atoms of the phenyl group are substituted with alkyl groups, halodane atoms, etc. ,
It is a substituted alkenyl group.

Polydisubstituted acetylene consisting of a repeating unit represented by the general formula (1) of the present invention/? For example, the liorganocloxane graft copolymer has a repeating unit of the general formula (2) % formula % () (in the formula, % represents an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group, and each repeating unit may be arbitrarily different from each other.) After reacting with a strong base, a polydisubstituted acetylene consisting of a polydisubstituted acetylene consisting of ) is reacted with a cyclosiloxane compound represented by the general formula B-8l-R' (V) (wherein B
is a halodane atom, and R3-R5 are the same as above. ) It can be synthesized by adding a triorganohalogenosilane compound represented by the following to stop the reaction. In addition to the above method, after reacting a polydisubstituted acetylene consisting of a repeating unit represented by the general formula (g) with a strong base, - general formula (6) % formula % (in the formula, B , R1-R5, Y and 2 are the same as above.

The polydisubstituted acetylene consisting of repeating units represented by the above general formula (-), which is a raw material, is a polymer of disubstituted acetylene which is 2-alkyne, 1-phenylpropyne or a derivative thereof.

In addition, as the branched chain A, propyl group, isozolobyl group,
Straight or branched alkyl groups such as pentyl and heptyl groups, substituted alkyl groups whose hydrogen atoms are substituted with other atoms, phenyl groups, and phenyl groups whose hydrogen atoms are substituted with fluorine atoms, etc. and substituted phenyl groups. More specifically, poly(2-hexyne) and poly(4-methyl-2-pentene).

Isu(4-methyl-2-hexyne), poly(2-octyne), ? Su(5-methyl-2-octyne), Isu(2-
decine), poly(1-7 enylprobyne), poly(1-
(pentafluorophenylpropyne), etc., and a copolymer consisting of a combination of repeating units of at least 2fi or more of these polydisubstituted acetylenes.

As a method for obtaining these polydisubstituted acetylenes, the raw material 1fjJ or two or more disubstituted acetylene compounds is treated with a group V or group II transition metal such as tantalum, molybdenum, tungsten, or a halodanide of niobium, such as pentachloride. Usually, 30 to 100
It is obtained by polymerization for 2 to 36 hours at a temperature of .degree.

Benzene as a solvent.

Aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, chlorine solvents such as chloroform, 1,2-dichloroethane, and carbon tetrachloride, etc. can be used. In addition, the above catalyst is used as the main catalyst, and the second catalyst is used as the main catalyst.
Organometallic compounds containing aluminum, silicon, tin, antimony, etc. as components, such as trimethylaluminum, triethylaluminum, hydrosilane derivatives, tetraphenyltin, tetra-n-butyltin, triphenylantimony, etc., are used as promoters to achieve the desired purpose. It is also possible to obtain polymers that

When reacting a polydisubstituted acetylene consisting of a repeating unit represented by the general formula (2) with a cyclosiloxane compound represented by the general formula or a one-end reactive polyorganosiloxane represented by the general formula (to) Examples of strong bases used include methyllithium, n-butyllithium,
Organolithium compounds such as t-butyllithium diphenyllithium and lithium diisopropylamide; alkali metal hydride compounds such as potassium hydride and sodium hydride;
Methylmagnesium iodide.

Examples include Grignard compounds such as ethylmagnesium bromide and phenylmagnesium bromide, but organic lithium compounds are preferred in terms of reaction efficiency. These strong bases are usually used in an amount of 0.1 to 4 equivalents based on the repeating unit of the 4-line substituted acetylene as a raw material, and the introduction rate of the polyorganosiloxane component can be controlled by this amount.

It is preferable to use a solvent in the reaction of the Iliny-substituted acetylene represented by the above general formula (to) with a strong base,
Any solvent may be used as long as it dissolves the polyni-substituted acetylene and does not participate in the reaction.
Entane, n-hexane, cyclopentane, cyclohexane.

Examples include organic solvents such as tetrahydrofuran, dimethoxyethane, toluene, benzene, and xylene, but it is preferable to use aliphatic hydrocarbons such as n-pentane, n-hexane, cyclopentane, and cyclohexane in terms of reaction efficiency. . Further, the reaction is preferably carried out at a temperature range of 0°C to 90°C for 20 minutes or more. Furthermore, it is preferable to carry out the reaction with the strong base in the presence of a noamine such as N 2 , N 2 , N', N'-tetramethylethylenediamine because the reaction proceeds smoothly.

The cyclosiloxane compound represented by the general formula 〇 is as follows: C) 12CH281 (CI(3)).

(However, m is an integer of 3 to 6). Furthermore, a mixture of two or more of these cyclosiloxane compounds may be used.

By using the cyclosiloxane compound represented by the general formula (I) in an amount of 0.5 to 50 equivalents based on the strong base, the desired product can be obtained with a good yield.

When adding the cyclosiloxane compound to the reaction system, it is preferable to dissolve the cyclosiloxane compound in a solvent beforehand, and the solvent used in this case is tetrahydrofuran, n-pentane, n-hexane, or cyclopentane.

Organic solvents such as cyclohexane can be mentioned. In addition, the reaction temperature during the reaction with the cyclosiloxane compound is preferably around room temperature. The reaction time is preferably 2 hours or more, more preferably 10 hours or more, and as the reaction progresses, the ring-opening polymerization of the υcyclosiloxane compound is completed.

The triorganohalogenoalan compound represented by the general formula (2) used to stop the above reaction is C
ASi(CHs)s-CABi(C2H5)
3 #CH, CH.

CH, CH.

etc. can be exemplified. Most of these triorganohalogenosilane compounds are commercially available, and can be easily synthesized by known methods. The reaction is completely stopped by adding 2 to 20 equivalents of these triorganohalogenosilane compounds to the reaction system based on the strong base used. In that case, the time required to stop the reaction is preferably 20 minutes or more.

Further, the one-end reactive/liorganosiloxane represented by the general formula (11'/D) is CH, CH.

? H302H5 CL-8l-CH2CH2-Z-8l -C2H5CH
2CH2 CH, CH.

CH, CH.

CH3CH3 etc. can be exemplified. However, 2 in the above formula is an organosiloxane chain in which the repeating unit is represented by the above general formula (U). Examples thereof are shown below.

CH.

+StO+ CH2CH2CH20CF(C10)2Hs OCH2CH2 Among the above-mentioned one-end reactive polyorganosiloxanes, the compound of group (1) is, for example, as shown in the reaction formula below, when an isovalent amount of n-BuLi is added to a trisubstituted silanol. It can be synthesized by living anionic polymerization of a cyclosiloxane compound using a silal anion obtained by adding as an initiator, and stopping the reaction using a halogenosilane compound having a reactive substituent. .

(In the formula, p represents an integer of 1 or more, and m represents an integer of 3 to 6.

B and B' are the same or different)・6 in logon atom
b, R' to R7 may be the same or different, and are hydrogen atoms, alkyl groups, substituted alkyl groups, alkenyl groups,
Substituted alkenyl group.

Indicates a phenyl group or a substituted phenyl group. However, uA
, n7 may be arbitrarily different for each repeating unit. ) In addition, the above-mentioned silal anion may be added to an equimolar amount of α,ω-dichloro? It can be synthesized by reacting with liorganosiloxane.

Furthermore, the single-end reactive polyorganosiloxane of Group (2) has the general formula cz-st-u (■) (in the formula R') instead of the compound represented by B-81-B' in the above reaction formula.
e R' is the same as above. ) can be synthesized by a similar method using a silane compound represented by , can be synthesized by a hydrosilylation reaction with a chlorosilane compound having a double bond.

The chlorosilane compound having a double bond used here is C! (, CH3 CH, CH.

CH.

etc. can be exemplified.

Add 0.5 to 3.0 equivalents, preferably 0.9 to 2.0 equivalents, of the polyorganosiloxane with one end reactive represented by the general formula (b) above, to the strong base, and stir for 5 minutes, usually around room temperature. By performing the above reaction, the target product can be obtained in good yield.

The graft copolymer of the present invention can be used in aromatic solvents such as toluene, benzene, ethylbenzene, and xylene, carbon tetrachloride,
It is soluble in halodanized hydrocarbons such as chloroform and trichloroethylene, hydrocarbon solvents such as n-hexane, cyclohexane, and cyclohexene, and chlorinated solvents such as tetrahydrofuran, and is insoluble in alcohols or water.

When the graft copolymer of the present invention is used as a gas separation membrane, the molar ratio of the mono-disubstituted acetylene repeating unit in the main chain to the I-liorganosiloxane repeating unit in the side chain is 99/1 to 5/5. 95 range, more preferably 60/4
It is desirable that it be in the range of 0 to 10/90. If the organosiloxane unit content is less than this range, the gas permeability coefficient of the membrane obtained will be almost the same as that of a gas separation membrane made of polydisubstituted acetylene as a raw material, and if it is too large, the graft copolymer will have poor film formability. Therefore, it becomes difficult to make the film thinner. The graft copolymer having this molar ratio range can be prepared in the above-mentioned production method by the amount of strong base, the amount of the cyclosiloxane compound represented by the general formula ω, or the one-end reactivity represented by the general formula (b). Iliol can be obtained by adjusting the amount and chain length of nosiloxane.

Further, the molecular weight of the graft copolymer of the present invention is desirably large from the viewpoint of membrane strength, and is usually 10,000 or more, particularly preferably 100,000 or more.

The method for remanufacturing the graft copolymer of the present invention is not particularly limited, and any known or well-known means can be used. For example, a method of forming a film by evaporating the solvent from a casting solution onto a metal, glass plate, water surface, etc. It is also possible to adopt methods such as immersing a porous support in a polymer solution, pulling it up, applying the solution, and drying.

The film of the present invention has a film thickness of o, oi to 100 μm, particularly 0
．． 01 to 50 μm is preferably used. If the film thickness is thicker than this, a sufficient amount of gas permeation will not be provided. Also, if it is thin, it does not have practical strength. For thin films with a thickness of 1 μm or less, it is preferable to use them together with a support. As the support, any porous material having sufficient strength to support the membrane can be used, such as a woven support, a nonwoven support, a microfilter, an ultrafiltration membrane, and the like.

The membrane of the present invention can be used in any form, such as a flat membrane, a tubular membrane, or a hollow fiber membrane.

When a membrane formed from the graft copolymer of the present invention is used to separate and concentrate a gas mixture as an example of its use, target gas mixtures include, for example, hydrogen, helium, Wl, nitrogen, carbon dioxide, - Gaseous mixtures such as carbon oxide, methane, ethane, proanine, ethylene, etc.

The film formed from the graft copolymer having polysiloxane chains as side chains of the present invention is particularly excellent in film strength, so it is a practical gas that can be made into a thin film of about 0.01 to 0.1 μm. It is a separation membrane.

[Effects of the invention] Polydisubstituted acetylene of the present invention/? The liorganosiloxane graft copolymer seems to have improved the drawback of conventional borini-substituted acetylenes, such as a low gas permeability coefficient, and the membrane formed from this copolymer is a practical gas separation membrane.

That is, the membrane formed from the graft copolymer having a polysiloxane chain as a side chain of the present invention has a good separation coefficient (for example,
The separation coefficient between oxygen and nitrogen is 2.0 or more. ), it becomes an excellent selective gas separation membrane with higher gas permeability, so it can be used to extremely efficiently separate and concentrate a quiet oxygen-enriched gas mixture from air. Can be done. Furthermore, because the membrane has particularly excellent mechanical strength, it can be made as thin as 0.01 to 0.1 μm, but it can also be used in any form such as flat membranes, tubular membranes, and hollow fiber membranes. can.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these.

Reference Example 1 Synthesis of poly(1-phenylzolopine) 1-7enylpropyne 55.491-) toluene 500d
3.4 g of tantalum pentachloride was added thereto, the tube was degassed and sealed in a stainless steel polymerization tube, and the mixture was shaken at 80° C. for 6 hours to obtain a viscous ripple-shaped polymer. This polymer was dissolved in toluene, reprecipitation was repeated several times in a large amount of methanol, and the resulting yellow-white fibrous solid was dried at 60° C. under vacuum.

The yield was 44.2 g (yield 79.8 g). The obtained polymer was subjected to IR, H-concentration measurements and elemental analysis, and was confirmed to be the desired poly(1-phenylpropyne).In addition, as a result of GPC measurement, Its number average molecular weight and weight average molecular weight are 1.55X10 and 5.47, respectively, in terms of polystyrene.
It was X10.

Example 1 Poly(1-phenylpropyne) obtained in Reference Example 15.
After dissolving 09 in 600 d of dry cyclohexane and heating it to 60°C under an alkali gas stream, N, N, N', N'-
Tetramethylethylenediamine 6, 45 ml (43
,0mmoA) and n-butyllithium hexane solution (1,6mob/l) 26.9ml (43,Or
rrmoL) was added and stirring was continued for an additional hour, and the reaction solution turned black-red. Next, the temperature of the reaction solution was cooled to room temperature, and hexamethylcyclotrisiloxane 47.
59 (213 mmot) dried THF 3501 nl
When a solution dissolved in 1 was added all at once, the reaction solution changed from black-red to black-purple, and then gradually changed to pale yellow. Further, stirring was continued for 17 hours at room temperature, and 2511 L/(197 mrnoL) of trimethylchlorosilane was added and stirring was continued for 2 hours to stop the reaction. At that time,
A white precipitate of lithium chloride was formed in the reaction solution. Finally, a white polymer was obtained by pouring the above reaction solution into methanol 51). The obtained polymer was dissolved again in 500 d of toluene, reprecipitated in 5 g of methanol/diethyl ether mixed solvent (80/20 molar), and the same reprecipitation was repeated several times to remove the contamination. The I-limer was purified by removing the polydimethylsiloxane.

The yield of produced I remer was 7.09.

When the obtained polymer was subjected to GPC measurement,
The number average molecular weight and weight average molecular weight are each 1.37×10 in terms of polystyrene.

It was 4.58×10.

Further, the results of IR spectrum, H-NMR spectrum and elemental analysis were as follows.

IR: 3100 (E), 3070 (
s) , 3 0 4 0 @ , 2 9
80 (s), 2920 (m)
.

2860 (c), 1950 (→, 1890 (→, 180
0 (b) = 1600 (s, characteristic absorption of the phenyl group of main chain - li (1-phenylpropyne)), 1so.

(s) = 1440 (a) −1415 (e) −1
370(a).

1260 (s, characteristic absorption of methyl group of side chain polydimethylsiloxane), 1100 (a, characteristic absorption of siloxane bond), 1020 (s, characteristic absorption of siloxane/bond),
910 (w), 860 (i).

800 (s), 770 (s), 695 (
m)'H-NMR: x, vector, δ(CDCt, ,
ppm): 0.10 (proton peak of methyl group of side chain polydimethylsiloxane), 1.60 (proton peak of methyl group of main chain poly(1-7 enylglopine)).

6.90 (Proton peak of phenyl group of main chain poly(1-phenylpropyne)) Elemental analysis value (a): C: 65.61, H near, 46 or higher results. Some of the hydrogens on the methyl group of 1-phenylpropyne are CH and CI.

It was confirmed that the copolymer was a poly(1-phenylbrone)/polydimethylsiloxane graft copolymer having a structure substituted with a group represented by the following.

Also, 0.10 ppm and 6.9 of H-hikisuiktor
The molar ratio of the poly(1-phenylzolopine) repeating unit in the main chain of this graft copolymer to the polydimethylsiloxane repeating unit in the side chain, determined from the proton peak area ratio at 0 ppm, was 44,156.

After dissolving the obtained graft copolymer in toluene, it was cast onto a glass plate and the toluene was slowly evaporated off, thereby obtaining a strong homogeneous film with a film thickness of 71 μm. This membrane was attached to a gas permeation device, and the permeability coefficients of oxygen and nitrogen at 25° C. were measured. The results are shown in Table 1.

Furthermore, when a 0.5% toluene solution of this graft copolymer was spread on the water surface, the film thickness was approximately 25%.
A thin film of 0 was obtained. Two layers of this thin film were laminated on Shellagard, which was attached to a gas permeation device, and the permeation rates of oxygen and nitrogen at 25° C. were measured. The results are shown in Table 2.

Note that no change was observed in this permeation rate even when remeasured 30 days later.

Example 2 The same operation as in Example 1 was performed except that the amount of hexamethylcyclotrisiloxane was changed to 71.3 g (320 mmot) to obtain a white/IJ mer of 7.99.

The number average molecular weight and weight average molecular weight determined by GPC measurement are 1.57X 10 in terms of polystyrene, respectively.
It was 4.83×10.

IR spectrum of the obtained polymer Oyohi'H-NMR
The suictor was almost the same as the measurement results of Example 1, and the elemental analysis values were as follows.

Elemental analysis value (a): C: 62.57. H: F, 65 Therefore, the resulting polymer is poly(1-phenylzolobin)/I having a structure similar to that of the polymer obtained in Example 1.
Polymethylsiloxane graft copolymer, i5, H
The molar ratio between the repeating units of poly(1-phenylpropyne) in the main chain and the repeating units of polydimethylsiloxane in the side chains, determined from the proton peak area ratio of -NMR spectroscopy, was 39/61.

The obtained graft copolymer was dissolved in toluene, then cast onto a glass plate, and the toluene was slowly evaporated off, thereby obtaining a strong homogeneous film with a film thickness of 69 μm. This membrane was attached to a gas permeation device, and the permeability coefficients of oxygen and nitrogen at 25° C. were measured. The results are shown in Table 1.

Furthermore, when a 0.5% by weight toluene solution of this graft copolymer was prepared and spread on the water surface, the film thickness was approximately 260X.
A thin film was obtained. Two layers of this thin film were laminated on Shellagard, which was attached to a gas permeation device, and the permeation rates of oxygen and nitrogen at 25° C. were measured. The results are shown in Table 2.

Note that no change in the permeation rate was observed even when remeasured 30 days later.

Example 3 The same operation as in Example 1 was performed except that the amount of hexamethylcyclotrisiloxane in Example 1 was changed to 95.0 El (427 mmoL), and 9.0 g of a white polymer was obtained.

The number average molecular weight and weight average molecular weight determined by GPC measurement are 1.67XI0. 4.
It was 73x10.

IR spectrum of the obtained polymer and '! (-N
The MR spectrum was almost the same as the measurement results of Example 1, and the elemental analysis values were as follows.

Elemental analysis value (a); C: 56.28. H near, 65 Therefore, the resulting polymer is poly(1-7 enylprobyn')/ having a structure similar to that of the polymer obtained in Example 1.
7f? I) It is a dimethylsiloxane graft copolymer, and the mole of the repeating unit of poly(1-phenylpropyne) in the main chain and the repeating unit of polydimethylsiloxane in the side chain is determined by the proton peak area ratio of the H-NMR spectrum. The ratio was 29/71.

After dissolving the obtained graft copolymer in toluene, it was cast onto a glass plate and the toluene was slowly evaporated off, thereby obtaining a strong homogeneous film with a film thickness of 60 μm. This membrane was attached to a gas permeation device, and the permeability coefficients of oxygen and nitrogen at 25° C. were measured. The results are shown in Table 1.

Furthermore, when a 0.5 weight-f1% toluene solution of this graft copolymer was prepared and spread on the water surface, the film thickness was approximately 23 mm.
A 0X thin film was obtained. Two layers of this thin film were laminated on Shellagard, which was attached to a gas permeation device, and the permeation rates of oxygen and nitrogen at 25° C. were measured. The results are shown in Table 2.

Note that no change was observed in this permeation rate even when remeasured 30 days later.

Example 4 The same procedure as in Example 1 was carried out except that the amount of hexamethylcyclotrisiloxane was changed to 142.5 g (640 mmot), except for 9, to obtain white polymers 11.4 and 9.

The number average molecular weight and weight average molecular weight determined by GPC measurement are 1.42XI0.
It was 4.95×10.

IR spectrum and 'H-NMR of the obtained polymer
The suictor was almost the same as the measurement results of Example 1, and the elemental analysis values were as follows.

Elemental analysis value (a): C: 50.06. )i near, 74 Therefore, the resulting polymer is poly(1-7 enylpropyne)/ having a structure similar to that of the polymer obtained in Example 1.
Polydimethylsiloxa/graft copolymer, )t
The molar ratio of the repeating unit of poly(1-7 enylprobyne) as the main group and the repeating unit of polydimethylsiloxane/ as the side chain was determined from the proton peak area ratio of the -NMR spectrum and was 21/79.

The thus obtained graft copolymer was dissolved in toluene, cast on a glass plate, and the toluene was slowly evaporated off, thereby obtaining a strong homogeneous film with a film thickness of 64 μm. This membrane was attached to a gas permeation device, and
The permeability coefficients of oxygen and nitrogen were measured. The results are shown in Table 1.

Furthermore, when a 0.5% by weight toluene solution of this graft copolymer was prepared and spread on the water surface, the film thickness was approximately 2,501 mm.
A thin film was obtained. Two layers of this thin film were laminated on Shellagard, which was attached to a gas permeation device, and the permeation rates of oxygen and nitrogen at 25° C. were measured. The results are shown in Table 2.

Unfortunately, no change was observed in this permeation rate even when remeasured 30 days later.

Example 5 The amount of hexamethylcyclotrisiloxane in Example 1 was set to 47.59 (213 mmot), and 100 g of tris(3,3,3-)lifluoroglobil)trimethylcyclotrisiloxane (213 mmot) was added to this.
) was carried out in the same manner as in Example 1, except that 13.6 g of a white polymer was obtained.

The number average molecular weight and weight average molecular weight measured by GPC are 2.26 x lO + 5.9, respectively, in terms of polystyrene.
It was 5xlO5.

The results of ti., IR spectrum, H-NMR spectrum, and elemental analysis were as follows.

IR squictor (cm-'): 31006Ti1.3
070 (c), 3040 (c), 2980 (s)
, 2920 (e).

1950 (w), 1600 (m, characteristic absorption of phenyl groups in main chain poly(1-phenylpropyne)).

1500 (c), 1440 (e), 1370 (e), 1
3NJ (c), 1260 (i, characteristic absorption of methyl group of side chain polyorganosiloxane), 1210 (s, characteristic absorption of C-F bond), 1130 (s)-1100 (s, characteristic absorption of siloxane bond) , 1070(s), 1020(
a, characteristic absorption of siloxane bonds), 900 (a),
840 (a), 800 (s), 770 (
s).

695(s), 550(to) 'H-NFiiR spectrum, δ(CDC23, pP'
): 0.10 (proton peak of methyl group of side chain polyorganosiloxane), 0.85 (3,3,3
- proton peak of the methylene group on the silyl group side of the trifluoropropylsilyl group), 1.60 (proton peak of the methyl group of the main chain poly(1-phenylpropyne)).

2.12 (proton peak of methylene group on trifluoromethyl group side of 3,3,3-trifluoropropylsilyl group), 6.90 (proton peak of phenyl group of main chain 29 (1-7 enylprobyne)) Elemental analysis Value (a); C:
52.31, H: 6.53 and above, the produced polymer is a polyorganosiloxane consisting of repeating units in which some of the hydrogens on the methyl groups of the raw material I-phenylpropyne are replaced. ) It was confirmed that it was a poly(1-phenylglobin)/polyorganosiloxane graft copolymer having a structure substituted with a group represented by the following.

In addition, 0.10 ppm of the H-NMR spectrum,
The molar ratio of the side chain I-liorganosiloxane units determined from the proton-to-area ratio of 0.85 ppm and 6.90 ppm is 51/49, and the main chain poly(1-7
The molar ratio of the repeating unit of enylprobyne) to the repeating unit of the side chain polyorganosiloxane was 33/67.

After dissolving the graft copolymer thus obtained in toluene, it was cast onto a glass plate and the toluene was slowly evaporated off, thereby obtaining a durable and homogeneous film with a film thickness of 58 μm. Ta. This membrane was attached to a gas permeation device, and
The permeability coefficients of oxygen and nitrogen at °C were measured. The results are shown in Table 1.

Example 6 In Example 1, the amount of hexamethylcyclotrisiloxane was 95.09 (427 mmol), and this K)
Add 100 g (213 mmot) of lis(3,3,3-)lifluorozolobyl)trimethylcyclotrisiloxane, and otherwise perform the same operation as in Example 1.
15.2 g of white 4-rimer was obtained.

The number average molecular weight and weight average molecular weight determined by GPC measurement are 2.14XI0. 4.
It was 19×10).

of the resulting polymer! R spectrum and 'H-NM
The R spectrum was similar to the results of Example 5, and the elemental analysis values were as follows.

Elemental analysis value (9): C: 45.21, H: 6.54 Therefore, the produced polymer has a structure similar to that of the polymer obtained in Example 5. It is a copolymer, 'H-
The molar ratio of the repeating units represented by the side chain polyorgan, determined from the zoloton peak area ratio of the Hatake α spectrum, is 62/38, and the molar ratio of the repeating units of the main chain poly(1-phenylglobin) and the side chain polydimethylsiloxane is 62/38. The molar ratio with the return unit was 21/79.

After dissolving the graft copolymer obtained in this way in toluene, it was cast onto a glass plate and the toluene was slowly evaporated off, thereby obtaining a strong homogeneous film with a film thickness of 54 μm. Ta. This membrane was attached to a gas permeation device, and
The permeability coefficients of oxygen and nitrogen at °C were measured. The results are shown in Table 1.

Furthermore, when a 0.5% by weight toluene solution of this graft copolymer was prepared and spread on the water surface, the film thickness was approximately 220X.
A thin film was obtained. Two layers of this thin film were laminated on Shellagard, which was attached to a gas permeation device, and the permeation rates of oxygen and nitrogen at 25° C. were measured. The results are shown in Table 2.

Note that no change was observed in this permeation rate even when remeasured 30 days later.

Table 1 Umbrella unit: 100m (s'rp)・-X-・Ki・WoundHgTable 2 Umbrella unit: cm” (STP)7m”・see・
zHg Comparative Example The poly(1-7 enylglopine) obtained in Reference Example 1 was dissolved in toluene and then cast onto a glass plate, and the toluene was slowly evaporated off to form a homogeneous film with a film thickness of 76 μm. This was attached to a gas permeation device and the permeability coefficients of oxygen and nitrogen at 25°C were measured. As a result, the oxygen permeability coefficient Po2 was 1.12 x 10 m” (STP
) m/m” - Crown/auxiliary Hg, nitrogen permeability coefficient PN2 is 3.
59X10cm"(STP)・cm/cwr"m・cm
The Hg e separation coefficient Po2//PN2 was 3.12.

Therefore, when comparing this result with the results shown in Table 1,
Are the graft copolymers obtained in Examples 1 to 6 used as raw materials? It is clear that the oxygen permeability coefficient is significantly increased by about 5 to 17 times compared to (1-7 enylderogine).

[- Kodaira Honda.

Claims (1)

[Claims] 1) The repeating unit has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A represents an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group. X is a hydrogen atom or a substituted phenyl group. Indicates a group represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.A and X may be arbitrarily different for each repeating unit.However, Y is an oxygen atom or a divalent organic group, and Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. The polyorganosiloxane chain shown by ▼, R^1 to R^5, R^6, and R^7 may be the same or different, and may be a hydrogen atom, an alkyl group, or a substituted alkyl group. , alkenyl group, substituted alkenyl group, phenyl group or substituted phenyl group), and the molar ratio of the repeating unit of polydisubstituted acetylene in the main chain to the repeating unit of polyorganosiloxane in the side chain is from 99/1 to 5/95 and a molecular weight of at least 10,000 or more. 2) The repeating unit is a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A represents an alkyl group, substituted alkyl group, phenyl group, or substituted phenyl group. X is a hydrogen atom or general formula ▲ Numerical formula, chemical formula , tables, etc. are available. Indicates a group represented by ▼. A and X may be arbitrarily different for each repeating unit. However, Y is an oxygen atom or a divalent organic group, Z is ▲ formula,
There are chemical formulas, tables, etc. The polyorganosiloxane chain shown by ▼, R^1 to R^5, R^6, and R^7 may be the same or different, and are hydrogen atoms, alkyl groups, substituted alkyl groups, alkenyl group, substituted alkenyl group, phenyl group or substituted phenyl group. ), the molar ratio of the polydisubstituted acetylene repeating unit in the main chain to the polyorganosiloxane repeating unit in the side chain is in the range of 99/1 to 5/95, and the molecular weight is at least 10,000 or more. A gas mixture separation membrane formed from a disubstituted acetylene/polyorganosiloxane graft copolymer.