CA1206681A - Polymer and a membrane having an improved gas- permeability and selectivity - Google Patents

Polymer and a membrane having an improved gas- permeability and selectivity

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Publication number
CA1206681A
CA1206681A CA000440435A CA440435A CA1206681A CA 1206681 A CA1206681 A CA 1206681A CA 000440435 A CA000440435 A CA 000440435A CA 440435 A CA440435 A CA 440435A CA 1206681 A CA1206681 A CA 1206681A
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Canada
Prior art keywords
polymer
membrane
propyne
polymers
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000440435A
Other languages
French (fr)
Inventor
Toshinobu Higashimura
Toshio Masuda
Koichi Takada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Chemical Industries Ltd
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Sanyo Chemical Industries Ltd
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Filing date
Publication date
Application filed by Sanyo Chemical Industries Ltd filed Critical Sanyo Chemical Industries Ltd
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Publication of CA1206681A publication Critical patent/CA1206681A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0248—Physical processing only
    • C01B13/0251—Physical processing only by making use of membranes
    • C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F138/00—Homopolymers of compounds having one or more carbon-to-carbon triple bonds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0046—Nitrogen

Abstract

TITLE OF THE INVENTION :
A POLYMER AND A MEMBRANE HAVING AN IMPROVED GAS-PERMEABILITY
AND SELECTIVITY

ABSTRACT OF THE DISCLOSURE

A permselective membrane having an improved gas-permeability and selectivity is obtained from a polymer of 1-alkyldimethylsilyl-1-propyne.

Description

~:~066~:~

BACKGROUND OF THE INVENTION

1. Field of the Invention:
This invention relates to a film-forming polymer. More particularly, it relates to a polyrner useful for a permselective membrane.
2. Description of the Prior Art:
As the materials for producing permselective membranes, there have been known heretofore, several polymers for example, polydimethylsiloxanes and copolymers thereof with polycarbonates or others (U.S. Patents
3,980,456, and 3,874,986 ; and Japan Patent Lay-open No. 26504/1981); as well as olefine polymers such as poly 4-methylpentene-1 (Japan Patent Lay-open No. 4203tl982). However, these polymers can not fulfill all the fundamental requirements, for use as permselective membranes, namely good permeability and selectivi~ty as well as processability to form thin film.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide a polymer capable of forming a membrane having an improved gas-perme-ability.

It is another object of this invention to provide a polymer formable a membrane having an irnproved selectivity.

~ t is still another object of this invention to provide a polymer which can be readily processed into a thin membrane.

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It is yet another object of the invention to provide a perm-selective membrane article, for separating or enrichin~ a specific gas from a gas mixture, having high gaseous permeability and other properties.

Briefly, these and other objects of the present invention as here-inafter will become more readily apparent have been attained broadly by a polymer having repeating units of the formula:

CIH3 `
_ ~--C
l (1) CH3-Si-CH3 R
wherein R is an alky1 radical having 1 - 4 carbon atoms.

BRIEF DESCRIPTION OF THE DRAWING
-FIGURE 1 is NMR charts of a~poly-l-trimethylsilyl propyne,FIGURE
2 and FIGURE 3 are IR charts of a poly-l-trimethylsilyl pro~yne and a poly-l-n-propyldimethylsilyl propyne, respectively.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the formula (1), R is an alkyl radical, which may be straight-chain orb,ranched. Examples of suitable alkyl radicals include methyl, ethyl, n- and ~- propyl, and n-, i-and t-butYl radicals.

The polymer having the repeating units of the formula (1) can be formed by polymerization of one or more l-monoalkyl (Cl-4) dimethyl-silyl-propynes. Suitable monomers include, for example, l-trimethyl-silyl-P~~yne(sold by Petrarch System Inc. and Chisso Corp., T-3728), i~. o~

and l-mono-n-propyldimethylsilyl propyne. The most preferned is 1-trimethylsilyl propyne.

Polymerization can be performed under a catalysis of one or more compounds, including halides, of transition metals of group V of Periodic lable, such as niobium and tantalum. Examples of suitable catalysts include NbCl5, TaC15, NbBr5 and TaBr5. The most preferred are TaCl5 and TaBr5. The catalyst is usually used in an amount of 0.01 - 2~ mol %, preferably 0.5 - 5 mol %, based on the monomer.

Polymerization may be carried out in the presence of a solvent.
Suitable solvents are, for instance, hydrocarbons, including aromatic hydrocarbons, such as benzéne, toluene, o-, m- and p-xylenes, ethyl benzene, styrene and naphthalene, cycloaliphatic hydrocarbons, such as cyclohexane, methyl cyclohexane, ethyl cyclohexane and cyclohexene, aliphatic hydrocarbons, such as n-pentane, n- and 4-hexanes, n-heptane, n- and ~-octanes, I-hexane, l-heptene, petroleum ether, and the like;
and halogenated hydrocarbons, such as 1, 2-dichloroethane, carbon tetrachloride, chloroform, 1, 2, 3-trichloropropane, trichloroethylene, chlorobenzene, chloroethylbenzene, and the like; as well as mixtures oF two or more of these solvents. Among these, preferred are toluene, cyclohexane, n-hexane, and 1, 2-dichloroethane. The solvent is gener-ally used in an amount providing a monomer concentration of 0.1 - 5 mole/~, preferably 1 - 2 mole/~.

Polymerization can be conclucted usually at a temperature of 30C -lQO~C, preferably 50C - 100C, more preferably 70C - 90C, for 12 -36 hours.

The polymerized product may be purified by any known rnethod, for example, by adding the polymer solution into a larger amount of a poor solvent (such as methanol) to precipitate the polymer, followed by filtrating and drying.

Alkyldimethylsilyl propyne polymers thus obtained are white solids in fibrous or powdered form.

Weight-average molecular weight of the polymers, determined by light scattering method, is usually at least 10,000, preferably at least 100,000. Polymers obtained by using TaC15 or TaBr5 as the catalyst have higher molecular weight, such as 100,000 - 2,000,000 or higher.
Intrinsic viscosity is generally at least 0.5 dl~g, preferably 1.0 -10.0 or more.

Polymers according to the present invention are film-forming, and soluble in various organic solvents as described above (solvents for polymerization) and bellow (solvents for forming membranes); and are particularly useful for producing permselective membranes.

In producing the membrane the polymer according to this invention is dissolved in one or more solvents to form a polymer solution, which is casted to form a film.
- 4 -Exemplary of suitable solvents are hydrocarbons, for instance, aromatic hydrocarbons, such as benzene, toluene and xylene, cycls-aliphatic hydrocarbons, such as cyclohexane, and the like; and halogenated hydrocarbons, such as carbon tetrachloride, trichloro-ethane, trichloroethylene, and the like.

Production of membranes from polymer solutions may be done according to any known methods, such as those described in Japan Patent Lay-open No. 166903/1981, for instance, by casting a polymer solution onto a smooth plain surface of solid (such as metal, glass and the like) or liquid (such as water) followed by evaporating the solvent. Preferred are methods by dropping a dilute polymer solution on a liquid surface (particularly water surface) and then spreading spontaneously on the surface followed by evaporating the solvent to form a ultra thin membrane, which methods can provide membranes free from any serious defeats (such as pin holes) and having a large area~.

Besides, ~olding or forming techniques (such as extrusion technique), generally employed for thermoplastics, may also be applied to obtain membranes.

Membranes composed of one or more alkyldimethylsilyl propyne polymers according to this invention may optionally contain, as mixture or as composite, one or more other polymers.

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Examples of suitable polymers include:
. .
(i) Polyorganosiloxanes, such as polydimethylsiloxanes, polymethyl-phenylsiloxanes, polydiphenylsiloxanes, and derivatives of them (such as polydimethylaminoalkyl (C2-5) methylsiloxanes); and (ii) olefinic polymers, for example, polymers'(including copolymers) of ~-olefines having 2 - 15 carbon atoms, such as 4-methylpentene-1.

Other examples of suitable polymers are:
(iii) cellulosic materials, including cellulose and derivatives thereof such as cellulose ethers (ethyl cellulose,'hydroxyethyl cellulose, carboxymethyl cellulose, and the like), and cellulose esters (cellulose acetates, such as triacetate, cellulose acetate butyrate, and the like);
.
(iv) polyalkylsulfones s'uch as copolymers of ~-olefines and 52 preferably polymers of long chain alkyl (C10-20) sulfones; and (v) nitrogen atom-containing polymers, including polymers of tertiaryam;ne-containing vinylmonomers, such as vinylpyridines, N, N-diethyl-aminoethylacrylate, N, N-dimethylaminostyrene, and the like.

Among these, preferred are polyalkyl (C10-20) sulfones, poly-~-oleFines and alkyl celluloses.

Membranes, composed of at least one alkyldimethylsilyl propyne polymer (a) and at least one other polymer (b), may be produced by m~xing these polymers (a) and (b) usually in the form of sblutions Followed by processing to a membrane~ or by processing one of the zo~

polymers [for instance, the polyrner (a)] to a membrane, onto ~Ihich thereafter the other polymer [the polymer (b)] is coated to form a multi-layer composite membrane; or by combination of these methods.

In membranes composed of said polymers (a) and (b), content of said polymer (a) is usually at least 20 %, preferably at least 70 %
by weight.

Membranes composed of said polymer (a) and optionally the other polymer (b), may contain5 if desired, various additives such as plasticizers (esters such as dioctyl phthalate; and higher alcohols or amines having at least 5 carbon atoms, and the like) to improve processability and spreadability of ultrathin membranes.

Membranes according to the invention can take any form of , membranes, such as plain filmy, tubular and hollow fibrous forms.
, Thickness of membranes, which may vary widely, is usually 0.01 100~U, preferably 0.05 - 20)~ , in view of practical strength and sufficient permeability.

If necessary, membranes may be supported on one more backing layers to form composites. Suitable mater;als, used as support, include porous or microporous materials manufactured by various ways, such as extraction, pa~er-making, phase separation, stretching, and so on. Examples of suitable supports are papers, including Japanese paper, ~ilter paper, synthetic paper, and the likei plastic films, including ultrafiltration membrane and filtration membrane, for example, porous polypropylene film, such ,:

''"'` 9Z~

as Duragard (brand Name, Celanease Corp.); fabrics, including textile materials such as woven fabrics, knits and non-woven fabr-iss; and porous glass. Among these preferred are porous polypropylene films such as Duragard and other ultrafiltration membranes.

Thickness of the support is not particularly critical, but is preferably 1~- 5 mm, more preferably 10J~- 1 mm.

Composite membranes can be produced by any known methods. For instance, a thin film formed on water surface is taken out and pressed on a support, or a thin film on water surface is dipped up with a support or sucked through a support to form a composite. If necessary, adhesive may be applied, preferably in scattered way, between the membrane and the support to adhere them. Composite membranes may undertake further heat treatment.

Permselective membranes according to the present invention exhibit an improved oxygen permeability constant, which may range generally 10 9 - 10 6 cc cm/cm sec cmHg, preferably 10 - 10 cc cm/
cm sec cmHg; and also enough oxygen/nitrogen separation factor, which may range l.S - 5.

Membranes of this invention have excellent selectivity comparable to those composed of polydimethylsiloxanes, as well as remarkably improved oxygen permeability, say about ten times as high as that of polydimethyls;loxanes.

In addition, alkyldimethylsilyl propyne polymers according to this invention can be readily processed into thin membranes, a~d their processability is comparable to that of poly-~-olefines.

Permselective membranes of this invention, having such outstanding virtues as above, yield great advantages for oxygen-enrichment from air, and can be applied to various oxygen-enriching devices, such as engines, boilers, stoves, and other combustors, so as to improve combustion efficiency. Saving of energy of 30 - 50 per cent woutd be expected by applying to combustion systems membranes according to this invention.
Membranes according to the invention can be applicable, for instance, to oxygen-enriching combustion system as described in "NIKKEI PLASTICS", October, 1981, Page 8.

Furthermore, membranes of this invention may be useful for breathing systems, such as incubators for premature or immature babys, curers for respiratory diseases, artificial lungs and artificial gills, as well as contact lens.

Having generally described the invention, a more complete under-standing can be obtained by reference to certain specific examples, which are included for purposes of illustration only and are not intended to be limiting unless otherwise specified.

, Example 1 Polymerization of 1-trimethylsilyl Propy~e (produced by Petrarch System Inc., T3728) was carried out using TaCl5 as the catalyst and toluene as the solvent, under the following conditions:

Monomer concentration : 1.0 M
Catalyst concentration : 20 m M
Polymerization temperature : 80 C
Polymerization time : 2~ hours The resulting viscous polymer gel was diluted with toluene to a concentration of 1 % by weight. Then the dilute solution was added into a larger amount of methanol to precipitate the polymer, which was then filtered off followed by drying.

The 1-trimethylsilyl propyne polymer thus obtained was identified by analysis of NMR ~nuclear magnetic resonance) spectra and IR
(infrared) spectrum, which were as shown in Figures 1 and 2, respectively;
as well as by analysis of UV (ultraviolet) spectrum and elemental analysis, results of which were as follows:

UV Spectral ~ata (in 5 m M cyclohexene solution) max : 273 nm ~ max : 120 cm~l (mol/4)~

Elemental analysis C 64.1 %, H 10.98 %, S~ 24.92%

G6~L
Examples 2 - 6 Example 1 was repeated except using the catalyst and tne solvent written in Table 1.

Polymers obtained in Examples 1 - 6 have intrinsic viscosity [~ ]
measured in toluene at 30C, and weight-average molecular weight (r~,J) determined by light scattering method, as shown in Table 1.

Table 1 Example SolventCatalyst Yield, [~ ], 1 Toluene TaC15 100 5.5 87 2 Toluene TaBr2 90 3.8 62 3 CyclohexaneTaCl5 100 6.0 93 4 Toluene NbCl5 100 0.99 32 Toluene NbBr5 100 0.63 27 6 1,2-Dichloro-TaC15 100 2.2 ~0 ethane Example 7 and 8 Example 1 was repeated except that, instead o~ l-trimethylsilyl prg wne, was used the monomer as written in Table 2.

The monomers, used in thes~ Examples, were produced by reacting lithium propyne with ethyl- or propyl-dimethylchlorosilane, which was prepared by reacting ethylene or propylene with dimethylchlorosilane.

Polymers obtai~ed in Examples 7 and 8 have [~ ~ and ~w as shown in Table 2.

- ~Z~6~

Table 2 Example Monomer Yield, [~-~, Mw, % dl/g x 1 -7 Ethyldimethylsilyl propyne 100 3.2 54 8 n-Propyldimethylsilyl ?ropyrle 100 2.8 46 Results of elemental analysis of these polymers were as follows:

Polymer of Example 7 : C 66.6 %, H 11.1 %, S~ 22.2 %
Polymer of Example 8 : C 68.6 %, H 11.4 %, S~ 20.2 %

IR spectrum of the polymer of Example 8 were as shown in Figure 3.

Example 7 - 11 : Each polymer of Example 1, 2, 3, 7 and 8 was dissolved again in toluene to a concentration of 2 % by weight, followed by casting the solution on a glass plate to form a membrane.
. , Oxygen, nitrogen and hydrogen permeabilities of these membranes were determined by using a gas permeability tester produced by RIKASEIKI KOGYO, JAPAN.

The results were as shown in Table 3.

Table 3 Example Polymer P * ~
PO2 PN2PH,2 PN2 7 of,Example 1 52 26 88 2.0 8 of,Example 2 63 28 101 2.2 9 of Example 3 57 28 12 2.0 10 of,Example 7 9.0 4.017.0 2.3 11 of Example 8 1.0 0.3' 3.2'3.3 * : Gas-permeability constant, 10 8 cm3(STP) cm / cm2 sec cmHg .. .

~, ~ . .
;

Claims (22)

THE EMBODIMENTS' OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polymer having repeating units of the formula :

(1) wherein R is an alkyl radical containing 1 - 4 carbon atoms.
2. A polymer as claimed in Claim 1, which has a molecular weight of at least 10,000.
3. A polymer as claimed in Claim 1 or 2, which is a polymer of 1 -trimethylsilyl-1-propyne.
4. A permselective membrane having an improved gas-permeability, said membrane being composed of a polymer having repeating units of the formula :

(1) wherein R is an alkyl radical containing 1 - 4 carbon atoms.
5. A membrane as claimed in Claim 4, wherein the polymer has a molecular weight of at least 10,000.
6. A membrane as claimed in Claim 4 or 5, wherein the polymer is a polymer of 1-trimethylsilyl-1-propyne.
7. A membrane as claimed in Claim 4, which has a thickness of 0.01 - 100.
8. A membrane as claimed in Claim 4 or 7, which has an O2 perme-ability constant of about 10-9 - about 10-6cc cm / cm2 sec cmHg.
9. A membrane as claimed in Claim 4 or 7, which has an O2/ N2 separation factor of about 1.5 - 5.
10. A membrane as claimed in Claim 4, composed of the polymer (a) having the repeating units of the formula (1), and at least one other polymer (b).
11. A membrane as claimed in Claim 10, wherein said polymer (b) is selected from the group consisting of polyorganosiloxanes, olefinic polymers, cellulosic materials, polyalkylsulfones, and nitrogen atom-containing polymers.
12. A membrane as claimed in Claim 10, which contains said polymer (a) in an amount of at least 20 % by weight.
13. A membrane as claimed in Claim 4, which has a backing layer of at least one porous material.
14. A membrane as claimed in Claim 13, wherein said material is selected from the group consisting of papers, porous or micro-porous plastic films, fabrics, and porous glass.
15. A method for separating a spesific gas from a gas mixture, by using a membrane as claimed in Claim 4, 10 or 13.
16. An oxygen-enriching device, in which is incorporated a mem-brane as claimed in Claim 4, 10 or 13.
17. A process for producing a polymer having repeating units of the formula :

(1) wherein R is an alkyl radical having 1 - 4 carbon atoms, which process comprises polymerizing 1-monoalkyldimethyl-silyl-propyne in the presence of at least one catalyst comprising a compound of a transition metal of group V of PERIODIC TABLE.
18. A process as claimed in Claim 17, wherein the compound is a halide.
19. A process as claimed in Claim 17 or 18, wherein the metal is niobium or tantalum.
20. A process for forming a membrane as claimed in Claim 4, which process comprises casting or flowing out on a smooth sur-face a solution of a polymer in a solvent, and evaporating the solvent.
21. A process as claimed in Claim 20, wherein the solvent is a hydrocarbon, a halogenated hydrocarbon, or a mixture of two or more of them.
22. A process as claimed in Claim 20, wherein the surface is water surface.
CA000440435A 1983-02-23 1983-11-04 Polymer and a membrane having an improved gas- permeability and selectivity Expired CA1206681A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP29,786/1983 1983-02-23
JP58029786A JPS59154106A (en) 1983-02-23 1983-02-23 Gas-separation membrane

Publications (1)

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CA1206681A true CA1206681A (en) 1986-06-24

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US (2) US4755193A (en)
JP (1) JPS59154106A (en)
CA (1) CA1206681A (en)
DE (1) DE3333991C2 (en)
FR (1) FR2541292B1 (en)
GB (1) GB2135319B (en)

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Publication number Publication date
GB2135319B (en) 1986-09-24
JPH0157613B2 (en) 1989-12-06
GB8332011D0 (en) 1984-01-04
FR2541292A1 (en) 1984-08-24
DE3333991C2 (en) 1994-09-29
GB2135319A (en) 1984-08-30
JPS59154106A (en) 1984-09-03
US4755193A (en) 1988-07-05
DE3333991A1 (en) 1984-08-23
FR2541292B1 (en) 1986-07-04
US4778868A (en) 1988-10-18

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