Ultrathin film, process for production thereof, and use thereof for concentrating a specific gas from a gas mixture

• US 4,644,046 A
• Filed: 06/19/1985
• Issued: 02/17/1987
• Est. Priority Date: 06/20/1984
• Status: Expired due to Term

• Current Assignee: Teijin Limited
• Original Assignee: Teijin Limited
• Inventors: Yamada, Takeyoshi
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US06/746,568
• Time in Patent Office: 608 Days
• Field of Search: 55/68, 55/159, 428/220, 428/447, 528/38, 528/28, 528/33
• US Class Current: 96/14
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: B01D 71/54 Polyureas; Polyurethanes
• CPC Class Codes: B01D 71/70 Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
• CPC Class Codes: C01B 13/0255 characterised by the type of membrane
• CPC Class Codes: C01B 2210/0046 Nitrogen
• CPC Class Codes: C08G 18/3893 containing silicon
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 77/54 Nitrogen-containing linkages C08G77/485 takes precedence
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

An ultrathin film composed substantially of a silicon-containing polymer comprising bonded units derived from

(A) at least one polyamine selected from the group consisting of silicon-containing polyamines containing in the molecule at least two primary and/or secondary amino groups not directly bonded to the silicon atom,

(B) at least one compound selected from the group consisting of polysiloxane-type compounds having at least two acidic hydroxyl groups in the molecule, and

(C) at least one polyisocyanate selected from the group consisting of polyisocyanates having at least two isocyanate groups in the molecule.

The ultrathin film on the supporting microporous substrate is useful for production of a gaseous mixture containing a specific gas such as O₂ in a higher concentration from a gaseous mixture of at least two gases such as air.

Claims

1. An ultrathin film composed substantially of a polyaddition polymer comprising bonded units derived from

(A) at least one silicon-containing polyamine containing in the molecule at least two primary and/or secondary amino groups not directly bonded to the silicon atom,

(B) at least one polysiloxane having at least two silanol-functional hydroxyl groups in the molecule, and

(C) at least one polyisocyanate having at least two isocyanate groups in the molecule.

2. The ultrathin film of claim 1 wherein the silicon-containing polyamine (A) is represented by the following formula (I) ##STR143## wherein R¹, R² and R³, independently from each other, represent a hydrocarbon group or fluorinated hydrocarbon group having 1 to 16 carbon atoms, or a group of the following formula (I)-1 ##STR144## in which R⁴, R⁵, R⁶, R⁷ and R⁸, independently from each other, represent a hydrocarbon or fluorinated hydrocarbon group having 1 to 16 carbon atoms, and n is zero or a number of at least 1,

A¹ and A², independently from each other, represent a divalent hydrocarbon group having 2 to 16 carbon atoms which may be interrupted by --O-- or --SO₂ --, B¹ represents a divalent hydrocarbon group having 2 to 16 carbon atoms, a is zero or 1, b is zero or 1, and R°

represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group of the following formula (I)-2 ##STR145## in which A²¹ is a group selected from the definition of A², B¹¹ is a group selected from the definition of B¹, R¹¹, R²¹ and R³¹, independently from each other, are a group selected from the definition of R¹, and b'"'"' is a number selected from the definition of b,

or R°

may be bonded to the group A² to form a 5- to 7-membered ring together with the nitrogen atom to which they are bonded.

3. The ultrathin film of claim 2 wherein

R¹, R² and R³ each represent methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, phenyl, tolyl, benzyl, perfluoromethyl, perfluoroethyl, 2-trifluoromethylethyl, trifluoromethylphenyl or the group of formula (I)-1 in which R⁴, R⁵, R⁶ and R⁷, independently from each other, are selected from the same groups as R¹ above, and n is as defined;

A¹ and A², independently from each other, represent alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, xylylene, methylenephenylene, naphthylene or a group of the formula (I)-1-1 ##STR146## wherein A¹¹ represents a single bond, --O--, --SO₂ --, --CH₂ -- or ##STR147## B¹ represents alkylene having 1 to 12 carbon atoms, cyclohexylene, phenylene, xylylene, methylenephenylene or naphthylene;

a is zero or 1;

b is zero or 1; and

R°

represents hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, or the group of formula (I)-2 in which R¹¹, R²¹, R³¹, A²¹, B¹¹ and b'"'"' are as defined above, or R°

is bonded to the group A² to form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded.

4. The ultrathin film of claim 1 wherein the silicon-containing polyamine (A) contains in the molecule one or more bonded units represented by the following formula (II) ##STR148## wherein R⁹ represents a monovalent hydrocarbon or fluorinated hydrocarbon group having 1 to 16 carbon atoms, R¹⁰ and R¹² are identical or different, and each represents a hydrogen atom, or a monovalent hydrocarbon group having 1 to 16 carbon atoms which may contain a primary or secondary amino group and a silicon atom, or R¹⁰ and R¹² may be bonded to each other to form an alkylene group interrupted by the group --NH--, p is an integer of 1 to 10, provided PG,83 that R¹⁰ and R¹² are not simultaneously hydrocarbon groups having no amino group;

and

at least two primary and/or secondary amino groups in the molecule.

5. The ultrathin film of claim 4 wherein not all, but at least some, of the bonded units of formula (II) are bonded units of the following formula (II)-a ##STR149## wherein R⁹, R¹⁰, and R¹² are as defined in formula (II) above, provided that the free bond from the silicon atom is bonded directly to another carbon atom or another oxygen atom, and the free bond from the oxygen atom is bonded directly to another silicon atom.

6. The ultrathin film of claim 4 or 5 wherein the silicon-containing polyamine containing units represented by the following formula (III) ##STR150## wherein R¹³ and R¹⁴ are identical or different and each represents a monovalent hydrocarbon, fluorinated hydrocarbon or tri-hydrocarbon silyl hydrocarbon group having 1 to 16 carbon atoms,

in addition to the units of formula (II) or (II)-a.

7. The ultrathin film of claim 4 or 5 wherein in formulae (II) and (II)-a, R⁹ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms, a phenyl group, a tolyl group, or a fluorinated derivative of any of these.

8. The ultrathin film of claim 4 or 5 wherein in formulae (II) and (II)-a, at least one of R¹⁰ and R¹² is a hydrogen atom.

9. The ultrathin film of claim 4 or 5 wherein in general formulae (II) and (II)-a, the monovalent hydrocarbon group R¹⁰ or R¹² is an alkyl group having 1 to 12 carbon atoms, an alicyclic group having 6 to 15 carbon atoms, an aromatic group having 6 to 15 carbon atoms or an aralkyl group having 7 to 15 carbon atoms each of which may containing a primary or secondary amino group and may be substituted by a trialkyl silyl group having 1 to 10 carbon atoms in each alkyl moiety.

10. The ultrathin film of claim 5 wherein p in formulae (II) and (II)-a is 2 to 6.

11. The ultrathin film of claim 4 or 5 wherein the silicon-containing polyamine is represented by the following formula (IV) ##STR151## wherein R¹³ and R¹⁴ are identical or different and each represents a monovalent hydrocarbon, fluorinated hydrocarbon or tri-hydrocarbon silyl hydrocarbon group having 1 to 16 carbon atoms, a plurality of R¹³ groups or a plurality of R¹⁴ groups are identical or different, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are identical or different and are selected from the groups defined for R¹⁰ and R¹², x and y are identical or different and each represents an integer of 1 to 10, and y represents zero or a number of 1 to 250.

12. The ultrathin film of claim 4 or 5 wherein the silicon-containing polyamine is represented by the following formula (V) ##STR152## wherein R¹⁹ and R²⁰ groups are identical or different and each represents a monovalent hydrocarbon or fluorinated hydrocarbon group having 1 to 16 carbon atoms, or a group of the following formula (V)-1 ##STR153## in which R²⁴ and R²⁵ are identical or different and are selected from the groups defined for R¹⁰ and R¹², and z is an integer of 1 to 10,

R²² and R²³ are identical or different and each represents a hydroxyl group, a monovalent hydrocarbon group, a fluorinated hydrocarbon group or a monovalent hydrocarbon--O-- group or a group of formula (V)-1 mentioned above and s is a number of 1 to 250, provided that a plurality of the groups of formula (V)-1 are not bonded to the same silicon atom simultaneously, and the compound of formula (V) contains at least 2 primary or secondary amino groups.

13. The ultrathin film of claim 1 wherein the silicon-containing polyamine (A) contains in the molecule at least one bond unit represented by the following formula (VI) ##STR154## wherein R⁹, R¹⁰ and R¹² are the same as defined in formula (II) and Ar represents a divalent aromatic hydrocarbon group,

and at least two primary and/or secondary amino groups in the molecule.

14. The ultrathin film of claim 1 wherein the silicon-containing polyamine (A) is represented by the following formula (VII) ##STR155## wherein D¹, D², D³ and D⁴, independently from each other, represent a hydrogen atom or a group of the formula (VII)-1 ##STR156## in which B¹, R¹, R² and R³ are as defined hereinabove, i and j are identical or different and each represents zero or a positive number, provided that the sum of i and j is at least 2, and at least one group of formula (VII)-1 is contained in the molecule.

15. The ultrathin film of claim 1 wherein the polysiloxane compound (B) contains at least two bonded units of the formula ##STR157## wherein R²⁶ represents a monovalent hydrocarbon or fluorinated hydrocarbon group having 1 to 18 carbon atoms,

in the molecule.

16. The ultrathin film of claim 15 wherein all of the bonded units of formula (VIII) form bonded units of the following formula (VIII)-a ##STR158## wherein R²⁶ is as defined above.

17. The ultrathin film of claim 1 wherein the polysiloxane compound (B) is represented by the following formula (VIII)-b ##STR159## wherein R²⁶, R²⁷, R²⁸, R²⁹, R³⁰ and R³² are identical or different and each represents a monovalent hydrocarbon or fluorinated hydrocarbon group having 1 to 18 carbon atoms, and q is a positive number.

18. The ultrathin film of claim 17 wherein the monovalent hydrocarbon group is an alkyl group having 1 to 18 carbon atoms, phenyl, tolyl or benzyl, and the movovalent fluorinated hydrocarbon group is perfluoromethyl, perfluoroethyl, 2-trifluoromethylethyl or trifluorophenylmethyl.

19. The ultrathin film of claim 1 wherein the polyisocyanate (C) is a silicon-containing polyisocyanate containing at least two isocyanate groups in the molecule.

20. The ultrathin film of claim 1 wherein the polyisocyanate (C) is represented by the following formula (IX) ##STR160## wherein R¹, R², R³, B¹, A², A¹ and a are as defined hereinabove, Y¹ represents a hydrocarbon group having 3 to 15 carbon atoms, R°

°

represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a group of the following formula (IX)-1

space="preserve" listing-type="equation">--CONH--Y.sup.1 --NCO (IX)-1

in which Y¹ is as defined,

a group of the following formula (IX)-2 ##STR161## in which A²¹, B¹¹, R¹¹, R²¹ and R³¹ are the same as defined for formula (I)-2, and Z² represents a single bond or a group of the following formula (IX)-3 ##STR162## wherein Y¹ is as defined above, or R°

° and

A² may be bonded to each other to form a 5- to 7-membered ring together with the nitrogen atom to which they are bonded, and Z¹ is a group selected from the definition of Z².

21. The ultrathin film of claim 20 wherein in formula (IX), R¹, R², R³, B¹, A², A¹ and a are the same as defined hereinabove, Y¹ represents an alkylene, cycloalkylene, arylene or alkylene-aryleene-alkylene group having 1 to 15 carbon atoms, and R°

° and

Z¹ are the same as defined hereinabove.

22. The ultrathin film of claim 1 wherein the polyisocyanate (C) is represented by the following formula ##STR163## wherein R¹³, R¹⁴, Y¹, r, x and y are the same as defined above, R³³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 16 carbon atoms, and t is zero or 1.

23. The ultrathin film of claim 1 wherein the polyisocyanate (C) is represented by the following formula (XI) ##STR164## wherein the definitions of R²⁰, R²², R²³ and s are the same as in formula (V), and a plurality of R³⁴ groups are identical or different and each is a group selected from the definition of R¹³ or a group of the following formula ##STR165## wherein R³³, Y¹, t and z are as defined above, provided that at least two groups of formula (XI)-1 are contained in the molecule.

24. The ultrathin film of claim 1 wherein the polyisocyanate (C) is represented by the following formula (XII) ##STR166## wherein R¹³, R¹⁴, Y¹, x, y and r are the same as defined above.

25. The ultrathin film of claim 1 wherein the polyisocyanate (C) is an aliphatic diisocyanate having 3 to 17 carbon atoms, an alicyclic diisocyanate having 8 to 17 carbon atoms, an aralkyl diisocyanate having 9 to 17 carbon atoms, a monocyclic or dicyclic aromatic diisocyanate having 8 to 17 carbon atoms, a tricyclic or higher aromatic tri- to dodecaisocyanate having about 23 to about 100 carbon atoms.

26. An ultrathin film composed substantially of a polyaddition polymer comprising bonded units derived from said silicon-containing polyamine (A) of formula (I) in claim 2 above and said polyisocyanate (C).

27. The ultrathin film of claim 1 which has a thickness of about 0.01 to about 1 micron.

28. The ultrathin film of claim 1 which has a thickness of about 0.03 to about 0.5 micron.