Process for producing polyamines

• US 3,912,693 A
• Filed: 04/02/1974
• Issued: 10/14/1975
• Est. Priority Date: 04/05/1973
• Status: Expired due to Term

• Current Assignee: Kiyoshi Shimizu, Susumu Harada
• Original Assignee: Kiyoshi Shimizu, Susumu Harada
• Inventors: Shimizu, Kiyoshi, Harada, Susumu
• Primary Examiner(s): Kight, III, John
• Application Number:
  US05/457,359
• Time in Patent Office: 560 Days
• Field of Search: 260/78.5BB,8.3R,8.3N,86.1R,86.1N 204/159.22
• US Class Current: 522/4
• CPC Class Codes: C08F 26/02 by a single or double bond to nitrogen
• CPC Class Codes: Y10S 526/923 Ethylenic monomers containing at least one salt group

Abstract

Polymers or copolymers of diallylamine derivatives of the formula,
wherein R1 is hydrogen or methyl: R2 and R3 are independently hydrogen, allyl, methallyl, straight-chain or branched-chain alkyl having 1-16 carbon atoms, phenylalkyl or hydroxyalkyl of the formula, HO-(-CH2-)m-, in which m ia an integer of 1-6 or R2 and R3 may form together with the adjacent N atom pyrrolidyl, piperidyl or morpholino; and Y is halogen or inorganic acid anion, are produced by conducting photopolymerization of a solution or slurry of at least one diallylamine derivative mentioned above with or without other comonomer such as maleic anhydride, maleic acid, or a vinyl compound, with irradiation of light having wavelengths of 150-500 m Mu . The polymerization rate can be accelerated in the presence of a special sensitizer such as benzophenone or acetophenone together with hydroquinone, dioxane, morpholine or derivative thereof, or a charge-transfer complex of sulfur dioxide and a diallylamine derivative.

Claims

1. A PROCESS FOR PRODUCING A POLYMER OR COPOLYMER OF DIALLYLAMINE DERIVATIVE OF THE FORMULA,

2. A process according to claim 1, wherein the solution or slurry comprises at least one diallylamine derivative of the formula (I) and a solvent or non-solvent in an amount of 30% by weight or less based on the total weight of the monomer or monomers.

3. A process according to claim 1, wherein the solution or slurry comprises at least one diallylamine derivative of the formula (I), maleic acid or maleic anhydride and a solvent or non-solvent in an amount of 30% by weight or less based on the total weight of the monomers.

4. A process according to claim 1, wherein the solvent or non-solvent is water, or methyl alcohol, ethyl alcohol, isopropyl alcohol, dimethylsulfoxide, acetone or an aqueous solution thereof.

5. A process according to claim 1, wherein the photopolymerization is carried out in the Absence of a sensitizer.

6. A process according to claim 1, wherein the photopolymerization is carried out in the presence of a sensitizer.

7. A process according to claim 6, wherein the sensitizer is a mixture of at least one compound of the formula,

8. A process according to claim 6, wherein the sensitizer is a mixture of at least one member selected from the group consisting of benzophenone and acetophenone and at least one member selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, hydroquinone monoethyl ether, dioxane, morpholine, N-methyl morpholine and N-( Beta -hydroxyethyl) morpholine.

9. A process according to claim 6, wherein the sensitizer is a charge-transfer complex of sulfur dioxide and a diallylamine derivative of the formula (I).

10. A process according to claim 9, wherein the diallylamine derivative of the formula (I) is a diallylammonium salt derivative.

11. A process according to claim 9, wherein the diallylamine derivative of the formula (I) is diallyldimethylammonium chloride, diallyldiethylammonium chloride or diallylmorpholinium chloride.

12. A process according to claim 1, wherein the photopolymerization is carried out at a temperature of from -10* to 100*C.

13. A process according to claim 1, wherein the photopolymerization is initiated at a temperature of 60*C or lower.

14. A process according to claim 1, wherein the solution or slurry is formed into a film or plate 0.1-5 cm in thickness.

15. A process according to claim 14, wherein said film or plate is covered by a thin film showing no absorption of light in the 300-450 m Mu region.

16. A process according to claim 1, wherein one or more fluorescent lamps, one or more low-pressure mercury-arc lamps or sunlight is used as a light source.

17. A process according to claim 1, wherein the photopolymerization is carried out with irradiation of light having wavelengths of 200-500 m Mu .

18. A process according to claim 1, wherein the diallylamine derivative of the formula (I) is at least one member selected from the group consisting of diallyldimethylammonium chloride, methyldiallylamine hydrochloride, diethyldiallylammonium chloride, diallylpyrrolidinium chloride, diallylmorpholinium chloride, methylbenzyldiallylammonium chloride and methyldiallylamine phosphate.

19. A process according to claim 1, wherein the vinyl compound of the formula (II) is at least one member selected from the group consisting of acrylamide, acrylic acid, N-vinylpyrrolidone, dimethylaminoethyl methacrylate hydrochloride and dimethylbenzylammoniumethyl methacrylate chloride.

20. A process according to claim 1, wherein the copolymerization ratio is 0.005-2.5 moles of N-vinylpyrrolidone or a vinyl compound of the foRmula (II) per mole of a diallylamine derivative of the formula (I).

21. A process according to claim 1, wherein the copolymerization ratio is 0.01-2.0 moles of maleic acid per mole of diallylamine derivative of the formula (I).

22. A process according to claim 7, wherein the sensitizer is dissolved in an alcohol.

23. A process according to claim 9, wherein the charge-transfer complex of sulfur dioxide and a diallylamine derivative of the formula (I) is dissolved in water or methyl alcohol, ethyl alcohol, isopropyl alcohol, dimethyldulfoxide, acetone or an aqueous solution thereof.

24. A copolymer of a diallylamine derivative of the formula (I) and maleic acid.

25. A copolymer of diallyldimethylammonium chloride and maleic acid.

26. A copolymer of diallylpyrrolidinium chloride and maleic acid.

27. A copolymer of diallylmorpholinium chloride and maleic acid.