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WO1998018833A1 - Analogues de poly(vinylamine) - Google Patents

Analogues de poly(vinylamine) Download PDF

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Publication number
WO1998018833A1
WO1998018833A1 PCT/US1997/019659 US9719659W WO9818833A1 WO 1998018833 A1 WO1998018833 A1 WO 1998018833A1 US 9719659 W US9719659 W US 9719659W WO 9818833 A1 WO9818833 A1 WO 9818833A1
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acyl
hydrogen
alkyl
aryl
group
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Bruce M. Novak
Jeffrey T. Cafmeyer
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University of Massachusetts Amherst
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University of Massachusetts Amherst
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    • 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
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen

Definitions

  • This invention relates to the formation of vinyl amine derivatives and their polymerization to form new poly (vinyl amine) analogs.
  • Poly (vinyl amine) and its analogs are members of an important class of cationic polyelectrolytes , which are very desirable materials with applications in the textile, adhesive and coatings, paper, petroleum, water treatment, cosmetic, and pharmaceutical industries.
  • poly (vinyl amine) analogs cannot be obtained through the polymerization of the obvious parent molecule, vinyl amine, because vinyl amine is unstable with respect to its imine tautomer, ethylimine.
  • Poly (vinyl amine) analogs therefore have been obtained by indirect methods , e.g., th Hofmann rearrangement of poly (aerylamide) or the Schmidt reaction of poly (acrylic acid) .
  • the invention is based on the discovery that new poly (vinyl amine) analogs can be prepared by polymerization of precursors obtained by the isomerization of allylamines, allylamides, or allylimides.
  • New copolymers can also be formed using the same precursors in combination with other poly erizable substrates. These new polymers and copolymers are polyelectrolytes, bearing side chains which become positively charged at low pH.
  • the new methods require fewer steps than methods previously employed to obtain poly(vinyl amines) .
  • the invention features a polymer having the formula (1) :
  • R through R 4 independently, are hydrogen; an alkyl, e.g., C a H 2a+1 , where a is 1 to 20 or higher; an aryl, e.g., phenyl or substituted phenyl, e.g., substituted with CH 3 , CF 3 , or 0CH 3 ; an acyl, e.g., COH, C0CH 3 , or COCF 3 ; or a halogen, e.g., F, Cl, Br, or I; R 5 and R 6 , independently can be hydrogen; alkyl; aryl; acyl; alkoxycarbonyl, e.g., C00CH 3 , COOC(CH 3 ) 3 , or COOCH 2 CH 3 ; or silyl, e.g., Si(CH 3 ) 3 , (CH 3 ) 2 SiC(CH 3 ) 3 or Si(CH(CH 3 ) 2 ) 3 ; and n is at least
  • R 1# R 2 , R 3 , and R 4 are all hydrogen to give a polymer having formula (2) .
  • R 5 also can be hydrogen, and R 6 can be an acyl, forming a poly(crotyl amide) .
  • Some specific examples include poly(crotyl formamide) , poly(crotyl acetamide) , poly(crotyl dichloroacetamide) , poly(crotyl trichloroacetamide) , and poly(crotyl trifluoroacetamide) .
  • R 5 and R 6 both can be acyl, forming a poly(crotyl imide) .
  • R 5 and R 6 can be attached to each other to form a ring structure, as in poly(crotyl N-succinimide) having formula (3) .
  • Another aspect of the invention is a method for preparing a polymer by obtaining and then subjecting to polymerization conditions, a vinylic monomer having formula (4) , where R 2 to R 6 are as defined above.
  • the monomer can be prepared by isomerization of the allylic species with the formula (5) .
  • Polymerization methods include, but are not limited to, those described in the detailed description.
  • the invention features a copolymer having the formula (6) :
  • repeating units (7) and (8) can be linked in any
  • R ⁇ to R 6 are defined as above;
  • R 7 and R 9 independently, are hydrogen, alkyl, aryl, acyl, or halogen.
  • R 8 and I Q / independently, are hydrogen, alkyl, aryl, acyl, NR n R 12 , OCOR 1;L , CONR 1;L R 12 , C0 2 " , CN, COOR l;L , or NR 11 C0R 12 ; where R l ⁇ and R 12 , independently, are hydrogen, alkyl, aryl, acyl, or silyl.
  • n is at least 2. n can be up to 10,000, 100,000, 1,000,000, or higher.
  • the copolymer has the formula
  • X can be O or NR 13 ; where R 13 can be hydrogen, alkyl, aryl, silyl, or ac
  • R 7 and R 9 are hydrogen.
  • the invention features a method for preparing a copolymer from monomers having the formulae (10) and (11) , where R x to R 10 are as defined above, by subjecting these monomers to polymerization conditions.
  • Monomer (11) can be, for example, maleic anhydride; maleimide; an N-alkyl maleimide, e.g., N-butyl maleimide; an N-aryl maleimide, e.g., N-xylyl maleimide; an N-silyl maleimide, e.g., N-trimethylsilyl maleimide; or an N-acyl maleimide, e.g., N-pivaloyl maleimide.
  • maleic anhydride maleimide
  • an N-alkyl maleimide e.g., N-butyl maleimide
  • an N-aryl maleimide e.g., N-xylyl maleimide
  • an N-silyl maleimide e.g., N-trimethylsilyl maleimide
  • N-acyl maleimide e.g., N-pivaloyl maleimide.
  • monomer (11) can be, for example, a vinylic amine, a vinylic ester, a vinylic amide, a vinylic carboxylate, or a vinylic nitrile.
  • An advantage of the new methods is the utilization of easily accessible allylic amine derivatives as monomer precursors. Allylic amine derivatives are inexpensive to prepare and are very stable. The facile isomerization described herein provides the reactive vinyl amine derivatives necessary for polymerization.
  • the polymers of the invention are unique in that they include not only the amine functionality attached at every other carbon atom along the polymer backbone, conferring polyelectrolytic properties, but also an alkyl or alkyl derivative attached to the intervening carbon atoms of the backbone. In the parent poly(vinyl amine), this position is simply occupied by a hydrogen atom. This allows for tremendous diversity in the realm of poly(vinyl amine) derivatives. For example, a lipophilic group at this locus can be used to create phase transfer catalysts or even hydrocarbon soluble polyelectrolytes. Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.
  • allylamines Three classes of substrates can be used to form stable or transient vinyl amine analogs upon isomerization: allylamines, allylamides, and allylimides. These substrates are catalytically isomerizable to enamines, enamides, and enimides, respectively, all of which are structurally similar to either vinyl amine or the protected vinyl amine monomer.
  • primary enamines, alkyl enamines, and aryl enamines are called unprotected monomers.
  • Enamides (acyl enamines), enimides (diacyl enamines) , vinylic carbamates (alkoxycarbonyl enamines) , and silyl enamines are protected monomers.
  • Unprotected Monomers Unprotected Monomers
  • Enamines offer the most direct approach to the preparation of vinyl amine-derived copolymers.
  • the polymerization of these compounds incorporates an amine functionality into the polymer without the need for deprotection of a precursor.
  • an enamine can be unstable with respect to its imine form.
  • less substituted enamines e.g., primary enamines
  • Secondary and tertiary enamines have alkyl or aryl substituents, e.g., ethyl, isobutyl, phenyl or substituted phenyls.
  • isoinerization catalysts include those derived from ruthenium, e.g., 10 mol% RuClH(CO) (PPh 3 ) in refluxing benzene for 1 to 15 hours; cobalt, e.g., 1 mol% CoH(N 2 ) (PPh 3 ) in tetrahydrofuran (THF) at 80°C for 15 hours; rhodium, e.g., 1 mol% [Rh(diphosphine) (THF) n ] +" Cl0 4 in THF at 40°C for 23 hours, the diphosphine ligand can be 2,2'- bis(diphenylphosphino)-l,l'-binaphthyl (BINAP) ; or molybdenum, e.g., 1 mol% trans-Mo (N 2 ) (Ph 2 PCH 2 CH 2 PPH 2 ) 2 in toluene at 100°C for 1.5 to 5 hours.
  • the isomerization can be catalyzed by base.
  • bases include potassium tert-butoxide or potassium amide on alumina.
  • Secondary enamines are less stable than tertiary enamines and tend to tautomerize to the corresponding imines, although the isomerization of secondary allylamines with a ruthenium catalyst allows selective, transient formation of secondary enamines.
  • it is necessary to polymerize the intermediate species before tautomerization e.g., at low temperature, e.g., -100°C to 100°C, and preferably -10°C to 25°C, and under anhydrous conditions, to produce vinyl amine polymers .
  • Silyl enamines e.g., bis(trimethylsilyl)amino-l- propene (12),
  • vinylic carbamates e.g., N- (ter -butoxycarbonyl) -1- propenylamine (14) ,
  • protected monomers are regarded as "protected” monomers, since their silyl or acyl substituents help to prevent tautomerization to the imines, but can subs' lently be removed under hydrolysis conditions, e. ⁇ ., in aqueous base or acid, to generate the free amine or ammonium salt, respectively.
  • protected monomers include 2- methyl-1-propenylacetamide, 1-propenyl-tert- butylcarbamate, 1-methyl-
  • the real advantage of using protected enamines is that they allow the preparation of unsubstituted poly(vinyl amine) derivatives, upon deprotection, while avoiding tautomerization.
  • polymers which can be obtained through polymerization of a protected monomer, followed by deprotection, include poly(l-(ethylamino) -2- methylpropene) , poly(l-amino-3-phenyl-l-butene) , and poly(l-cyclohexylamino) -l ⁇ pentene) .
  • Enamides, enimides, and enamines differing in the protecting groups attached to nitrogen can be copolymerized. Some protecting groups are easier to hydrolyze, or deprotect, and thus can be selectively deprotected to give partially deprotected polymers or copolymers.
  • An example is the partial deprotection of poly(vinyl trifluoroacetamide- co-vinyl acetamide) to give poly(vinyl amine-co-vinyl acetamide) (17) , where n is as defined above.
  • Tertiary enamines e.g., N,N-dimethyl-N- propenylamine and 2-methyl-N-propenylpiperidine
  • electron-deficient monomers including maleimide, N-ethyl maleimide, N-butyl maleimide, N-phenyl maleimide, and maleic anhydride.
  • the copolymerization reactions are carried out, for example, using free radical initiators.
  • Free radical initiation was effected by a diazo compound, azobisisobutyronitrile (AIBN) , and a perester, tert-butylperoxybenzoate.
  • Other free radical initiators include water-soluble diazo compounds, such as 2,2'- azobis(amidinopropane) hydrochloride, peroxides, such as tert-butylhydroperoxide and benzoylperoxide, and dithiuram disulfides, such as tetraethylthiuram disulfide.
  • an acceptable temperature range for the polymerization reactions is -100°C to 100°C, more preferably 0°C to 65°C.
  • Benzene, THF, toluene, water, and isopropyl alcohol have been successfully employed as solvents, although solvent is not essential.
  • Secondary and tertiary enamides due to the beneficial electronics imparted by the protective groups, are stable precursor monomers in the production of vinyl amine derivative polymers. Once polymerized, the precursor polymers can then be hydrolyzed to give poly(vinyl amine) derivatives.
  • the allylamide isomerization products, N-propenylformamide (NPF) and N- propenylacetamide (NPA) were polymerized using either free radical initiators, as described above, or cationic initiators.
  • the cationic initiators used include a Lewis acid, tin(IV) tetrachloride, and a stabilized cation, triphenylcarbenium pentachlorostannate.
  • Other cationic initiators include protic acids, such as perchloric acid and trifluoromethanesulfonic acid, and Lewis acids, such as boron trifluoride, aluminum trichloride, and titanium tetrachloride.
  • Other initiators include iodine, diaryliodium salts, and ionizing radiation.
  • the NPF and NPA monomers were copolymerized with electron deficient monomers, such as vinyl formamide, maleimide, N-ethyl maleimide, N-butyl maleimide, N-phenyl maleimide and maleic anhydride, using, for example, free radical initiation, as described above.
  • the N- propenylamide monomers should also copolymerize with vinyl acetate, acrylamide, sodium acrylate, acrylonitrile, methyl methacrylate and n-butyl acrylate, all of which have been previously copolymerized with N- vinylformamide (NVF) .
  • N-propenylamides have also been shown to copolymerize with other N-propenylamides and with NVF.
  • a reaction flask was charged with 5 A molecular sieves (20g) , A10 3 (4g) , diethyl ether (40 Ml) , piperidine (5.12g, 8.26 mmol) , and a stir bar. Isobutyraldehyde (3.60g, 49.9 mmol) was added slowly to the mixture. The flask was then equipped with a condenser and was allowed to stir for 2 hours. The mixture was filtered and fractionally distilled at 80°C with a pressure of 40 mmHg to give the desired enamine product, having the formula (18).
  • Proton nuclear magnetic resonance ( 1 H-NMR) was used to analyze a solution of the product in deuterated chloroform.
  • the 1 H-NMR spectrum collected on a 200 MHz instrument had a multiplet at a chemical shift of 5.3 parts per million (ppm) which integrated to one proton, a triplet at 2.5 ppm which integrated to four protons, two doublets at 1.66 ppm and 1.59 ppm which integrated to three protons each, and a multiplet from 1.4-1.2 ppm which integrated to six protons.
  • ppm parts per million
  • a reaction vial was charged with N-ethylmaleimide (EtMI) (0.1090 g, 0.087 mmol) and a stir bar.
  • EtMI N-ethylmaleimide
  • a solution of 2-methyl-l-propenylpiperidine (0.55 M) and AIBN (0.004 M) in benzene was prepared, as described in Example 1.
  • the 2-methyl-l- propenylpiperidine and AIBN solution (1.55 mL, 0.085 and 6.2 x 10- 3 mmol) was then added to the vial containing EtMI. Upon mixing the solution became light yellow in color.
  • the vial was capped, sealed with TEFLONTM tape, and quickly brought out of the drybox and placed in the photolysis chamber. During photolysis at 366 nm, the polymer precipitated from solution. The polymer was isolated by precipitation into diethyl ether and dried in vacuo, and had the formula (19) . In all examples, n is as defined
  • Thermolysis of the AIBN initiator was also effective for the copolymerization of the enamides.
  • the procedure used was the same as above except that the reaction mixture was sealed in an ampule under vacuum and placed in an oil bath at 100°C using maleic anhydride and EtMI as comonomers.
  • reaction tube Wc.s charged with N,N- dimethylallylamine (0.5013g, 5.90 mmol) and RuClH(PPh 3 ) 3 (0.032g, 0.091 mmol) .
  • the reaction tube was heated to 60°C overnight.
  • the iso erized monomer having the formula (20) was isolated from the catalyst by vacuum distillation.
  • Proton nuclear magnetic resonance ( 1 H-NMR) was used to analyze a solution of the product in deuterated chloroform.
  • the 1 H-NMR spectrum collected on a 200 MHz instrument had a doublet at a chemical shift of 5.88 parts per million (ppm) which integrated to one proton, a multiplet at 4.19 ppm which integrated to one proton, a singlet at 2.5 ppm which integrated to six protons, a doublet at 1.60 ppm which integrated to three protons, and a broad peak at 0.8 ppm which integrated to two protons.
  • a vial was charged with N,N- dimethylamino-1-propene (0.0850 g, 1.00 mmol), EtMI (0.1250 g, 1.00 mmol), and a stir bar.
  • a solution of AIBN (0.500 L, 0.032 M, 5.11 x 10- 4 mmol) in benzene was then added to the vial containing the monomers.
  • the vial was capped, sealed with TEFLONTM tape, and quickly brought out of the drybox and placed in the photolysis chamber. During photolysis at 366 nm, the polymer precipitated from solution. The polymer was isolated by precipitation into diethyl ether and dried in vac o, and had the formula (21) .
  • Proton nuclear magnetic resonance ( 1 H-NMR) was used to analyze a solution of the product in deuterated chloroform.
  • the 1 H-NMR spectrum collected on a 200 MHz instrument had a broad pea at a chemical shift of 8.5 parts per million (ppm) which integrated to one proton and four multiplets at 8.0 ppm, 6.7-6.2 ppm, 5.3-4.8 ppm, and 1.6 ppm which integrated to one proton each.
  • 1-Propenylacetamide was prepared by the method of Stille and Becker (J. Org. Chem . 1980, 45, 2139-2145), by refluxing N-allylacetamide with HRuCl(PPh 3 ) 3 in benzene under argon for 40 hours. The 1-propenylacetamide was isolated by distillation.
  • an ampule was charged with 1- propenylacetamide (0.2103 g, 2.15 mmol) and a stir bar. The ampule was removed from the drybox and tert-butyl peroxybenzoate (0.0073 g, 0.038 mmol) was added under an argon atmosphere using Schlenk techniques. The ampule was then degassed, sealed under vacuum and placed in a 150°C oil bath. After several hours the ampule contents were dissolved in DMF, precipitated into acetone and dried in vacuo .
  • a reaction flask was charged with 1- propenylacetamide (0.2505 g, 2.56 mmol), benzene (0.5 mL) and a stir bar. The flask was then sealed with a septa and removed from the drybox. A solution of ZnCl 2 (25 ⁇ L,1.0 M, 0.025 mmol) in 1,2-dichloroethane was added to the flask via syringe. After several hours at room temperature the contents became very viscous. The contents were then dissolved in DMF, precipitated into acetone, and dried in vacuo, , having the formula (23).
  • a reaction vial was charged with maleimide (0.0969 g, 1.00 mmol), 1-propenylacetamide (0.1019 g, 1.04 mmol) and a stir bar.
  • a solution of AIBN (0.01 M) in benzene was prepared.
  • the AIBN solution (0.50 Ml, 5.0 x 10 "4 mmol) was then added to the vial containing the monomers.
  • the vial was capped, sealed with TEFLONTM tape, and quickly brought out of the drybox and placed in the photolysis chamber. During photolysis at 366 nm, the polymer precipitated from solution. The polymer was isolated by precipitation into diethyl ether and dried in vacuo, and had the formula (24) .
  • thermolysis of the initiator was also effective for the copolymerization of the enamides.
  • the homopolymers and copolymers of the invention have commercial utility including, but not limited to the known applications of vinyl amide and vinyl amine homopolymers and copolymers.
  • these polymers have applications in the textile, adhesives and coatings, paper, petroleum, water treatment, cosmetic, and pharmaceutical industries.
  • These polymers have broader application than the parent poly(vinyl amine) , because the novel alkyl side chains attached at alternate positions on the polymer backbone provide an added diversity element to the new polymers, which allows the properties of the polymer, e.g., solubility, to be specifically tailored for a desired use.
  • an n-butyl group attached at every other position of the polymer backbone would increase solubility in non-polar solvents, e.g., hydrocarbons.
  • a substituted aryl, e.g., 4-phenol, attached at every other position of the polymer backbone would increase the solubility in polar organic solvents, e.g., ethyl acetate.
  • polymers of this invention can include flocculence enhancement in the paper manufacturing and water treatment, and maintenance of high viscosity for petroleum products, to facilitate pumping.
  • the polymers can also be used to prepare ion- exchange membranes.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

D'une façon générale, cette invention concerne un polymère représenté par la formule (1), où les éléments R1 à R4, pris séparément, représentent hydrogène; un alkyle, par exemple CaH2a+1, où a est égal à un nombre compris entre 1 et 20 ou plus; un aryle, par exemple phényle ou phényle substitué, notamment substitué par CH3, CF3 ou OCH3; un acyle, par exemple COH, COCH3 ou COCF3; ou un halogène, par exemple F, Cl, Br ou I; R5 et R6, pris séparément, peuvent représenter hydrogène; un alkyle; aryle; acyle; alcoxycarbonyle, par exemple COOCH3, COOC(CH3)3, ou COOCH2CH3; ou silyle, par exemple Si(CH3)3, (CH3)2SiC(CH3)3 ou Si(CH(CH3)2)3; et n représente un nombre égal ou supérieur à 2, n pouvant aller jusqu'à 100, 10000, 1000000, voire plus.
PCT/US1997/019659 1996-10-29 1997-10-27 Analogues de poly(vinylamine) Ceased WO1998018833A1 (fr)

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US60/029,487 1996-10-29

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0024682A1 (fr) * 1979-08-21 1981-03-11 Consortium für elektrochemische Industrie GmbH Procédé de préparation de n-propyl-n-propylidène-acétamide ou de di-n-propyl-acétamide
US4260714A (en) * 1979-05-18 1981-04-07 Dynapol Acetamidoethylene copolymers
EP0709367A1 (fr) * 1994-10-27 1996-05-01 BASF Aktiengesellschaft Procédé pour la préparation d'amides carboxyliques N-alkényle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4260714A (en) * 1979-05-18 1981-04-07 Dynapol Acetamidoethylene copolymers
EP0024682A1 (fr) * 1979-08-21 1981-03-11 Consortium für elektrochemische Industrie GmbH Procédé de préparation de n-propyl-n-propylidène-acétamide ou de di-n-propyl-acétamide
EP0709367A1 (fr) * 1994-10-27 1996-05-01 BASF Aktiengesellschaft Procédé pour la préparation d'amides carboxyliques N-alkényle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL ORGANIC CHEMISTRY, 1980, Vol. 45, STILLE J.K. et al., "Isomerization of N-Allylamides and Imides to Aliphatic Enamides by Iron, Rhodium and Ruthenium Complexes", pages 2139-2145. *

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