Synthesis of polyvinylamine and polymer analogous reactions

Macromol. Chem. Phys. 195, 679-687 (1994) 679

Synthesis of polyvinylamine and polymer analogous reactions

Thomas Fischer, Walter Heitz*

Philipps-Universitat Marburg, FB 14 Physikalische Chemie, Institut fur Polymere und Wissenschaftliches Zentrum fur Materialwissenschaften, Hans-Meerwein-StraBe, D-35032 Marburg, Germany

(Received: April 16, 1993; revised manuscript of June 7, 1993)

SUMMARY Polyvinylamine (PVVAm) was synthesized using the precursor poly(tert-butyl N-vinylcarba-

mate) (PTBNVC). The monomer synthesis was improved, and the control of the molecular weight of the PTBNVC and the PVAm by a transfer reaction with the solvent is demonstrated. TBNVC was radically polymerized. In suspension polymerization molecular weights of 1 O6 g/mol are accessible. Different polymer analogous reactions were carried out. The resulting polymers are methylated polyvinylamine, poly(N-vinylureas), poly(N-vinylalkanamides) and PVAm-adducts with acrylic acid derivatives.

Introduction

Polyvinylamine (PVAm) has been synthesized in numerous ways -' ') using different precursor materials. It turned out that only the precursors poly(tert-butyl N-vinylcarbamate) (PTBNVC) 1 2 * 3, and poly(N-vinylformamide) IJ, Is) result in a polyvinylamine with no defect structure and reasonable molecular weights.

This paper deals with the synthesis of polyvinylamine using the precursor PTBNVC; the monomer synthesis is improved, the control of the molecular weight of the PTBNVC (and therefore of the PVAm) by the solvent will be demonstrated. Some polymer analogous reactions of the PVAm result in new materials. They are obtained by treating PVAm with methyl iodide, acyl chlorides, and acrylic acid derivatives.

Results and discussion

Synthesis of TBNVC

According to the literature I*) tert-butyl N-vinylcarbamate (TBNVC) is synthesized via acryloyl chloride. After the reaction with NaN,, acrylazide is obtained which is decomposed to the vinyl isocyanate (VIC), which reacts with tert-butyl alcohol in the presence of pyridine to form TBNVC.

A procedure is described showing that the formation of the highly toxic VIC and the subsequent reaction with tert-butyl alcohol can be carried out in a closed reaction apparatus. The VIC formed is directly distilled into a mixture of tert-bury1 alcohol and catalyst. Furthermore, if dibutyltin dilaurate is used as the catalyst, the reaction time can be shortened, the amount of tert-butyl alcohol can be reduced to 60% with respect to the literature procedure and the yield of TBNVC increases to 81 To.

0 1994, Huthig & Wepf Verlag, Basel CCC 1022-1 352/94/$08.00

680 T. Fischer, W. Heitz

Synthesis of PTBNVC

TBNVC is polymerized radically in solution and in suspension with AIBN at 60°C. With dilauroyl peroxide under the same reaction conditions no polymer was formed. Tab. 1 indicates that the control of the molecular weight of the PTBNVC is obviously determined by the different solvent transfer constants. In suspension very high molecular weight samples (up to m,, = lo6 g/mol) are accessible.

Tab. 1. Molecular weight of the PTBNVC obtained under different conditions a)

I 2 3 4 5 6 7 8 9 10 1 1 12

Toluene Toluene Toluene Toluene Toluene Hexane Benzene Benzene Benzene tert-Butyl alcohol tert-Butyl alcohol In suspensionc)

40 700 47 900 50 200 52 300 57 600 83 200 229900 304810 385 100 857 300 822 300

1 191 000

71 800 76 300 79 100 75 800 82 500 136 900 385 100 445 500 565 800 1200000 1182000 1 687 000

0,71 0,59 0,58 0,45 0,43 0,65 0,56 0,46 0,45 0,44 0,40 0,47

a) Reaction conditions: TBNVC (25 wt.-Vo), AIBN, solvent, T = 60°C. b, Determined by SEC in THF, 5 pm-polymer-mixed-gel (polystyrene), flow rate: 0,4 mL/min,

the M , and the dispersity ratios were determined by the universal calibration method using a viscodetector and PS standards.

') Polymerization of TBNVC with AIBN in suspension.

Synthesis of polyvinylamine hydrochloride (PVAmHCl)

The deprotection of the NH, group was carried out with HCl gas in toluene; in this way it is possible to obtain anhydrous PVAmHCl in contrast to the literature procedure. The structure of the anhydrous PVAmHCl can be studied more easily by elemental analysis and proton NMR spectroscopy (indicating the absence of the t-boc group).

PVAm was obtained by treating an aqueous PVAmHCl solution with an ion- exchange resin. The molecular weight of the PVAm was determined by measuring the limiting viscosity number and using the Mark-Houwink relation published by Bloys van Treslong (for a PVAm with an I%& between 15000 and 160000 g/mol)'2) ( [q] in dL/g):

[q] = 0,062 . Mo'88

It could be shown that even for higher molecular weights of PVAm the published Mark-Houwink relation is valid (Mi up to 250000 g/mol) (Tab. 2).

Synthesis of polyvinylamine and polymer analogous reactions 68 1

Tab. 2. Molecular weights of polyvinylamines obtained by hydrolysis of PTBNVC

No. aw (precursor)") [q]/(dL/g) b, a, (PVAm) ') a, (PVAm)d)

14 304800 1,83 91 700 113200 15 385 100 2,09 115800 139500 16 857300 3.28 257 800 232900

a) a, of the precursor in g/mol. b, Limiting viscosity number in 0,l M N a g , 0,Ol M NaOH, at 25 "C in dL/g. ') a, of the PVAm calculated from the M, of the precursor in glmol. d, Mw of the PVAm calculated from the limit. visc. no. according to ref. Iz).

The PVAm samples were examined by IR spectroscopy, NMR spectroscopy (in CD,OD) and viscosimetric measurements. No defect structure could be detected.

Polymer analogous reactions

There are a lot of papers dealing with the synthesis of PVAm, but not much is known about the modification of this homopolymer. Kobayashi et al. describe the crosslinking of this material with Mt2+ in aqueous medial5) and the crosslinking with bis- epoxides 1 6 ) . Bloys van Treslong reported the modification of PVAm by copolymeriza- tion of the precursor monomer ").

In this work the polyvinylamine homopolymer is modified by polymer analogous, homogeneous reactions. In all the cases methanolic PVAm solutions are used to react the amino group with reagents like alkyl iodides, isocyanates, acyl chlorides and acrylic acid derivatives.

Reaction with methyl iodide: Partially methylated poly(viny1ammonium iodide) (N- MePVAm) (1) was synthesized by treating a methanolic PVAm solution with MeI. Varying the mole ratio PVAM/MeI between 1 : 1, 1 : 2 and 1 : 20 results in different conversions; the average degree of methylation varies from 38070, 48% to 69% (determined by elemental analysis from the C/N ratio), respectively. The products are insoluble in methanol but soluble in water.

1: R, R = H, CH,


Reaction with isocyanates: Substituted vinylureas can be homopolymerized, but the resulting molecular weights are low Is).

Methanolic PVAm solutions were treated with phenyl and cyclohexyl isocyanate at 25 "C (2). The reaction results in a high conversion of the amino groups (98% and 82% respectively), determined by elemental analysis. The products were insoluble in water and organic solvents.

This reaction offers the possibility to synthesize high-molecular-weight poly(N- vinylurea); the %,-values calculated from that of the PVAm are in the order of 4 los g/mol.

Reaction with acyl chlorides: The only known poly(N-vinylacidamides) are poly(N- vinylformamide) and poly(N-vinylacetamide), synthesized radically or anionically from the corresponding monomers 19-21) .

By treating methanolic PVAm solutions with octadecanoyl chloride and hexadecanoyl chloride (in the presence of NEt,) high conversions of the amino groups are obtained. With short chain acyl chlorides the efficiency of the reaction under these conditions is low.

The long side chains are able to crystallize in the polymer. In poly(N-vinylhexadeca- noylamide) the side chains melt at 12,6 "C, whereas poly(N-vinyloctadecanoylamide) melts at 39,6 "C (DSC). This reaction opens a route to new comb-like polymers (3).

c=o NH-R R

2: R = C,H,, cyclohexyl 3 R = n-C,,H,,, n-C,,H,,

Reaction wifh acrylic acid derivatives: A further possibility to modify the PVAm homopolymer is the addition of the NH, groups of the polymer to acrylic acid derivatives. Acrylonitrile as well as ethyl acrylate and methyl acrylate were used to synthesize the new polymer structures 4 and 5 (Tab. 3).

f

CN

4 R = H, CH2CH2CN

pq R

" 5 R = H, CH2CH2R

R' = COOEt, COOMe

-CH2-CH I I

N-CH,-CH,-COOGNaO

y 2

y2

COOQNa"

6

Synthesis of polyvinylamine and polymer analogous reactions 683

If an excess of the reactant is present, more than one molecule of the acrylic acid derivatives reacts per N-atom. These products are soluble in common organic solvents like CHCl,, DMF and THE

Treating the ethyl acrylate adduct with 1 M aqueous NaOH results in hydrolysis of the ester groups and water-soluble products are obtained. The resulting polymer 6 strongly resembles a polymeric form of the complex-building agent EDTA.

Tab. 3. Characteristics of addition products of PVAm to acrylic acid derivatives

No. Reactant M, (PVAm)a) PVAm b, Reaction Cow.') Vred. d, Tg - - ~~

dL/g "C in Yo

React. time in h

Acrylonitrile Acrylonitrile Ethyl acrylate Ethyl acrylate Ethyl acrylate Methyl acrylate

232 000 1 :47 50 71 3,38 (DMF) 23,4

232000 1 :5 20 69 1,28 (THF) 2,l 232 000 1 : 5 20 64 1,34 (THF) -2.8 113000 1 : 5 20 66 0,53 (THF) -11,8

232 OOO 1 : 100 25 100 0,69 (DMF) -3,6

232 000 1 :50 69 >looe) 1,38 (DMF) 18,6

a, of the starting PVAm material in g/rnol. Mole ratio PVAm/acrylic acid derivative. Conversion of the amino group: e.g., 100% indicates that 2 rnol of reactant react with one NH, group. Values determined by elemental analysis. Reduced viscosity, c = 0,5 g/dL, T = 30°C. Product was probably contaminated with PMA.

Experimental part

tert-Butyl N-vinylcarbamate (TBNVC)

Vinyl isocyanate was synthesized following the literature procedure but the VIC formed (4.9 mol) was directly distilled into a mixture of tert-butyl alcohol (9,8 mol) and dibutyl tin dilaurate (0,03 mol) at 0 "C. After heating up to room temperature, the mixture was stirred for 6 h, precipitated in water, washed with water, dried with CaC1, overnight and dried i. vac. at 40 "C (yield: 81 Yo). It is possible to recrystallize the product from hexane, but for the polymerization step it turned out to be necessary to purify the product by sublimation; m. p. 64 "C (lit. I,):

63 -64 "C). IR (KBr): 3300, 2980, 2977, 1718, 1648, 1539, 1501, 1395, 1368, 1254, 1164 crn-I. 'H NMR (CDCI,, 300 MHz): 6 = 1,44 (s; 9H, CH,), 4,18 (d; 1 H, cis-H rel. to t-boc), 4,39

(d; 1 H), trans-H rel. to t-boc), 6,64 (m; 1 H, =CH-t-boc).

(C=C), 152.68 (C=O). I3C NMR (CDCI,, 75 MHz): 6 = 28,27 (CH,), 80,34 K-CH,), 91,90 (C=C), 130,02

C,H[$O, (1432) Calc. C 58,69 H 9,08 N 9,78 0 22,36 Found C 58,61 H 9,15 N 9,78 0 22,32


Poly(tert-butyl N-vinylcarbarnate) (PTBNVC)

Polymerization in solution: TBNVC was polymerized in the solvents toluene, hexane, benzene and tert-butyl alcohol with azoisobutyronitrile (AIBN) under Ar at 60 "C for 72 h (sample no. 6: 42 h). Tab. 4 summarized exact reaction conditions for the synthesis of PTBNVC samples.

Polymerization in suspension: 3 g (20,96 mmol) of TBNVC, 7,5 mg of AIBN and 0,3 mL (0,9 mL) of benzene were added to 3,3 mL (3,9 mL) of water containing the suspending agent (2% aqueous PVAc (88% hydrolyzed)). The solution was polymerized with a stirring rate of 500 rpm at 60°C for 72 h (sample no. 12, 13 resp., see Tab. 4).

'H NMR (CDCl,, 300 MHz): 6 = 1,39 (s; 3 H, CH,), 1,60 (m; 2H, CH,), 337 (m; 1 H, CH), 4,84 (m; 1 H, NH).

13C NMR (CDCl,, 75 MHz): 6 = 28,52 (CH,), 45 (broad; CH, CH,), 78,87 (C-0), 157,00 (C=O).

(C,HI,NO,)~ (143,2), Calc. C 58,69 H 9,08 N 9,78 0 22,36 Found C 58,68 H 9,22 N 9,74 0 22,31

Tab. 4. Reaction conditions for the synthesis of PTBNVC

a) No. Solvent Amount of TBNVC Amount of AIBN Yield - flred

dL/g in wt.-qo in mol-Yo in '70

1 Toluene 25,O 0,384 72 0,12 2 Toluene 25,O 0,192 61 0,13 3 Toluene 25,O 0,192 77 0,13 4 Toluene 25,O 0,180 66 0,13 5 Toluene 25,O 0,089 70 0,16 6 Hexane 27,6 0,086 88 0,3 1 7 Benzene 25,5 0,086 83 0,43 8 Benzene 25,4 0,086 88 0,65 9 Benzene 25,4 0,086 71 0,73

10 tert-Butyl alcohol 27,5 0,086 76 1,77 1 1 tert-Butyl alcohol 27,6 0,086 90 139 I2 In suspension 0,238 87 1,66 i 3 In suspension 0,238 85 4,35

a) Reduced viscosity, measured in toluene at 25 "C, c = 0,5 g/dL.

PoIyvinyIamine hydrochloride (PVAmHCI)

PTBNVC was dissolved in dry toluene (c = 0,172 mol/L) and the reaction mixture was flushed with Ar. At 0°C HC1 was bubbled slowly through the solution for 7 h and the PVAmHCl precipitated during the reaction. Pure, white PVAmHCl was obtained by filtration (under Ar) and washing the product with large amounts of dry ethanol and methanol (Tab. 5) .

'H NMR (D,O, 300 MHz): 6 = 2,27 (s; 2H, CH,), 3,85 (s; 1 H, CH). 13C NMR (D,O, int. stand. dioxane, 75 MHz): 6 = 38,40 (CH,), 45,96 (CH).

(C2H6NCl)n) (79,6)n Calc. C 30,18 H 73.5 N 17,61 C1 44,65 Found No. 17a: C 30,54 H 7,85 N 15,92 C143,21

No. 18a: C 32,38 H 7,92 N 15,69 C1 42,28 No. 19a: C 30,22 H 7,67 N 17,60 C143,Ol


Tab. 5. Synthesis of polyvinylamine hydrochloride (PVAmHCI)

No. Wt. of FTBNVC Vol. of toluene Yield of PVAmHCl in g in mL in g

17a 18a 19a

40,91 63,15 37,00

700 1 200 1500

19,84 34,72 17,82

Polyvinylamine (PVAm)

1 g of PVAmHCl was dissolved in 25 mL of H,O overnight and eluted over a column packed with Amberlite-IRA 400 (Aldrich), having an exchange capacity five times higher than the equivalent theroretical value. The resulting PVAm solution was freeze-dried and the resulting powder dried over P,O, at 60°C.

IR (film): 3346, 2926, 1594 , 1469, 1440, 1383, 1325, 1 127, 938, 825, 719 cm-I. ' H NMR (CD,OD, 300 MHz): 6 = 1,41 (s; 2H, CH,), 3,05 (s; 1 H, CH). I3C NMR (CD,OD, 75 MHz): 6 = 40,OO (CH), 44,65 (CH,).

(C2H5N)n (43,04)n Calc. C 55,81 H 11,63 N 32,56 Founda) No. 17b): C 54,29 H I1,85 N 31,30 0 2,45

No. 18b): C 55,85 H 11,88 N 30,91 0 1,45 No. 19b): C 56,26 H 12,51 N 29,37 0 1,78

Poly(viny1-N-methyl-ammonium iodide) (1)

PVAm (no. 14) was dissolved in dry methanol (c = 1 mg/mL) and treated with methyl iodide (MeI) for 3 h at 30°C varying the mole ratio between the NH,-group and the Me1 from 1 : 1 (no. 20), 1 : 2 (no. 21) to 1 : 20 (no. 22). The polymer precipitates, it is washed with methanol, and dried at 60 "C i. vac. The extent of methylation was calculated from the C/N ratio obtained by elemental analysis.

IR (KBr): 3447,2922, 1589, 1438, 1381, 1262, 1097 cm-I. ' H NMR (D,O, 300 MHz):

No. 21: 6 = 1,80 (s; CH,), 2,67 (s; CH,-N), 3,24-3,41 (m; CH-N', CH,-N'). No. 22: 6 = 1,95 (s; CH,), 2,69 (s; CH,-N), 3,24-3,5 (m; CH-H+, CH3-N+).

NO. 2 0 6 = 1,62 (s; CH,), 2,55 (s; CH,-N), 3,23 (s; CH-N'), 3,58 (s; CH3-N').

Elemental analysis: No. 20: C 36,25 H 7,23 N 15,93 I38,14 0 2,74 No. 21: C 31,53 H 6,41 N 13,44 14759 0 1,OO No. 22: C 27,07 H 5,79 N 10,59 I54,63 0 1,38

Poly(N- vinylureas) (2)

PVAm (1 0 mmol) was dissolved in 50 mL of methanol, and 15 mmol of isocyanate (cyclohexyl or phenyl isocyanate) were added at r. t. under vigorous stirring. The polymer precipitated during the reaction; it was washed with methanol and dried i. vac. at 60 "C. For each reaction the control

a ) In all the cases no CI was found. b, Sample no. 17 obtained from no. 17a, no. 18 obtained from no. 18a, no. 19 obtained from

no. 19a.


reaction was made by adding the isocyanate to methanol. In these cases no precipitation of products took place. The polymers are insoluble in common organic solvents like chloroform, THF, DMF, N-methyl-2-pyrolidone (NMP) and propylene carbonate.

Poly(N-vinyl-N-phenylurea) (no. 23):

1R (KBr): 3325, 3055, 2949, 1664,1599, 1550, 1439, 1312, 750, 692 cm-I.

(C,H,,N,O), (162,15), Calc. C 66,66 H 6,17 N 17,28 0 9,88 Found C 65,39 H 6,28 N 17,Ol 0 11,30

Poly(N-vinyl-N-cyclohexylurea) (no. 24):

IR (KBr): 3349, 2919, 2850, 1692, 1646, 1534, 1468, 1258 cm-'.

(C,H,,N,O), (168,13), Calc. C 64,29 H 9,52 N 16,67 0 9,52 Found C 62,21 H 9,65 N 15,46 0 12,94

PoIy(N-vinylalkanamides) (3)

To a solution of 10 mmol of PVAm in methanol (c = 0,2 mmol/mL) 15 mmol of acyl chloride (hexadecanoyl chloride: sample no. 25, octadecanoyl chloride: sample no. 26) and 15 mmol of NEt, were added and refluxed for 24 h. The precipitating polymer was filtered off, washed with methanol and dried i. vac. at 60 "C. The poly(N-vinyl-amides) are insoluble in common organic solvents like chloroform, THF, DMF, NMP and NMC (N-methylcaprolactam).

Poly(N-vinylhexadecanamide) (no. 25):

IR (KBr): 3294, 2921, 2851, 1730, 1647, 1543, 1468 cm-I.

(CI&~,NO), (281,2), Calc. C 76,87 H 12,46 N 4,98 0 5,69 C1 - Found C 75.20 H 12,03 N 5,11 0 5,92 C1 1,24

Poly(N-vinyloctadecanamide) (no. 26):

IR (KBr): 3311, 2919, 2850, 1742, 1 652, 1541, 1468 cm-I.

( C Z O H ~ ~ N O ) ~ (3093, Calc. C 77,67 H 12,62 N 4,53 0 5,18 C1 - Found C 76,44 H 12,40 N 4,15 0 5,64 C10,96

PVCAm-acrylic acid derivatives (4 - 6)

To methanolic PVAm solutions (c = 0,25 mol/L) freshly distilled acrylic acid derivatives were added and refluxed. The derivatives were acrylonitrile, ethyl acrylate and methyl acrylate. The polymer was precipitated in THF in the case of the samples no. 27,28,32, washed with THF and dried i. vac. at 60°C. The samples no. 29, 30, 31 were isolated by evaporating the excess acrylate and methanol at r. t. Tab. 3 summarizes the reaction conditions. The polymers are solublein DMF, the adducts with ethyl acrylate (no. 29-31) are even soluble in CHCI,, DMF and THF at r. t. All the samples stay in solution during the reaction because of the excess of acrylic acid derivative; they are all insoluble in pure methanol.


IR: No. 27 (KBr): 3378, 2955, 2248 (CN), 1779, 1721, 1680, 1601, 1255, 1 166 cm-I. No. 28 (KBr): 3336, 2920, 2837, 2247 (CN), 1734, 1669, 1261, 1110 cm-I. No. 29 (film): 3450, 3340, 2953, 2847, 1732 (CO), 1615, 1437, 1 178 cm-I. No. 30 (film): 3450, 3336, 2953, 2849, 1738 (CO), 1437, 1175 cm-I. No. 31 (film): 3450, 3336, 2953, 2846, 1732 (CO), 1437, 1 174 cm-I. No. 32 (film): 3450, 2954, 2848, 1732 (CO), 1437, 1363, 1326, 1261, 1 196 cm-I. ‘H NMR (DMF-d,, 300 MHz): No. 27,28: 6 = 1,38 (m; CI-12-CH,-NH), 136 (m; CE2-CH2-N), 3,33 (m; C&-CN;

‘H NMR (CDCI,, 300 MHz): N9. 29-31: 6 = 1,25 (m; CH,), 1,35 (m), 1,60 (m) (CI%,-CH-NH, CE2-CH-N), 2,45

‘ H NMR (DMF-d7, 300 MHz): No. 3 2 6 = 1,45 (m), 1,59 (m; CH,-CH-N, CH,-CH-NH), 1,74 (m), 2,22 (m), 2,37 (m),

CH-N and CH2-N are hidden under the DMF-peaks).

(m; Cu2-C0), 2,76 m (CH-N, CH,-N), 4,lO (s; CH,-0).

2,62 (m; CH-N, CH-NH, CH2-NH, CH,-N, CH2-CO), 3,53 (s; CH,-O).

Elemental analysis: No. 27: C 61,06 H 7,87 N 27,70 0 2,02 No. 28: C 62,72 H 8,23 N 27,21 0 1,73 No. 29: C 56,54 H 8,45 N 7,39 0 27,41 No. 30: C 56,14 H 8,02 N 7,75 0 27,19 No. 31: C 57,32 H 7,74 N 7,74 0 26,86 No. 32: C 56,27 H 7,70 N 3,92 0 32,28

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Synthesis of polyvinylamine and polymer analogous reactions