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Eur. fo/w.

Pergamon PII: S00143057(96)000618

J. Vol. 32, No. 10, pp. 1235-1242, 1996 Copyright 0 1996 Ekevier Science Ltd Printed in Great Britain. All rights reserved 0014-3057/96 $15.00 + 0.00

DIBENZYLIC STRUCTURES ON MACROMOLECULAR CHAIN: IX. THE INTERACTION OF URETHANE-ISOCYANATE GROUPS IN POLYURETHANE FORMATION
ADRIAN A. CARACULACU*, IOAN AGHERGHINEI, PAUL BARON, GEORGETA CARACULACU and SERGIU COSERI*
41

Romanian Academy, Institute of Macromolecular Chemistry P. Poni, Aleea Gr. Ghica Voda No. A, 6600 Jassy, Romania
(Received 3 February 1995; accepted in final form 17 October 1995)

Abstract-The interaction of isocyanate-urethane and isocyanate-amide groups in urethane group formation is studied. Bibenzil-2,2-di-yl diisocyanate (27 BBDI) presents specific behaviour due to the steric specificity of its structure. Rotation of the two aromatic nuclei around ethylenic bridges favours strong intramolecular anchimeric assistance in the second step of the 2,2 BBDI with n-butanol (BuOH) reaction. This assistance also enhances secondary reactions leading to unexpected cyclic allophanate structure. Mechanisms for these reactions are proposed in concordance with kinetic measurements. Copyright 0 1996 Elsevier Science Ltd

INTRODUCTION

Dibenzyl structures have variable geometry owing to the rotation around the ethylenic bridge. In previous

~
*To whom all correspondence should be addressed.

studies concerning the introduction of such structures on a macromolecular backbone, a series of polymers which contain these structures were presented [l-3]. As was pointed out in these studies, a special case was that of polymers which contain dibenzylic structures derived from monomers, having their functional groups placed in the 2,2 position.
These polymers are characterized by lower

NC0

+
Scheme 1 1235

1236

A.

A. Caraculacu et al.
Table 1. Model compounds

molecular weights compared to those derived from homologous monomers substituted in the 4,4 or 2,4 positions [l-3]. In some cases we have also succeeded in pointing out the formation of small cyclic oligomers [I, 21, even when their appearance implies greater energies of formation such as the cyclic urea II. This is the case of the reaction between 2,2 BBDI and water [l]. As was shown, the structure of the cyclic urea II has aromatic nuclei simultaneously distributed in an eclipsed cis conformation, related to the ethylenic bridge, similar to the structure of the orthocyclophane [l] (Scheme 1). Further studies proved that these specific features of the isomer 2,2 BBDI are due not only to any steric hindrance that limits the access of the reaction partner to the functional groups. It also seems that a considerable reciprocal anchimeric assistance between functional groups in the 2 and 2 positions modifies substantially their chemical behaviour during the reaction. In a previous work, we have studied the specific behaviour of 2,2BBDI in the reaction with BuOH 141.After the first sten of the reaction the urethane gioup formed, has increased considerably reactivity of the second NC0 group:

Typ GHIN(R)COOR NO. R -H -H -H -CH, R: -CHI _(CHz),CH, -CHzCH, -CHICHI Reference IO 11 10 13

I
2 3 4

Type R-OCONH-(o Ph) -(CHz),(o Phj-NHCOOR: R 5 6 CH>(CH+ CHr CHr Other 8 R: CH,(CH+ CH,(CH+ CHr Reference 4 4 4

COOBU

COOBu

where kz >> k, Thus when the reaction is performed in benzene, the monoreacted product m is not able to be isolated even when working with excess 2,2 BBDI [4]. On the other hand, the kinetic study of the reaction between isocyanates and alcohols or glycols [S-7] has enabled us to point out some new aspects of the mechanism of this reaction in which a decisive role is played by the hydrogen bond associated with the alcohol-alcohol or alcohol-urethane types, as well as between isocyanate-alcohol or isocyanate-urethane ones. As the isocyanate-urethane interaction is generally ignored or even doubted [8], we consider that the

study of the reaction between 2,2 BBDI and BuOH can offer strong evidence with this subject due to its specificity. Before undertaking the study of the complex behaviour of the 2,2 BBDI reaction in the first part of this paper we have attempted to define more accurately the influence of urethanes and amides in the simplest case, represented by the reaction between phenylisocyanate (PhNCO) and BuOH. The conclusions obtained have been verified in the case of the 2,2 BBDI reaction with BuOH. Necessary model substances for the kinetic study by high performance liquid chromatography (HPLC) were synthesized (see Table 1).

Dibenzylic structures on macromolecular chain

1237

4000

3000

2000

1600 -I

1200

800

600

400

Fig. 1. IR spectra for tht:yclic

allophanate, Al.

EXPERIMENTAL

AnalaR PhNCO, minimum 99.9% purity, verified chromatographically, was used. 2,2 BBDI was synthesized according to the data available in the literature [9]. The NC0 content and purity were established by chemical methods [5] and HPLC.
Solvents

Tetrahydrofuran (THF) and benzene (Bz) were dried with sodium and distilled before use. P.a. grade N,N-dimethylformamide (DMF) was dried for 24 hr with 2% (weight) 4,4-methylenediphenyldiisocyanate (MDI), at 60C and then vacuum distilled. P.a. grade BuOH was dried with calcium hydride and then distilled. The melting points were established by means of a capillary tube. IR (KBr pellets) measurements were carried out on a Specord M 80 Carl Zeiss Jena spectrophotometer. IH-NMR measurements were performed with a 60 MHz JEOL spectrometer.
Model synthesis

Carbanilic

acid methyl ester (CME), carbanilic

acid

n-butyl ester (CBE) and carbanilic acid ethyl ester (CEE) models (Table 1, nos l-3) were obtained starting from a 3/l alcohol-PhNCO molar ratio mixture. To the corresponding quantity of the alcohol, a solution of 25% PhNCO in Bz was added over 1 hr at 60C. The reaction mixture was additionally stirred for 2 hr and maintained overnight at 60C. After removal of Bz and alcohol excess by vacuum distillation, the crude product was recrystallized. Ethylformamide (EFA) and N-methyl carbanilic acid ethyl ester (MCEE) (Table 1, no. 4) models were synthesized according to literature methods [l2, 131. 1,2-Ethylene bis(o-carbanilic acid) di-n-butyl ester, 1,2-ethylene bis(ocarbanilic acid) methyl, n-butyl ester and 1,2-ethylene bis(o-carbanilic acid) dimethyl ester models (Table 1, nos 57) were synthesized and purified according to previously published methods 14, 141. The cyclic allophanate (Al) (Table 1, no. 8) was obtained as a secondary product of the reaction between 2,2 BBDI and BuOH in a l/l molar ratio, beside no. 5 representing the main reaction product. The solvent used was a mixture of Bz/DMF = 3 (vol.). The insoluble Al in the reaction mixture was separated by filtration and purified by recrystallization from DMF-H20 l/l vol. mixture. Melting point: 32l-325C; molecular weight for CXIHZNZOS: calculated, M = 338.41, found = 356 (a Knauer vapour

co-o
I 1

-CHz-CHI-CH~-CH, 3 4

5 2 i 1

5 6 @pm)

Fig. 2. NMR spectra for the cyclic allophanate, Al.

1238

A. A. Caraculacu ef al.
Table 2. HPLC conditions Mobile phase Water MeOH (% vol.) 40 60 Flow (mL:min) Wavelength Retention tune .______ Model

No.

Isocvanate PhNCO

Column Lichrosorb RP IB-10pm

(nm)
237

SWXS

Mtn 4.45 5.41 7.43 10.85 4.48 8.38 19.5 23.07

?I Additwe I Additive 2

I 7
h X 5

I
2.2 BBDl ii 67 Llchrosorb RP 8-10 pm

254

II n, Al h

No I 11= unreacted PhNCO (blocked as I): r = reacted PhNCO (model 2); additwe I = CEE; additive 2 = MCEE No.?. K = unreacted dlisocyanate (blocked as 7); m = monoreacted diisocyanates (blocked as 6): Al = cychc allophanate (model X): h = blreacted dlisocyanates (model 5).

pressure osmometer. solvent DMF. was used); elemental analysis: calculated. C, 70.92; H. 6.1 I; N. 7.98: found: C. 70.98; H. 6.55; N. 8.28. IR and NMR spectra arc given in Figs I and 2.
Kinetics

RESULTS AND DISCUSSION

A similar technique to that described previously


diisocyanateebutanol, PhNCO-glycols or alcohols

for reactions

was used [5, 141.


HPLC ana1wi.t

A Hewlett-Packard 1084 A chromatograph fitted with UV variable wavelength detector 1030 B was used. The reversed-phase method was preferred using Lichrosorb RP-18 and respective RP-8 columns 10 pm (Brownie Labs. USA) of 250 mm length and 4.6 mm internal diameter. Injection volume 5 mm3, column temperature 40C. flow 1 cm min-I. The chromatography conditions are given in Table 2.

As indicated in previous work [4] and from Table 3. the urethane (CEE) addition in the reaction between PhNCO and BuOH produces a significant increase of the reaction rate constant. This catalytic action requires the presence of the urethanic hydrogen in the urethane molecule. The substitution of the urethane group hydrogen with an alkyl as in MCEE determines the disappearance of the catalytic effect and even the appearance of an inhibiting effect. This inhibition takes place as a result of alcohol oxydrilic hydrogen blocking by a hydrogen bond with the N-alkyl urethane group of MCEE, similar to the cases of the reaction in the presence of esters or of ethers [4] (Table 3, no. 3). Taking into account the amide group being similar

Table 3. Reaction of PhNCO wth I-BuOH at 60 C Concentration (mol/l) ~~__.. ~_~~ NO. Alcohol + additve I-BuOH
I-BuOH +

_ x-1x IO (mol -I min ~I LJ Solvent 32.92 78 32 BZ B7_

Extent of secondary reaction (%) with: ...____. DMF Trace of moisture


0.2

Ratio OH/NC0 2:l 2:I

Alcohol and additive 0.3502 0.3506 0.7092 0.3491 0.702) 0.3496 0.7034 0.3501 0.7093 0.3499 6.4P 0.17.50 3.241 0.3500 0.1750 0.3501 6.17,

PhNCO 0. I758 0. I792

Urethane

EFA

0.3

CEE I BuOH

2 I

0.1761

lb

Ih

BZ

17

M&E
I-BuOH + DMF ImBuOH EZA ImBuOH D&F I-BuOH
7

?:I

0. I706

105.36

BZ

8.1X

?.I

0. I747

5x4
731

BZ

39

05

2.1

0 1749

BziDMF I:1 BqDMF 3:1

4.74

I.?

0.3493

772

2.39 x 10

3.18

0.32 x 10~

+
DMF I-BuOH 2:I 0.1747 26.4

BZ

x
I-BuOH

3.75 _~

TAF

2:1

0.1792

17.06

9 I

TliF

Bz/THF I:1

8.1

The mixture Bz/DMF = l/l (vol.) represents 6.49 mol/L DMF in Bz. The mixture Bz/DMF = 3/I (vol.) represents 3.24 mol/L DMF in Bz. The mixture Bz/THF = l/l (vol.) represents 6.17 mol/L THF in Bz. teading to GHs-N = CH-N(CH,)s. Leading to C6HrNHCSNH-CaH~. Leading to allophanate formation type: CaHrN(COOB~)-C~NH-CsHI. Leading to C6HINH-CGN(CzHS~H0.

Dibenzylic

structures

on macromolecular

chain

I239

to the urethane one, as regards the hydrogen bonding possibilities, a special situation is presented by the influence of the DMF addition. In line with the considerations above, we ought to expect an inhibiting action similar to that of N-alkylated urethane, MCEE. the DMF being an amide without amide hydrogen. The results obtained do not confirm this supposition. The reaction rate has increased considerably (see Table 3, nos 4, 6 and 7). The situation can be explained by supposing that in the DMF case, two opposite effects take place. In the first, DMF inactivates the alcohol reactivity due to the appearance of hydrogen bonding between an OH group and DMF (equation (3)). The second effect of DMF is that of activation of the PhNCO by -NC0 group polarisation presented by structures a in equation (4). At higher temperatures the interaction between -NC0 and DMF can ease even a total movement of electrons, resulting in the formamidinic group appearance (equation (4)). In our kinetic conditions the formamidine is not observed; the precision of our detection could even determine 0.32 x IO- mol/L formamidine.

The possible perturbatory secondary reaction between EFA and PhNCO we found to be below 0.5% in our
reaction conditions: + CzH<NHCHO-+PhNHCON(C?H)CHO (5)

Ph NC0

After these introductory studies concerning the simplest reaction between PhNCO and BuOH. we were able to understand better the behaviour of the more complicated system represented by the reaction between 2,2 BBDI and BuOH and also to explain the effects of DMF addition. In concordance with our recent proposed general urethane reaction mechanism [7], the reaction of 2,2 BBDI with BuOH is not a simple process. For the reaction it is necessary that both -NC0 and -OH groups be activated. Thus the process starts in the first step of reaction by the interaction of one alcohol molecule (activated by hydrogen bonds) with one from the two -NC0 groups of 2.2 BBDI (activated also by other alcohol or urethane molecules). This first step of the reaction is characterized by a rate constant, k,. and is also sensitive to the catalytic

R-OH---O=CH-N (3) \
CH3

Inhibition

R-N-

&-0
(CH&N

-7-c
-CH-0

l(4)

a Activation

Regarding these two effects, the experimental results presented above demonstrate that during the reaction between PhNCO and BuOH, the activating effect of DMF (equation (4)) is prevalent. Taking into account the difference between the catalytic effect of unsubstituted and substituted urethanes mentioned above (see Table 3, nos 2 and 3), by also considering the mechanism represented by equations (3) and (4). a monosubstituted amide (which posses an amidic group hydrogen) ought to show, similarly to unsubstituted urethanes, a more activating effect even than that of DMF. Indeed. according to the experimental data (see Table 3, no. 5) the addition of ethylformamide instead of DMF, determines a further (EFA). increase of reactivity, six times higher than in the case of the addition of an equivalent quantity of DMF.
EPJ 321&F

action of DMF, as in the case of the reaction between PhNCO and BuOH (Table 3). As we have shown in the Introduction. when the first stage of the 2,2 BBDI reaction is achieved, the appearance of the resulting urethane group creates the condition of a powerful intramolecular catalytic action, accelerating considerably the second step of the reaction. In this stage the supplementary catalytic effect of the DMF becomes imperceptible. Moreover the inhibition effect of DMF on alcohol reactivity (equation (3)), could even decrease the k2 value. Indeed, the kinetic measurements (see Table 4 no. 2) confirm these suppositions. Thus, the addition of 3.24 mol dm- DMF. results in a 30-times increase in the k, value. Simultaneously the value of k, decreases to a half of its initial magnitude. Further, on increasing the DMF concentration it is expected to result only in an increase of

I240

A. A. Caraculacu

et al

Table 4. Reactmn of 2,2 BBDl wth I-BuOH m benzene at 60 C (rate constants m mol- minm L) Extent of secondary reaction (%) with: Concenrrauon No. I 2 3
kt =

mol.L

Ratlo OH/NC0 I.2 1.2 I :2

Alcohol 0.1750 0.1750 0.1750 2.2 BBDI 0.1751 0.175 I 0.175 I

Concentrauon of additive (DMF), mol:L None 3.24 6.49

h, I IO ,I 64 147
=

K=

kt:k:

ky x IO

k, x IO

H>O 0 3.6 2.66 formation;


kl =

Urethane to Al 0.97 14.2 7.17 reaction rate

0.0082 0.49 1.07

280 140 137

6.85 69 43
b,

reaction rate constant for monourethane. m. formation: k. constant for allophanate. Al. formation (equation (8)).

reaction rate constant for biurethane,

k,. the kl value remaining practically unchanged due to the fact that the BuOH is already entirely hydrogen bonded with the DMF. The experimental results wholly verified these suppositions (see Table 4, no. 3). A more detailed analysis of the reaction mixture composition in the reaction of 2,2 BBDI with BuOH has evidenced the formation of an unexpected product for these mild conditions of reaction. that is the cyclic allophanate (Al) (see Table 1, no. 8). We have supposed that this product appears as a result of a secondary reaction of the intramolecularly activated state X (Scheme 2) formed after the first stage of the reaction of 2,2 BBDI and it is caused by the intramolecular urethane-isocyanate group interaction. The DMF addition inhibits the alcohol reactivity. lowering the k2value. The internal cyclization leading to allophanate (Al) consequently facilitates and increases the value of kz (see Table 4, nos 1 and 2). To verify this hypothesis, two reaction routes were considered for the allophanate appearance. The first starts from the monourethane m, without the assistance of another alcohol molecule; the second implies the internal activation complex X (Scheme 2). which involves the supplementary participation of an alcohol molecule.
In the first case, the formation of Al could be

where [Al] = the concentration and [M] = the concentration product, m.

of allophanate, Al, of the monoreaction

In the second case, the kinetic equation becomes: d[Al]/dt = k,[M][A] where [A] = the concentration of the alcohol (a). The graphic representation of the dependence In F+V~O regards the 7 value in both cases is given in as Figs 3 and 4.
-o-o-

r
0 5 IO IS 20

25

30

T x 10m3 mol min drnm3 Fig. 3. Dependence of In I& (%), function of [T], for allophanate Al formation, considering equation (7): 0,

determined by the kinetic equation: d[Al]/dr = k,[M]


(7)

kinetic no. I; 0,

kinetic no. 2: 0, kinetic no. 3 (from Table 4).

IOOO-

750 $

50

100

150

200 z mol min dm-

250

300

350

400

Fig. 4. Dependence of In iGclP(%), function of [T], for allophanate Al formation, considering equation (8): 0, kinetic no. 1; $, kinetic no. 2: 0, kinetic no. 3 (from Table 4).

Dibenzylic structures on macromolecular chain

1241

I242

A. A. Caraculacu

et 01. V. Cozan. J. Mnwo~~~ol. Sci. Chenl.


A27, 1547

The fact that equation (8) demonstrates a better linear dependence (Fig. 4) supports the hypothesis that the Al probably arises from the same activated state X which also leads to biurethane product b appearance. The above shows that the seemingly unexpected behaviour of the 2,2 BBDI reaction with BuOH might not have been understood without considering the urethane reaction mechanism previously proposed by us [7].

(1990).

6. 7.

8. 9. 10.

REFERENCES II.

1. A. A. Caraculacu and L. Misina. Rerisrcr Ma~eri& P/mice 32, 38 (1995). 2. A. A. Caraculacu and G. Caraculacu. J. MNU~~W/. .%i. Chefs. A22, 63 I (1985). 3. E. Scortanu. A. A. Caraculacu. G. Caraculacu and I. Agherghinei. Eur. PO/WI. J. 29, 999 (1993). 4. A. A. Caraculacu. I. Agherghinei. Cr. Prisacariu and

II!. 13. 14.

A. A. Caraculacu. 1. Agherghinei. P. Baron and S. Coseri. Rer. Rournnirte de C/h. 41. 539 (1996). A. A. Caraculacu. 1. Agherghinei. P. Baron and D. Timpu. Rev. Rowmine de C/h.. in press. A. A. Caraculacu, I. Agherghinei. G. Caraculacu. P. Baron and D. Timpu. Rer. Rounmine de C/h.. in press. A. E. Oberth and R. S. Bruenner. J. fh,vs. C/tern. 72. 845 (1968). A. A. Caraculacu. 1. Bestinuc, Z. Kellemen. V. Popescu. Romanian Patent 81570 (May 1983). R. L. Shriner and F. B. Cox. J. Ain. Clrew. Sot. 53, 1601 (1931). G. T. Morgan and A. E. J. Pettet. J. C/rear. Sot. I I24 (1931). F. Gamier. L;ehigs Anncrlen r/w Chemie 4, 241 (1887). J. van Romburgh. Rewed de.7 Trnwws Chirtlie des Pqs-Bus 48, 925 (1929). A. A. Caraculacu. I. Agherghinei, M. Gaspar and Cr. Prisacarium. J. C/tent. Sot. Perkin Trans. 2, 1343 .^^_ (IYYO)