Adhesionenhancement of chromiumtannedheavy-dutyleather (Salzleather) underextremeconditions using photoreagents as surfaceprimers

Catalin Foteaa, , Claudius DSilvab,

a b

,
,

LBSA, School of Pharmacy, University of Nottingham Department of Chemistry and Materials, The Manchester Metropolitan University, John Dalton Building, Chester Street, Manchester M1 5GD, UK Accepted 18 December 2002. Available online 23 March 2005. http://dx.doi.org/10.1016/j.ijadhadh.2002.12.001, How to Cite or Link Using DOI Cited by in Scopus (2) Permissions & Reprints

Abstract
The work described investigates the development of photoreagents as surfaceprimers for the enhancement of adhesion with heavy-dutyleathersurfaces (Salz). Several reagents were investigated which included 4-azidophenol (1), 3-azidophenol (2), 4-(2,2-iminodiethanol)-3nitrophenylazide (4) and 4-azido-(2,2-iminodiethanol)benzamide (6) and used as an intimate mixture with commercial polyurethane adhesive (Solibond PU39) to enhance the adhesion of Salzleathersurfaces. The photoreagents upon UV irradiation covalently attach to the leathersurface enriching it with new functionalities to provide sites for bonding with the adhesive layer. The adhesion strength of photo primer treated leather samples were tested using the T-peel test against abraded leathersurfacesunder dry and wet conditions. Compounds 4 and 6 on T-peel testing were found to enhance adhesion strength by 99% under dry conditions and 163% and 157%, respectively, under wet conditions. The observed failure type was cohesive within the substrate when photoreagents were used, suggesting covalent bonds formation at the interface in addition to the usual van der Waals forces and hydrogen bonds affecting adhesion.

Keywords

Coupling agents; Surface treatment; Destructive testing; Chromiumtannedleather

1. Introduction
Leather is a naturally occurring material containing collagen as its major protein constituent. The characteristic properties of leather result after re-tanning, colouring, fat-liqouring and finishing [1]. The above treatments irremediably alter leather's chemistry (surface and bulk), with many groups on the peptide backbone being appreciably affected by the tanning process, making adhesion a problem. In an attempt to improve adhesion, we recently reported a method of bonding based on increasing the degree of molecular contact between adhesive and the leathersurface by enhancing adsorption [2]. In this approach an IPN (Interpenetrating Polymer Network) was created by polymerisation of monomers of the structure X3SiRY to form a cross-linked polysiloxane network which chemisorbed onto the leathersurface via H-bonds or van der Waals interactions whilst the Y group reacted with an isocyanate reagent to increase the overall hydrophobicity and adherence of the resultant IPN [2]. Although the joints formed using an IPN based on 3-(2-aminoethylamino) propyltriethoxysilane (AEAPES) showed an increased total joint strength, of 96.9 N under dry and 51.2 N under wet conditions[2], further improvements in the joint under wet conditions were considered necessary to meet the stringent requirements for use of this technology to heavy-dutyleather boots. Chemisorbed bonds weaken under wet conditions therefore an ideal solution would involve the formation of a covalent bond between the adhesive and leather. The tanning process together with the waterproof treatments applied on the skin side make it chemically inert. Therefore surface enrichment with active chemical groups was sought to enhance adhesion and to produce strong, durable joint assemblies.

1.1. Surfaceprimers
Aryl azides belong to a group of compounds capable of generating reactive electron deficient species (nitrenes) on irradiation with a UV light. Nitrenes are reagents of electrophilic character sharing chemical similarities with other electrophilic nitrogen reagent [3] and [4], but posseses four non-bonded electrons which can accept electrons from electron rich species [5], to form covalent bonds (see Fig. 1).

Fig. 1. Decomposition pathways of aryl azides with the amino acid residues of proteins. Inset: 1, 3-Dipolar nature of azides. The thermal stability of azides are critically dependent on the nitrogen substituent, whilst aryl azides have high thermostability, alkyl or acyl structures are unstable and can decompose violently on exposure to heat, mechanical shocks or aggressive chemical reagents. Aryl azides have been used to investigate the binding site of macromolecules and to bond polymers to glass [6]. In the latter approach a photoreactive siloxane primer of the structure N3RSi(OR)3 was used to react with functional groups (OH) present on the glass surface via the siloxane function. On photoactivation of the aryl azide group a nitrene species is generated which bonds covalently to the backbone of the polymer film. In the approach proposed to functionalise leather we considered the preparation of a variety of hydroxyl functionalised aryl azides which on photoactivation could covalently bond to the leathersurface and introduce hydroxyl groups to facilitate covalent bond formation with the adhesive (see Fig. 2). In this paper we report on the synthesis of two hydroxyl and two new dihydroxyl photoprimers (see Fig. 3) and their evaluation in the enhancement of adhesion to leathersurfacesunder dry and wet conditions.

Fig. 2. Schematic representation for the use of aryl azides as coupling agents.

Fig. 3. Structures of hydroxy and dihydroxy aryl azides evaluated as surfaceprimers for leather.

2. Experimentation
2.1. Chemicals
Phloroglucinol.2H2O, 4-hydroxylaniline and 2,4-dinitrobenzene were from Avocado, UK; diethanolamine (2,2-iminodiethanol), sodium azide and 4-aminobenzoic acid were from Aldrich Chemical Co. Ltd. (UK). Preparative silica gel plates Analtech (1212 cm; 2 mm) were obtained from Alltech. Chem. Co. The adhesive used was Solibond PU39 (CrispinAdhesives Ltd) an opaque one component polyurethane polymer solution which hardened on solvent release. Manufacturer's specification: d 0.860.88 g cm3, drying time at 20 C: 10 to 30 min. Solvents: acetone, EtOAc. Melting points were uncorrected. ATR and FT-IR spectra were analysed with Spectrum Lite software (PerkinElmer). 1H and 13C NMR spectra were recorded at 270.05 and 67.80 MHz, respectively, using TMS as an internal standard. MS were recorded at 70 eV and ESIMS at 3.5 or 3.0 kV, 70 C, in a H2O/MeOH (1:1) matrix.

2.2. Aryl azide synthesis

2.2.1. 4-Azidophenol (1) To a stirred ice cooled solution of 4-hydroxylaniline (1.0 g; 0.01 M) dissolved in a (1:1) mixture of AcOH/ H2O (50 cm3) was added NaNO2 (2.1 g; 0.03 M) slowly. After 5 min were added sodium azide (2 g; 0.03 M) and diethyl ether (50 cm3). The diethyl ether layer was separated, washed with water, dried on MgSO4, evaporated and the resultant black oil triturated with hexane (2x) and decanted. The residue was applied to a prep plate (1212 cm) eluted with CHCl3 and the upper band isolated as a reddish black oil on evaporation in vacuo (0.63 g: 65%). H1 NMR (CDCl3) 6.8 (s, 4x ArH); C13 NMR (CDCl3) 116, 120, 132 (COH), 152.5 (CN3); HREIMS (high resolution electroionisation mass spec) calc for C6H5N3O (M+) 135.0433, found 135.0433; IR () 2112 cm1 (N3), 3330 cm1 (OH); UV (THF) max 258 (max 1123), 290 nm (max 277 m2 mol1). 2.2.2. 3-Azidophenol (2) 3-Azidophenol (2) was obtained using the same procedure as for (1) but with 3hydroxylaniline as the starting material. After 20 min of reaction the solution was filtered to remove black insoluble polymeric residues, extracted with CHCl3, separated, washed with water, dried MgSO4, and evaporated in vacuo to give a yellow/brown oil. The oil was applied

to a prep plate (1212 cm) eluted with CHCl3 and the product on evaporation in vacuo isolated as a dark brown oil which on standing solidified to give a brown semi-solid (0.14 g; 11.3%); H1 NMR (CDCl3) 7.15 (t, , ArH), 6.6 (d, , 2x ArH), 6.5 (s, 13 ArH); C NMR (CDCl3) 106, 111, 112, 113, 130 (COH), 157 (CN3); EIMS m/z 135.1(M+), 29), 107.0 (M+N2), 100); HREIMS calc for C6H5N3O (M+) 135.0433, found 135.0432; IR (thin film) () 2115 cm1 (N3), 3300 cm1 (OH); UV (THF) max 210 (max 2036), 250 (max 719), 282 (max 451), 324 (max 219), 380 nm (max 207 m2 mol1) (see Fig. 4).

Fig. 4. Schematic for the synthesis of 4-azidophenol (1) and 3-azidophenol (2). 2.2.3. 4-Fluoro-3-nitrophenylazide (3) To a stirred ice-cold solution of 4-fluoro-3-nitroaniline (3.9 g; 0.025 M) dissolved in 1.2 M HCl (50 cm3; 0.06 M) was added dropwise a solution (20 cm3) of sodium nitrite (2.07 g; 0.03 M). After 5 min sodium azide (3.25 g; 0.05 M) dissolved in water (30 cm3) was added (see Fig. 5). The reaction mixture was stirred for 0.5 h at RT and then extracted with EtOAc, washed in water, dried (MgSO4) and evaporated to yield 3 (2 g; 75%), re-crystallized (EtOAc); mp 5455 C (lit. 5152 C [7]); IR () 2132 cm1 (N3). H1 NMR (D6MSO) 8.3 (dd, Ar-6H), 7.8 (s, Ar-2H), 6.95 (d, Ar-5H).

Fig. 5. Schematic for the synthesis of 4-(2,2-iminodiethanol)-3-nitrophenylazide (4). 2.2.4. 4-(2,2-Iminodiethanol)-3-nitrophenylazide (4) A mixture of 4-fluoro-3-nitrophenylazide (3) (1.18 g; 0.0065 M), diethanolamine (2,2iminodiethanol) (0.68 g; 0.0065 M) and EtOAc (20 cm3) was heated overnight on an oil bath with stirring, at 50 C. The reaction mixture was washed with water (320 cm3), dried (MgSO4) and evaporated in vacuo to give the product as a red solid, re-crystallized from EtOAc to give 3 (38%). H1NMR (CDCl3) 7.41 (d, J=8.8, ArH), 7.35 (d, J=2.6, ArH), 7.17 (dd, J=2.6, 8.8, ArH), 3.7 (t, J=5.1, 2xCH2OH), 3.3 (t, J=5.1, 2x(CH2)N), 2.3 (bs, 2x OH); HRESIMS (high resolution electrospray ionisation mass spec) calc for C10H14N5O4 (M+H) 268.1045, found 268.1042; IR () 2110 cm1 (N3). 2.2.5. 4-Azidobenzoic acid (5) To a stirred ice-cold solution of 4-aminobenzoic acid (4.2 g; 0.03 M) dissolved in 1.2 M HCl (30 cm3; 0.06 M) was added dropwise a solution (60 cm3) of sodium nitrite (6.2 g; 0.09 M). After 90 min, diethyl ether (45 cm3) was added followed by sodium azide (9.75 g; 0.15 M)

dissolved in water (90 cm3, see Fig. 6). The resultant solution was stirred at 5 C for 15 min and 90 min at RT. The ether layer was decanted and the aqueous layer extracted with diethylether (3x). The combined ether layers were washed with water, dried (MgSO4) and evaporated to yield a solid, re-crystallized from ethanol and then ethanol-water to give 5 (3 g; 61.3%); mp 185187 C with decomposition (lit. 183 C [8]). IR () 2105 cm1 (N3), 1681 cm1 (C O).

Fig. 6. Schematic for the synthesis of 4-[(2,2-iminodiethanol)carbonyl]phenyl azide (6). 2.2.6. 4-Azidobenzoyl chloride The reflux of 4-azidobenzoic acid (5) (0.5 g; 0.003 M) with SOCl2 (30 cm3) for 1 h followed by evaporation of the reagent yielded 4-azidobenzoyl chloride as an oil [9]. Repeated addition of benzene (10 cm3) followed by evaporation (3x), removed the excess SOCl2 (azeotrope mixture) and yielded crude 4-azidobenzoyl chloride (0.5 g; 90%) as a pale brown solid. The acid chloride had to be prepared within hours as the reagent was highly susceptible to hydrolysis by atmospheric moisture (6). 2.2.7. 4-Azido-(2,2-iminodiethanol)benzamide (6) To a solution of diethanolamine (2,2-iminodiethanol) (0.23 g; 0.0022 M) in THF (15 cm3) containing anhydrous K2CO3 (0.3 g; 0.002 M) was added 4-azidobenzoyl chloride (0.36 g; 0.002 M). After 20 h the solution was evaporated to a small volume and the resultant oil extracted with ethyl acetate, washed with HCl, sat NaCl and evaporated to give a solid (0.5 g). Purification on a silica gel prep plate (1212 cm) eluted with EtOH/CHCl3 (1:20) gave the product as a brown oil 6 (0.04 g; 12.5%). H1 NMR (CD3OD) 7.5 (d, , 13 ArH), 7.1 (d, , ArH), 4.9 (s, 2xOH), 3.6 (q, J=18, 39 Hz, 2x(CH2)2O); C NMR (CD3OD) 54, 60, 119.4, 120, 130, 134, 142.9; CIMS m/z 251.1 ((MH+), 100), 225.1 ((MH+C2H2), 60); HRCIMS m/z calc for C11H14N4O3 (M+H) 251.1144, found 251.1144 IR () 2127 cm1 (N3), 3381 cm1 (OH).

3. Results
3.1. Photoproperties of azides
Photodecomposition studies were undertaken on solutions of aryl azides dissolved in THF at the following concentrations: (1; 0.65104 mol l1), (2; 0.82104 mol l1), (4; 5104 mol l1), (6; 0.77104 mol l1), irradiated at a distance of 5 cm, using a CAMAG UV lamp (6 W; 254 nm), type TL 900/U at periodic intervals. UV/VIS spectra were recorded between 200 and 500 nm using a Lambda 40 PerkinElmer series spectrophotometer.

Compounds 1 and 2 were dark oils indicating a high degree of internal and through space (charge transfer) conjugation, between the OH and the azide group, respectively, which is supported by the values of max 258 nm (max 1123) for 1 and 250 nm (max 719) and 380 nm (max 207) for 2. Photolysis of 1 (0.65104 mol l1) in THF was monitored by following the decrease in the absorbance peak at 258 nm and the formation of a pronounced long wavelength product, max 300 nm. The photolysis of 1 showed two isobestic points one tightly centred at 275 nm and the other at 230 nm (see Fig. 7), with an apparent first-order rate constant of 6.9103 s1 ( ). The prominent product formed at 300 nm (see Fig. 7) may be a quinoneimine formed as a result of internal conjugation of the electron deficient nitrene with the hydroxyl-activated aromatic ring rather than ortho addition to give an azanorcaradiene intermediate, which undergoes electrocyclic rearrangement to an azepine (see Fig. 1).

Fig. 7. UV decomposition of 4-azidophenol (1). Spectra recorded at 0, 0.5, 1, 1.5, 2, 3, 4, 5, 6, 8 and 10 min intervals. The photolysis of 2 (0.82104 mol l1) under the same conditions as 1 was monitored by following the decrease in the peak at 250 nm. The photolysis showed a tight isobestic point at 270 nm with an apparent first-order rate of decomposition of 2.88103 s1 ( ) which was slower than 1. The photolysis of 4 (5104 mol l1) under similar conditions showed an isobestic at 315 nm but was biphasic in character indicative of a complex photolytic process (Fig. 8). Nitro-substituted aryl azides generate reactive nitrenes on irradiation but their chemical properties are profoundly affected by the photolytic properties of the nitro-substituent. The conclusion for 3-nitrophenylazides (4) from several reviews [10] and [11] is that they obey higher-order kinetics.

Fig. 8. UV decomposition of 4-(2,2-iminodiethanol)-3-nitrophenylazide (4). Inset UV decomposition. Photolysis of 6 (0.77104 mol l1) resulted in the decrease in the peak at 264 nm. The photolysis showed a tight isobestic centred at 284 nm (Fig. 9) with an apparent first-order rate constant of 8.9103 s1 ( ) similar in magnitude to 1 with the formation of a product with a broad adsorption around 290 nm.

Fig. 9. UV decomposition of 4-azido-(2,2-iminodiethanol)benzamide (6). Spectra recorded at 0, 0.5, 1, 1.5, 2, 3, 4 and 5 min intervals.

3.2. Surface treatment and testing

The surface treatment and testing for adhesion was reproduced according to our initial studies on the subject [2]. Leather panels cut to size (25.530.5 cm) were washed with a liquid soap solution (1:1 v/v Mardsen Chem Ltd in warm tap water, on the skin side). The samples were rinsed with cold tap water and stored open to the atmosphere in dust proof boxes to dry. After drying they were superficially abraded with abrasive paper (Buehler P60, both skin and inner flesh side).

The adhesive (Solibond PU39, Crispin-Adhesives Ltd) was spread with an adhesive spreader (B&Q, UK), only on the skin side of some test panel. The adhesive treated panels were left in the open at RT for solvent flash-off. The total flash-off time was 14 min (determined experimentally elsewhere [2]) which was divided into two parts a 9 min allowance for solvent evaporation in the open atmosphere followed by a 5 min photo-irradiation at a distance of 30 cm using a convection cooled 75 W Xenon arc lamp (Ushio) vertically mounted on an A1010 lamp unit. The lamp was fitted with a pyrex window and f/4.5 reflector (Photon Technology International-PTI) and was powered by a direct current power supply (LPS-220) with igniter (PTI). The spectral characteristics of the xenon lamp were continuous in the visible range, extending far into the UV and NIR. After flash-off and irradiation the panels were pressed together (ca. 0.4 kg cm2), the adhesive coated skin side to the superficially roughened flesh side of an uncoated panel, for a minimum of 5 min and allowed to set overnight at RT (similar to [2]). Quantities of compounds 1, 2, 4 and 6 dissolved in EtOAc (8 cm3) were uniformly mixed with adhesive (80 cm3) and the resultant mixture applied to leather panels for T-peel testing. The washings and roughening procedures applied to leather panel before adhesion increase its surface area, make it very porous and introduce the necessary hooks and grooves to effect adhesion via mechanical interlocking mechanisms in the first instance. An azide dissolved in an organic solvent (acetone or EtOAc) if applied to this surface would penetrate the superficial layer and enter the corium. It was for this reason that mixtures of azide and adhesive solution were used, to ensure the localization of the primer at the interface and not in the corium. The molar concentrations of photoreagents4 and 6 used and the average peel strength recorded are presented in Fig. 10, Fig. 11 and Fig. 12, respectively.

Fig. 10. Determination of optimum concentration of compound 4 on T-peel strength.

Fig. 11. Determination of optimum concentration of compound 6 on T-peel strength.

Fig. 12. T-peel test values under wet conditions. Adry and Awet from [2]. T-peel tests used for the testing of various surface treatments and assessment of adhesion strength were undertaken using ASTM D1876-72 as a reference. The test consisted of peeling apart two lap bonded pieces of leather (25.4 mm wide, 10 test samples cut from the large panels described before) fastened in the roll-over jaws of a tensiometer (Hounsfield with H.T.M. series software). Common practice requires first the initiation of a crack with the first and the last centimetre of the joint being ignored when recording the peel force. The speed of peeling is kept constant during the joint fracture, 254 mm min1 and the average force (N) required to separate the parts recorded over a fixed distance of 127 mm. To test the quality of joints underconditions of water saturation, bonded leather assemblies were soaked in a water basin for 24 h at RT, prior to removal and testing (whilst wet, Fig. 12). Compounds 1 and 2 showed limited adhesion strength on testing under dry conditions. Samples failed at small loads and they could be easily peeled off by hand and therefore they were not investigated further on the Hounsfield. This correlates with the UV decompositions studies namely the possibility of internal conjugation in the case of 1 and azepine formation in the case of 2 reducing the reactivity of the nitrene to external addition so the bridges between surface and the adhesive layer did not develop, hence the easy failure of the joints. Compound 4 showed the highest values of joint strength at the corresponding concentrations in Fig. 11. The maximum recorded value was attained at a concentration of 4.2 mM of photoreagent in the adhesive mixture. Unlike compounds 1 and 2 the presence of a nitrogroup in this compound deactivates the aromatic ring to addition by the nitrene and so is capable of forming bridges with the surface hence the higher joint strength.

Compound 6 gave a similar maximum value for the peel strength but at a slightly higher concentration, 5.5 mM (adhesive solution) see Fig. 12. In this case the presence of a carbonyl group in the aromatic ring deactivates the nitrene to addition with the ring and therefore it forms productive bridges with the surface so the greater peel strength of joints. The observed failure type in both cases was of the cohesive type within the leather substrate. Wet tests on 4 and 6 were performed at the optimum concentrations determined on dry samples and gave the results shown in Fig. 12. The observed failure type for wet samples was of the adhesive type at the substrateadhesive interface. For comparison purposes Fig. 12 shows values obtained for the standard procedure of surface treatment: liquid soap washings followed by superficial abrasion with a 10% dilution of the adhesive solution and 14 min solvent flash-off time (referred to as Aabraded samples, from [2]).

4. Discussion
Several factors influence surfaceadhesion: the nature of the surface, chemical impurities, the rate of adsorption of the adhesive into the surface and its solvent evaporation. To achieve optimum adhesion and reproducibility these factors have to be addressed in the preparation of samples prior to testing. Regarding adhesion to the leathersurface one of the conclusions of our previous work on the subject [2] was the requirement of aggressive surface treatments to achieve adhesion. In this respect we found that in addition to superficial roughening the use of washing with liquid soap and organic solvents (CHCl3) removed most of the weak boundary layers and significantly improved the joint strength. In all subsequent testing we used the standard procedure of liquid soap washing (Mardsen Chem.) and superficial abrasion (Buehler P60) with the respective joint strengths reported (T-peel test, 55.2 Ndry and 33.7 Nwet for A samples). These values were used as a reference for comparison against the testing of photoreagents. Both compounds 4 and 6 gave a total increase in peel strength of 99% compared to the standard procedure. In our previous studies, AEAPES gave an increase in peel strength of 75% dry and 53% for wet samples [2]. Adhesive bonds are believed to be accomplished via mechanical interlocking, the further increase in strength using azides suggests the formation of covalent bonds across the surface. These observations hold even for testing under wet conditions as both compounds showed much higher strength values than the wet standard (A) and wet AEAPES samples. Water is the most common hazard encountered by bonded joints exposed to the elements. Under water attack joints would fail due to diffusion through the adherent and/or adhesive or chemical attack of the adhesive layer (swelling, wicking). In this respect water would attack the most vulnerable position on an assembly: the interface region. The high values obtained for 4 & 6 suggest a better stress transfer across the surface and stronger bonds at the interface. The overall increase in peel strength for wet tests was 163% for 4 and 157% for 6. Looking at the chemical structures of compounds 1, 2, 4 and 6 it would appear that molecules like 1 and 2 with an electron donating hydroxyl group directly attached to the nitrene ring are not suitable as photo primers due to problems of direct or indirect conjugation, respectively,

reducing the reactivity of the nitrene species. Compounds 4 & 6 with the hydroxyl groups not directly conjugated to the nitrene ring and containing electron withdrawing groups (nitro, carbonyl) produce nitrenes capable of forming covalent bonds with the surface, due to deactivation of the aromatic ring discouraging the formation of an azepine ring by intermolecular addition. The presence of two hydroxyl ethylene groups give twice as many strong hydrogen bonds with the adhesive layer (physical bonds are additive). This explains the higher values for peel strength recorded with this type of reagent.

5. Conclusion
The excellent behaviour of photoreagents as surfaceprimers makes them a prime candidate for industrial applications. The technology is easy to implement and presents limited health and safety hazards. The irradiation stage uses a powerful UV lamp and it can be contained in a confined space for continuous batch process [12]. However even the use of this type of coupling agents does not exclude the necessary requirement of a abrasion stage which removes most of the weak boundary layer but at the same time affects the water proof layers. In this respect, the abrasion areas must be kept to a minimum and restricted to the regions to be bonded only. Future work aims at the design and use of new types of primers/photoprimers or combinations of photoreagents to produce strong joints under adverse conditions that would replace the need for stitches in boot manufacture.

Acknowledgements
The authors thank the Defence Logistics OrganisationResearch and Project Support (DLORPS) for a grant (Molecular Adhesives for Leather Seam Sealing) and the Overseas Research Award Scheme (ORS) for financial support. Thanks is expressed to D.E. Games of the EPSRC mass spectrometry Service Centre, Swansea, United Kingdom for EIMS, CIMS and HREIMS measurements.