Chinese Journal of Chemical Engineering, 16(3) 446—450 (2008)

Mechanism of Chrome-free Tanning with Tetra-hydroxymethyl

Phosphonium Chloride*

SHAO Shuangxi (邵双喜)1,**, SHI Kaiqi (史楷岐)1, LI Ya (李亚)1, JIANG Lan (蒋岚)1 and
MA Chun’an (马淳安)2
1
Institute of Applied Chemistry, Ningbo University of Technology, Ningbo 315016, China
2
Zhejiang University of Technology, Hangzhou 310014, China

Abstract Tetra-hydroxymethyl phosphonium chloride (THPC) has been considered as an important chrome-free
tanning agent. To understand the THPC tanning mechanism, the structure, charge distribution, activity and tanning
ability of each phosphorous compound in THPC tanning system were studied, by 31P NMR, FT-IR spectroscopy,
differential scanning calorimetry (DSC) and computational chemistry method, etc. When pH raised to 6.0, the de-
composition of THPC would take place, which results in a production of free formaldehyde, tri-hydroxymethyl
phosphonium (TrHP) and tri-hydroxymethyl phosphine oxide (TrHPO). At pH 9.0, THPC will be converted com-
pletely to TrHP and most TrHP is further oxidized into TrHPO. It is possible that, in reaction of phosphorous com-
pounds and collagens, both P C and C O bonds would break simultaneously or individually. From molecular
charge distribution and bond polar properties, it is deduced that, if P C bonds break, the activity is in order of
TrHPO＞THPC＞TrHP, whereas if C O bonds break, the order is TrHP＞THPC＞TrHPO. It is more possible that
P C bonds will break in reaction with collagen, and TrHPO may be more active in the THPC tanning system. The
results of tanning and DSC also prove the above conclusion. Furthermore, the fact that the shrinkage temperature of
THPC tanned leather was below 70°C when basified to pH 5.0 or lower suggests that the hydroxymethyl groups of
THPC and TrHP are less possible to combine directly with amino groups of collagen.
Keywords tetra-hydroxymethyl phosphonium chloride, chrome-free tannage, green chemicals, charge distribution,
tanning mechanism

1 INTRODUCTION rimetry (DSC) and the Wang-Ford charge distribution

based on extended Hückel theory [7, 8] have been ap-
With the increasing concerns on environment and plied to study these issues. The results obtained from
human health, the traditional chrome tannage is facing this study are hopeful to improve the wide application
tremendous challenge [1, 2]. In order to overcome the of THPC and other tanning agents based on THPC in
shortage of chromium resources and pollution of green tanning processes [9].
chromium salts, increasing attentions are paid to the
chrome-free tanning chemicals [3]. Tetra-hydroxymethyl 2 EXPERIMENTAL
phosphonium salt (THP salt) is an important one of
them, which has been mainly used as textile flame 2.1 Materials and instruments
retardant for a long time [4], and as biocides winning Main materials and instruments used in the ex-
the Designing Safer Chemicals Award in the Presiden- periments are listed in Table 1.
tial Green Chemistry Challenge Awards Program of
EPA in 1997. Although there are some leather tanning Table 1 Main materials and instruments used in
chemicals containing tetra-hydroxymethyl phospho- experiments
nium chloride (THPC), such as Clariant’s FCC and Main material Supplier
TFL’s Sellatan PFD liquor, the shrinkage temperature
pickled sheep skin Ningbo Feifan Leather Co., China
(Ts) of leather tanned solely by the sample (pH 4.0,
THPC sample (pH 4.0, purity of Zhejiang Zengxin Chemistry Co.,
THPC content being 71.98%) remains around 80°C. It 71.98%) China
is the fact that THPC can link mostly with amino
groups and less with hydroxyl and carboxyl groups and acetylacetone (purity of 99.50%) Shanghai Reagent Co., China
peptide bonds of collagen in leather, but the tanning FTIR 8000 Shimadzu, Japan
mechanism of THPC is still unknown [5]. It is reported DSC 200/1/H PHOXC520L Netzsch, Germany
that THPC would be converted into tri-hydroxymethyl
AVANCE 300 Bruker, Germany
phosphonium (TrHP) and tri-hydroxymethyl phosphine
oxide (TrHPO) during the tanning process [6].
The questions are open to answer: what are the
effective crosslinking agents when pelt is tanned with 2.2 Preparation of THPC samples with different pH
the sample? How does the tanning proceed? And, how
is the molecular charge distributed when THPC is THPC samples were neutralized by sodium car-
converted into TrHP or TrHPO during tanning? In this bonate fines to pH 6.0 and pH 9.0, respectively, for
article, 31P NMR, FT-IR, differential scanning calo- later use.

Received 2007-09-22, accepted 2008-01-23.

* Supported by the National Basic Research Program (2007CB616909), Startup Foundation of Applied Chemistry of the Key
Discipline of Zhejiang University of Technology and Zhejiang Provincial Science and Technology Plan (2006C21107).
** To whom correspondence should be addressed. E-mail: nbssx@126.com
 Chin. J. Chem. Eng., Vol. 16, No. 3, June 2008 447

2.3 Leather tanning and shrinkage temperature

determination

Pickled sheep skin was used in the tanning ex-

periment. Firstly 8 pieces of pickled skin were de-
pickled to pH 2.5, tanned with 8% (percentage based
on pickled skin mass) THPC sample (pH 4.0, purity of
71.98%), for 3 h and then basified to pH 3.5, 4.0, 4.5,
5.0, 5.5, 6.0, 6.5, 7.0 by sodium bicarbonate fines,
respectively. Finally, the tanning drum was run for 1 h Figure 1 Influence of basifying pH on Ts
and Ts of each tanned leathers was determined by the
Ts testing instrument. Meanwhile, another pickled
sheep skin was also tanned with 8% THPC sample of up to 6.0. Ts reaches the peak at 83°C at the basifying
pH 6.0 (percentage based on pickled skin mass), then pH 6.0. Then it drops slowly as pH＞6.0.
basified to pH 6.0 and its Ts was tested.
3.2 Free formaldehyde and THPC content
2.4 THPC and free formaldehyde content analysis
The reaction,
The iodimetric method was employed to deter- ZZX P(CH 2 OH)3 + HCHO + HCl (1)
P(CH 2 OH)4 Cl YZZ
mine the THPC content in the samples at pH 4.0 and
pH 6.0 [10, 11]. The acetylacetone method was adopted may take place in THPC tanning process to release
to determine the free formaldehyde content in the free formaldehyde [14]. The free formaldehyde content
of the sample increased from 27.49 mg·L 1 to 232.96
－
samples at pH 4.0 and pH 6.0 [12].
－1
mg·L with the pH changing from 4.0 to 6.0. Mean-
2.5 Chain structure and group changes determi- while the THPC content decreased from 71.95% to
nation of THPC 68.72%. Theoretically, the reduction of 3.23% THPC
content should give about 6690 mg·L 1 of free for-
－

31 maldehyde which is much higher than determined

P NMR was employed to describe the different 205.47 mg·L 1. This indicates that the formaldehyde
－

structure of phosphorous compounds of the samples at did not exist in the form of free formaldehyde. Fur-
pH 4.0, 6.0 and 9.0. H3PO4 was used as the internal thermore, the free formaldehyde tends to react with
standard. FT-IR was used to determine the changes of amino groups of collagen easily due to its high reac-
functional groups of phosphorous compounds in the tivity, which will result hydroxymethylation of amino
samples at pH 4.0 and pH 6.0. groups and may promote the THPC tanning ability.

2.6 Analysis of structure and charge distribution 3.3 FT-IR analysis of the sample at different pH

Chemical software of Cambridge was used to Figure 2 is the FT-IR spectra of the samples at pH
predict the tanning properties of phosphorous com- 4.0 and pH 6.0. Comparing the two curves, we can find
pounds. The chemical formula was input and then it that there is no obvious change of functional groups in
was converted into Chem3D to give the the samples at pH 4.0 and 6.0. The higher Ts at pH 6.0
three-dimensional structure. Then, the MM2-minimize may due to the higher content of TrHP or TrHPO, but
energy was used to get the stable 3D structure. The not to the change of functional groups after basifying.
Wang-Ford charge distribution was calculated ac-
cordingly [13]. 31
3.4 P NMR analysis of the sample at different pH
2.7 DSC analysis
Figure 3 (a) shows that the sample at pH 4.0
mainly contains 3 phosphorous compounds. As can be
The hide powders were soaked in the THPC sam- seen from Fig. 3 (b), the component TrHP increased
ples of pH 4.0, 6.0 and 9.0 for 24 h respectively. Then after basifying to pH 6.0. In Fig. 3 (c), THPC decom-
the three pieces of treated powder were separated from posed completely and converted to TrHPO. In the
THPC sample and tested by DSC. The heating rate is whole basifying process, the content of THPC de-
3°C·min 1 and the range of temperature rise is
－
creased meanwhile the content of TrHP and TrHPO
30°C-100°C. increased (see also Table 2). Hence, the main reactions
(R1)-(R3) may take place when basifying the pH to
3 RESULTS AND DISCUSSION 6.0 in the tanning process, in which THPC is con-
verted into TrHP, TrHPO and tri-hydroxymethyl
3.1 Influence of basifying pH on Ts phosphine hydroxide (TrHPOH):
TrHP + OH − YZZ
ZZX TrHPOH (2)
Figure 1 shows that there is a dramatic increase
[O]
in Ts of tanned sheep skin with the basifying pH rising TrHP ⎯⎯→ TrHPO (3)
448 Chin. J. Chem. Eng., Vol. 16, No. 3, June 2008

Figure 2 FT-IR spectra of THPC at pH 4.0 and pH 6.0

Table 2 Results of 31P NMR analysis

Relative content/%
(based on mole of total
Phosphorous
δ phosphonium)
compound
THPC THPC THPC
(pH 4.0) (pH 6.0) (pH 9.0)
49.5 TrHPO 1.28% 2.92% 86.23%
26.5-27.2 THPC, 94.55% 70.25% 0.00%
+ －
P ( CH2OH)3CH2O ,
(a) Sample of pH4.0
P+(CH2OH)2(CH2O )2,
－

P+(CH2OH)(CH2O )3
－

－23.8 TrHP 4.17% 25.47% 10.34%

－27.9 TrHPOH 0.00% 1.36% 3.43%

are listed in Table 3. THPC molecules are tetrahedral

with P in center and TrHP forms a standard pyramidal
cone with P atoms in corners. TrHPO is also the stan-
dard pyramidal cone, but with the O atoms in peaks.
(b) Sample of pH6.0 In the molecule of THPC, TrHP and TrHPO, the
charge of phosphorous are +1.621, +0.542 and +1.704,
respectively. C and O in each phosphorous compounds
are negative charged, forming a number of P C
bonds and C O bonds.

3.6 Analysis of activity of phosphorous com-

pounds

The activity of phosphorous compounds relates

closely to the asymmetric properties of their mole-
(c) Sample of pH9.0 cules, their structure and bond breaking process in
Figure 3 31
P NMR spectra of THPC at pH4.0, pH6.0 reaction, etc. In the THPC tanning system, P C or
and pH9.0 C O bonds may break in reaction between phospho-
rous compounds and collagens. The more asymmetric
the charge distribution is, the more polar the bond and
3.5 Analysis of structure and charge distribution the more possible its breaking. The comparisons of the
charge of P, C, O in P C and C O bonds of phos-
The structure and charge distribution of each phorous compounds are listed in Table 4. It is obvious
phosphorous compound in the THPC tanning system that the asymmetric charge distribution in P C bond
 Chin. J. Chem. Eng., Vol. 16, No. 3, June 2008 449

Table 3 Analyses using chemical software

Phosphorous compound 3D structure Charge distributions

(1)P 1.621, (2)C － 0.039, (3)C － 0.044, (4)C － 0.046, (5)O

－0.379, (6)O －0.363, (7)O －0.363, (8)C －0.044, (9)O －0.358,
P+(CH2OH)4 (10)H 0.028, (11)H 0.033, (12)H 0.028, (13)H 0.028, (14)H 0.028,
(15)H 0.027, (16)H 0.201, (17)H 0.196, (18)H 0.196, (19)H 0.027,
(20)H 0.028, (21)H 0.196

(1)P 0.452, (2)C －0.011, (3)C －0.011, (4)C －0.011, (5)O －0.378,
(6)O －0.378, (7)O －0.378, (8)H 0.021, (9)H 0.021, (10)H 0.021,
TrHP (11)H 0.021, (12)H 0.021, (13)H 0.021, (14)H 0.196, (15)H 0.196,
(16)H 0.196

(1)P 1.704, (2)C － 0.071, (3)C － 0.071, (4)C － 0.071, (5)O －

0.363, (6)O －0.363, (7)O －0.364, (8)O －1.155, (9)H 0.028, (10)H
TrHPO 0.027, (11)H 0.028, (12)H 0.027, (13)H 0.028, (14)H 0.027, (15)H
0.195, (16)H 0.196, (17) H 0.196

Table 4 Charge distribution of P C bond and C O bond TrHP in the sample at pH 6.0 is higher than that in the
Phosphorous Charge of P in Charge of O in sample at pH 4.0 as shown in Table 2. However, the
Charge of C fact that Ts of leather tanned by the sample of pH 6.0
compound P C bond C O bond
THPC 1.621 －0.044 －0.363
is not higher than that with the sample of pH 4.0 im-
plies that TrHP is not the effective tanning agent. The
TrHP 0.452 －0.011 －0.378 charge distribution of TrHP also reveals it is a stable
TrHPO 1.704 －0.071 －0.363 phosphorous compound with lower reactivity.
The 31P NMR analysis (see Fig. 3 and Table 2)
indicates that THPC is the chief component of the
is in the order of TrHPO＞THPC＞TrHP, and that of sample (at pH 4.0). However, according to Fig. 1,
C O bond is in the order of TrHP＞THPC＞TrHPO. when tanning with the sample (at pH 4.0) and basi-
Therefore, if P C bond breaks in reaction, the activity fying to pH 5.0 or lower pH, the obtained Ts is below
of phosphorous compounds follows the order of 70°C. So THPC is not the efficient tanning agent as
TrHPO＞THPC＞TrHP; if C O bond breaks and the well. Whereas, the experimental results show clearly
hydroxymethyl groups will be removed, the order may that TrHPO is the efficient tanning agent, in accor-
become TrHP＞THPC＞TrHPO. dance to Klaus et al [16].
All the three main types of phosphorous com-
pound play roles in tanning process. The tanning
3.7 DSC analysis
mechanism can be simply considered as three major
steps. Firstly, the decomposition of THPC takes place
Results of DSC are listed Table 5. From Tables 2 as described by reaction (1). When basifying to pH 6.0,
and 5, it can be found that the content of TrHPO in the the equilibrium moves far to the left, which produces
THPC (pH 9.0) sample was higher than the others, excess of formaldehyde and TrHP in the tanning solu-
and the denaturalization temperature (Td) of treated tion. Meanwhile, the nucleophilic substitution between
hide powder was also higher. The fact that Td of hide formaldehyde and amino groups of collagen takes place.
powder treated with THPC (pH 4.0) and THPC (pH Secondly, TrHP is oxidized into TrHPO at higher pH
6.0) are lower indicates that the activity order of which is supported by Fig. 3 and Table 2. Finally, the
phosphorous compounds is TrHPO ＞ THPC ＞ TrHP, hydroxylmethylated amino groups of collagen com-
which supports the above conclusion. bine with highly reactive phosphorus in TrHPO. The
hydroxylmethyl groups of TrHPO combined with col-
Table 5 Td of hide power treated with different lagens dissociate continuously and nucleophilic reac-
THPC samples
tion between formaldehyde and amino groups of col-
THPC sample Td/°C lagen take place, too. Therefore, combination between
pH 4.0 69.3 hydroxylmethylated amino groups and phosphorus
pH 6.0 63.8 results in a large number of cross-links in collagen fi-
pH 9.0 77.8
bers and accomplishes the tanning process. The proc-
ess can be expressed by reactions (4), (5), (6) and (7):
(4)
3.8 Deduction of the tanning mechanism

It is reported that TrHP is an effective main tan-

ning agent [15]. In our study, the pickled pelt has been (5)
tanned with the samples of pH 4.0 and pH 6.0, its Ts
were 83.3°C and 82.6°C respectively. The content of
450 Chin. J. Chem. Eng., Vol. 16, No. 3, June 2008

354-359 (2005).
2 Nishad Fathima, N., Chandrabose, M., Avarindhan, R., Raghava Rao,
(6) J., Unni Nair, B., “Iron-phosphonium combination tanning: Towards
a win-win approach”, J. Am. Leather. Chem. Assoc., 100, 273-281
(2005).
3 Nishad Fathima, N., Prem Kumar, T., Ravi Kumar, D., Raghava Rao,
J., Unni Nair, B., “Wet white leather processing: A new combination
tanning system”, J. Am. Leather. Chem. Assoc., 101, 58-65 (2006).
4 Donaldson, D.J., Normand, F.L., Drake G.L., Reeves, W.A., “A du-
(7) rable flame retardant finish for cotton based on thpc and urea”, J. Ind.
Text., 3, 250-256 (1974).
5 Li, Y., Shan, Z.H., Shao, S.X., Shi, K.Q., “Reaction mechanism of
where the symbol stands for collagen chains. tereakis hydroxymethyl phosphonium with collagen protein”, J. Soc.
Leath. Tech. Chem., 5, 214-216 (2006).
6 Shi, K.Q., Jiang, L., Li, Y., Shan, Z.H., Shao, S.X., “Study on tan-
4 CONCLUSIONS ning action of THPC”, Chin. Leath., 9, 9-10 (2006). (in Chinese)
7 Wang, B.Z., Ford, G.P., “Atomic charges derived from a fast and ac-
curate method for electrostatic potentials based on modified AM1
When basifying pH to 6.0 in the THPC tanning calculations”, J. Comput. Chem., 15, 200-207 (1994).
process, the decomposition of THPC takes place, 8 Hoffmann, R., “An extended Hückel theory. I. Hydrocarbons”, J.
Chem. Phys., 39, 1397-1412 (1963).
which results in production of free formaldehyde and
9 Han, Y., Shao, S.X., Yan, Q., Cao, H.Y., “Application and develop-
TrHP, and part of TrHP would be oxidized into ment of green chemistry in leather industry”, J. Ningbo Uni. Tech. 4,
tri-hydroxymethyl phosphine oxide (TrHPO). In the 1-6 (2007). (in Chinese)
THPC tanning system, the activity of phosphorous 10 Shi, K.Q., Li, Y., Shan, Z.H., Shao, S.X., “Methods in THPC content
compounds is likely in order of TrHPO＞THPC＞ determination”, Leather Sci. Eng., 3, 16-19 (2005). (in Chinese)
TrHP. THPC, TrHPO, TrHP and HCHO play their re- 11 Frank, A.W., “The iodometric determination of P(III) in flame retar-
dants for cotton Part IV: Reaction of THPC with iodate”, Textile Res.
spective roles during tanning. The decomposition of J., 47, 60-61(1977).
THPC yields TrHP, and TrHP is easily oxidized into 12 Isai, S.V., Vas’kovskii, V.E., “Methods for the quantitative determi-
TrHPO, which is the most reactive phosphorous com- nation of formaldehyde and their use in the analysis of natural com-
pound in the THPC tanning system. The formaldehyde, pounds”, Chem. Natural Compounds, 9, 439-451 (1975).
however, could be considered as an accelerator in the 13 Connolly, M.L., “Computation of molecular volume”, J. Am. Chem.
Soc., 107, 1118-1124 (1985).
whole tanning process. 14 Albrecht, G., “Kinetic study of the reaction of Tetrakis (hydroxy-
methyl) phosphonium cation with urea”, J. Am. Chem. Soc. 99,
REFERENCES 2648-2652 (1977).
15 Collins, G.R., Jones, C.R., Talbot, R.E., Williams, J., Zakikhani, M.,
“Tanning leather”, U.S. Pat., 6540790 (2003).
1 Chandra Babu, N.K., Venba, R., Jothi, G., Ramanaiah, B., Radha, G., 16 Klaus, S., Frank, A., Artur, H., Peter, P., “Leder und dessen Herstel-
Asma, K., Rose Kumari, I., “Elimination of hexavalent chromium in lung”, E.P. Pat., 0808908 (1997).
leather using reducing agents”, J. Am. Leather. Chem. Assoc., 100,