Pelli

Tanning chemistry
1. Collagen and skin structure

2. Skin and its components
3. Curing and preservation of hides
4. Soaking
5. Unhairing
6. Liming
7. Deliming
8. Bating
9. Pickling
10. Tanning
11. Vegetable tanning
12. Other tannages
1
Tanning chemistry
13. Miscellaneous tannages
14. Fungicides
15. Post tanning
16. Some definitions
17. Some pictures
1
Collagen and skin

structure
• Coded at position A 64 of human genome

• 28+ different types of collagen.
• Major component is Type I collagen
• Hydroxyproline is almost exclusive
• No Tryptophan
2

HIERARCHYCAL STRUCTURE OF COLLAGEN
AA sequence: -(Gly-X-Y)n-
In particular:
Gly-Pro-Y + Gly-X-Hyp ≈ 44%
Gly-Pro-Hyp ≈ 12%
Pro+Hyp = 44/3+12x2/3 ≈ 23% (13% Pro, 10% Hyp)
TRIPLE HELIX = 2 x α(1) + 1 x α(2)

6
3
3 LEFT HANDED
helices form a
RIGHT HANDED
SUPER HELIX.
4
• Helical structure ends with non-helical
telopeptides
• Telopeptides are partly responsible for
intermolecular cross-linking
• 5 “rows” of molecules with staggered stacking
leads to:
– Gap region with 4 stacking molecules (space for
stain, dark region)
– Overlap region with 5 stacking molecules
– A periodic structure occurs (D-period)
• Collagen fibrils combine into collagen fibers
9
10
5
11
12
6
13
Hyp is the major responsible for collagen stability
Source Pr/Hyp residues per 1000 Shrinkage temperature (°C)

Calf 232 65
Carp 197 54
Cod 155 40
14
7
Role of water on the stability
Water content Freezing point Desorption Structural function

(g/g) (K) energy (J/mol)
0.00-0.07 Not freezable 71 Bound by two H-bonds
0.07-0.25 <180 50 Bound by one H-bond
0.25-0.50 265 38 Bound to side chains and
peptide links
0.50-2.0 273 Mechanically Interstitial
removable
! Properties change upon drying

15

Hyp contributes with 98 J/K mol to the entropy
of bound water Freezing of 4
H2O/Hyp
An alternative/concurrent explanation is
Inductive Effect
Peptide Unfolding transition (°C)
(Gly-Pro-Pro)10 41
(Gly –Hyp-Pro)10 69
(Gly-Flp-Pro)10 91
Flp = 4-(R)-Fluoroproline
16
8
Skin and its components
17
18
9
Main structural components are:
Collagen (triple helix)
Elastin (double helix)
AA type Elastin Collagen

Gly 355 330
Apolar 431 170
Acidic 14 120
Basic 10 96
Hydroxy 20 57
Pro 125 126
Hyp 23 93
19

Non-structural components
Glycosaminoglycans (GAGs) = disaccharides
made up by an amino sugar + uronic sugar
• Hyaluronic acid (HA)
• Dermatan sulfate (chondroitin sulfate B)
• Chondroitin sulfate A and C (minor
components)
Melanin
20
10
Hyaluronic acid (HA)
21

Dermatan sulfate (chondroitin sulfate B):
associated with a protein core that sticks to the
collagen fiber backbone = Proteoglycan
22
11
Chondroitin sulfate C
23
Curing and preservation

of hides
24
12
Conditions favoring putrefaction
• pH 6-10
• Moisture content > 25%
• Temperature > 20°C
• Ca2+/Mg2+ ! halophilic bacteria growth
25

Preservation methods
Technique Hides processed in the district

of Arzignano
Wet salting 60 %
Refrigeration (short term) 38 %
Brining <2%
Dry salting 0%
26
13
Wet salting
About 40 % of NaCl is added to the flayed hides.
Fate of salt for 1 ton of hides
35 60 Leachate during curing
Falling during transportation
55
40 Falling during handling
De-salting
15 1st soak
130 65 2nd soak
Carried over
27

Preservation methods
28
14
29
30
15
31
32
16
33
Mechanical de-salting
34
17
BEAMHOUSE
The BEAMHOUSE process prepares the hides for

tanning by the:
1) Removal of non-collagenous components (HA

and other GAGs, non structural proteins, fats,
hair, etc.)
2) Splitting up the fiber structure to the level of
fibril bundles
35
BEAMHOUSE
Typical beamhouse process for bovine hides

Step Chemicals Water % pH Time (h)
Dirt soak H2O 150-200 7 1-2
Main soak H2O + Na2CO3/NaHS 150 8-9 4-8
Unhairing/liming Na2S, Ca(OH)2 120+ 12-13 18-24
Rinsing H2O 150 12-13 1
Deliming (NH4)2SO4 100 8-9 1-2
Bating Proteol. enzyme 100 8-9 1-2
Rinsing H2O 100 8-9 1-2
Pickling H2SO4, HCOOH 50+ 2-3 2-6
36
18
BEAMHOUSE
The reactor of choice is the DRUM
37
BEAMHOUSE
38
19
BEAMHOUSE
39
BEAMHOUSE
40
20
BEAMHOUSE
Mechanical action in the drum

ωB·dB ≈ k
(ωB = angular speed; dB = diameter).
For dB >> dC the
optimum speed is:
dB 0.424 / / 10 +,
ω" = 2
ωC (" -ℎ
ωB
dC
MC
ω0 / (0 = ω1 / (1 ≈ 47 − 55
41
4. Soaking
Soaking
42
21
4. Soaking
Soaking has the aim of
• Cleaning and rehydrating the pelt

• Removing salt
• Removing non-structural proteins
• Removing dung (with lignocellulosic enzymes)
• Removing hyaluronic acid
43
4. Soaking
Sebaceous grease
Component Sheep Bovine Human
Squalene 0 15
Sterols 12 1
Sterol esters 46 2
Wax esters 10 11 25
Triacyl esters 0 53 41
Phospholipids 21
Free acids 0 10 16
Free alcohols 11 0
44
22
4. Soaking
Mass exchange is regulated by transportation

phenomena between heterogeneous phases.
!Chemistry of emulsions
45
4. Soaking
Anionic surfactants
sodium laureth sulfate
sodium lauryl sulfate
dodecylbenzene sulfonate
46
23
4. Soaking
Cationic surfactants
Esterquath
47
4. Soaking
Amphoteric (Zwitterionic) surfactants
Cocamidopropyl betaine
48
24
4. Soaking
Non ionic detergents
Ethoxylathed fatty alcohols
CnH2n+1(CH2CH2O) mH
49
4. Soaking
Hydrophilic - Lipophilic Balance (HLB)
HLB = 20 x Mh/M
Example: lauryl ether sulfate 2M (n=2)

CH3(CH2)11(OCH2CH2)2OSO3- ; M = 353.5 g/mol,
Mh = 184.2 g/mol
HLB = 20 x 184.2/353.5 = 10.4
50
25
4. Soaking
HLB RANGES AND APPLICATIONS
HLB Range Water solubility Application

1-4 Insoluble Antifoam
3-6 Poorly soluble Emulsifier W/O
6-8 Unstable milky dispersion Wetting agent
8-10 Stable milky dispersion Wetting agent,
Emulsifier O/W
10-13 Transparent dispersion Emulsifier O/W
>13 Solution Emulsifier O/W,
solubilizer
51
4. Soaking
52
26
4. Soaking
Measure of HLB:
cloud point
Solution of 5 %
fat in water
53
5. Unhairing
Unhairing
54
27
5. Unhairing
55
5. Unhairing
Protein Total nitrogen Total sulfur
Collagen 17.8 % 0.2 %
Elastin 16.8 % 0.3 %
Keratin 16.5 % 3.9 %
+ Ox
Red
Cystine content of hair: 60 mmol/100g
56
28
5. Unhairing
HAIR BURNING
1) Sulfide reaches the bulb and dissolves
prekeratinised areas.
2) Reductants act on softer keratins (cortex,
epidermis). Melanin affects the dissolution
rate.
3) Cuticle and medulla are not reduced but
hydrolyzed
57
5. Unhairing
58
29
5. Unhairing
Semi-reaction Redox potential EO (mV)

H2S ⇔ S + 2H+ + 2e- -0.142
HS- + OH- ⇔ S + H2O + 2e- +0.478
S22- ⇔ 2S + 2e- +0.428
S2- ⇔S +2e- +0.476
59
5. Unhairing
60
30
5. Unhairing
Only S2- is eﬀecUve for unhairing → pH ≥ 12

Ca(OH)2 buffers the solution due its limited
solubility (1.7 g/l @20°C):
Ca(OH)2 (s) Ca(OH)2 (aq) Ca2+ + 2OH-
14-log[OH-]= 14-log(2*1.7/ Ca(OH)2)= 12,7
At such pH values the hides swell.

61
5. Unhairing
Hair amounts to ca. 10% of hide weight. Since Cys

content is 0.60 mol/kg of hair the stoichiometric
consumption of sulfide is:
0,60 x Na2S (78,04 g/mol)/purity (70%) ≈ 67 g
0,07 kg/kg x 10 % = 0,7 % on hide weight
For kinetic reasons the rate is around 2-3% wt.
62
31
5. Unhairing
Unhairing reductive agents
Name Formula E0 (mV) @pH 12

Thiourea dioxide (sulfinic acid) (H2N)(NH)C-S(O)OH 610
Sodium sulfide Na2S 550
Thioglycolic acid HS-CH2-CO2H 410
Cysteine NH2-CH-(CH2SH)-CO2H 400
Sodium dithionite Na2S2O4 220
63
5. Unhairing
Immunization of hair
At pH ≥ 11 the OH- ion can attack the methylene
group at the disulfide bond of cystine,
originating Cys and Ser.
This latter loses water and forms
dehydroalanine, that reacts with Cys giving rise
to a stable tioether link →
The hair becomes resistant to chemical burning
64
32
5. Unhairing
This reaction is exploited in hair saving processes

65
5. Unhairing
Oxidative unhairing
Sodium chlorite (Imprapell CO - Hoechst) is used to
produce ClO2 in situ, that oxidizes cystine’s sulfur
bridge:
4ClO2- +2H+ 2ClO2 + ClO3- + Cl- + H2O
4 R-S-S-R + 10 ClO2 + 4 H2O 8 RSO3-+ 8 H+ + 5 Cl2
66
33
5. Unhairing
Oxidative unhairing
Modern processes make use of hydrogen

peroxide in alkaline environment (NaOH).
Temperature control is mandatory due to the
risk of grain damages due to over oxidation.
67
5. Unhairing
Since sulfide degradates some organo-sulfur
based biocides, Imprapell CO is also used to
effectively eliminate excess sulfide:
8 ClO2 + 5 S2- + 4 H2O 8 Cl- + 5 SO42- + 8 H+
68
34
6. Liming
Liming
69
6. Liming
A – No salt
B- 2M NaCl
70
35
6. Liming
Hydrolytic action on non-structural proteins
(albumins, globulins).
Opening up of the fibre bundles.
Not opened up Opened up
71
6. Liming
72
36
6. Liming
Mechanisms of alkaline swelling:
A) Charge effect
—CO2-··· H3N+— —CO2- + H2N—

Neutral Anionic
73
6. Liming
B) Lyotropic effect of
cations
>C=Oδ-···δ+H—N< + Ca2+ >C=Oδ-···Ca2+ ↔δ+H—N<
anions
>C=Oδ-···δ+H—N< + Cl- >C=Oδ- ↔ Cl- ···δ+H—N<
and neutral molecules:

>C=Oδ-···δ+H—OC=Oδ-···δ+H—N<
R
74
37
6. Liming
The magnitude of the peptizing effect is
proportional to the polarizability of the ion
Salting out of negatively charged proteins Salting in
Most stabilizing for protein structure Most destabilizing
Strongly hydrated anions Weakly hydrated anions
Citrate 3- > SO42- > Ac- > Cl-> Br- > I- > NO3- > ClO4-
NH4+ > K+ > Na+> Li+ > Mg2+ > Ca2+ > Mg2+ > Al3+
Weakly hydrated cations Strongly hydrated cations
(Hofmeister series)
Basing on the series it results that:
Na2SO4 < NaCl < CaCl2
PEPTIZING POWER 75
6. Liming
Hydrolysis of amide sidechains:
Asn → Asp
Gln → Glu
76
38
6. Liming
And, with a different mechanism:
Arg
Prt-(CH2)3-NH-C(=NH)-NH2 + H2O
Prt-(CH2)3-NH-C(=O)-NH2 (citrulline)
Prt-(CH2)3-NH2 (ornithine)
77
6. Liming
IEP shifts from 7.4 to 5-6

78
39
6. Liming
Shop floor
79
6. Liming
Fat released by
hides inside the
liming drum
80
40
6. Liming
Grain layer
partially
damaged by
microorganisms
81
6. Liming
Web-like
pattern due
to
insufficient
fiber
opening
82
41
7. Deliming
Deliming
83
7. Deliming
The purpose of deliming is:
1) Lower pH from 12.6 to 8-9

2) Removal of lime
3) Deplete pelt from excess water (unswelling)
84
42
7. Deliming
85
7. Deliming
Deliming agents
A) Weak organic acids

Lactic acid can be safely used
Formic, acetic, phthalic, glycolic and other

dicarboxylic acids are found in deliming
formulations.
86
43
7. Deliming
B) Acidic salts
The most used is ammonium sulfate. Buffering
effect of NH4+ (pKa = 9.25)
NH4+ NH3 + H+
pH = pKa – log([NH4+]/[NH3])
long float: dissolution (2 g/L)
Risk of CaSO4 medium float: precipitation
short float: Ca[(NH3)2]2+
87
7. Deliming
NH4Cl may be used, beware of lyotropic Cl-
Metabisulfite (Na2S2O5) is often part of deliming

formulations:
S2O52- SO32- + SO2
2HS- + HSO3- 3S + 3OH-
88
44
8. Bating
Bating
89
8. Bating
Bating is an enzymatic process aimed at the
removal of unstructured proteins.
Traditional sources of enzymes were:

• Bird guano (mastering)
• Dog dung (puering)
• Bran drenching
Beginning of XX century: industrial enzymes

(Oropon, pancreatic formulation by Otto Röhm –
Rohm&Haas – Dow/Evonik)
90
45
8. Bating
k1 k2
E+S ES E+P
k-1
E = Enzyme; S = Substrate; P = Product
(7
− = 90 : 7 − 9;0 :7
(8
([:7]
= 90 : 7 − 9;0 :7 − 91 [:7]
(8
91
8. Bating
>?
At the steady state: =0
>!
90 : 7
:7 =
9;0 + 91
Since [E]0=[E] + [ES] ! [E]= [E]0 - [ES]
90 [:]# 7
:7 =
9;0 + 91 + 90 [7]
92
46
8. Bating
90 [:]# [7]
:7 =
9;0 + 91 + 90 [7]
([$] 91 90 [:]# 7
= 91 [:7] =
(8 9;0 + 91 + 90 [7]
Combination of rate constants into Km:

9;0 + 91
%& =
90
93
8. Bating
Michaelis-Menten equation
(7 ($ 91 [:]# 7
'=− = =
(8 (8 %& + [7]
'&() = 91 [:]#
'&() [7]
'=
%& + [7]
94
47
8. Bating
Practical measurement of Km
95
8. Bating
Effect of the temperature
96
48
8. Bating
Effect of pH
97
8. Bating
Reaction mechanisms of selected enzymes

Enzyme Site of attack
Trypsine Pancreatic protease. Highly specific. Carbonyl side of Lys
and Arg. Only on telopeptide regions.
Chymotrypsine Carbonyl side of aromatic sidechains (Phe, Tyr). pH 7-9
Nagarase, subtilisin From Bacillus subtilis. Non-specific, prefer small
polypeptides.
Papainase Sulfhydryl protease from papaya.
Leucine Active on Leu at N-terminus
aminopeptidase
Prolidase From pig kidney, acts on Pro and Hyp
Pronase From Streptomyces griseus, very broad activity range
98
49
8. Bating
Nowadays pancreatic enzymes are hardly

available and bacterial bates are prevalent.
These latter contain also elastolytic enzymes ->
active on elastin.
99
8. Bating
Monitoring of bating
1) Thumbprint
2) Air bubble
3) Biuret test: a drop of concentrated CuSO4 +
one drop of NaOH -> purple color
100
50
8. Bating
101
9. Pickling
Pickling
102
51
9. Pickling
Pickling is an acidic treatment that adjusts the

reactivity of collagen and prepares it for the
tanning reaction.
Acid hydrolysis is slower than alkaline, unless it

is used as preservative action or as an
alternative to the alkaline opening up of
woolskins.
103
9. Pickling
100.0%
Collagen
90.0% Asp/Glu
80.0%
70.0%
60.0%
50.0%
40.0% CATIONIC ANIONIC

REGION (+) REGION (-)
30.0%
20.0%
10.0%
0.0%
1.5 2.5 3.5 4.5 5.5 6.5 pH
IEP
104
52
9. Pickling
Acid swelling is unwanted: addition of min 1 M

NaCl (6%). (Beware of the water that is carried
over and released by the pelt.)
OSMOTIC LYOTROPIC
105
9. Pickling
Widely used acid species for pickling are:

H2SO4 (1:20 before addition)
HCOOH (1:10 before addition)
Non swelling acids:
106
53
9. Pickling
107
9. Pickling
Check of acid penetration with bromochresol

green (BCG):
pH ≥ 5,4 ?
pH ≤ 3,8 YELLOW
108
54
9. Pickling

green (BCG):
pH ≥ 5,4 BLUE
pH ≤ 3,8 YELLOW
109
9. Pickling

green (BCG):
110
55
10. Tanning
Tanning
111
10. Tanning
Tanning coverts the raw pelt into a stable

material that resists putrefaction by spoilage
bacteria.
Most tannings also imply an increase of Ts,
although ΔTs= 0 for
Material Effect of water
Solvent dried pelt Reverts to raw
Aluminum tawed Al(III) is washed out
Oil tanned None
112
56
10. Tanning
Hydrothermal stability
Ts corresponds to the breaking of the hydrogen
bonds in the triple helices
Triple helix → random coil
Ts is measured with ISO 3380. Since T x R = k
(R=rate of heating), R is fixed at 2 °C/min.
Boil test is typically used for leather tanned with
chromium (Ts > 100 °C)
113
10. Tanning
Hydrothermal stability
114
57
10. Tanning
A phase transition takes place at Ts that can be

detected with a DSC measurement.
115
10. Tanning
800 Thermodynamics of collagen shrinking @60°C

700
ΔHǂ
600
TΔSǂ
500 ΔGǂ
KJ/mol
400
300
200
100
0
0 2 4 6 8 10 12 14
pH
116
58
10. Tanning
Chemical agents used for tanning

Cr salts
Al, Zr, Ti, Fe salts
Vegetable tannins
Synthetic tannins
Melaminic resins
Dicyandiamidic resins
Urea-formaldehyde resins
Acrylic resins
117
Vegetable tanning
118
59
Plant extracts are used since ancient times to

convert skin into leather.
The reactive species are of polyphenolic nature;
although it seems that they preferably interact
with the gap region, it is considered that the
reaction takes place throughout the whole
collagen structure.
Ar-OH···O=C<
119
Vegetable tannins are divided in two major

classes:
1) Hydrolysable (or pyrogallol) tannins.
They are based on glucose (or sucrose) gallates:
120
60
Hydrolysable tannins are divided in

a) Gallotannins
Glucose is esterified with gallic acid; the gallate
groups can be esterified themselves (depside
esterification)
121
b) Ellagitannins
In addition to gallic acid, esterification of
saccharides takes place with ellagic and chebulic
acids
122
61
Hugo Schiff
123
Castalagin:
an hydrolizable tannin
of ellagic acid found in
oak and chestnut
wood
124
62
Caesalpinia spinosa: TARA
125
2) Condensed (or catechol) tannins are flavonoid

ring structures where the B ring is often a
catechol group
B
7
A C
5
Flavan structure
126
63
Schematic
representation of
a condensed
tannin molecule.
Condensed
tannins can be
linear (with 4→8
bounds) or
branched (with
4→6 bounds -
dotted line)
127
(epi)catechin ! procyanidines
(epi)afzelechin ! propelargonidines
(epi)gallocatechin ! prodelfinidines
128
64
Florotannins
Found in algae (Eklonia cava).
8 or more condensed rings
DIECKOL
129
Plant Source Class T Cont (%) NT Cont (%)

Chestnut Wood Hydrolysable 5 – 15 1–2
Myrobalan (Terminalia chebula) Nuts Hydrolysable 25 – 48 14 – 17
Sumac Leaves Hydrolysable 22 – 35 14 – 15
Oak Wood Hydrolysable 4 – 10 1–2
Oak Bark Condensed 6 – 17 5–6
Quebracho Wood Condensed 14 – 26 1–2
Mimosa Bark Condensed 22 – 48 7–8
Mangrove Bark Condensed 16 - 50 9 - 15
130
65
A comparison of the two classes
Hydrolizable Condensed
Bond type Hydrogen bond H + covalent bonds (Lys)
Ts (°C) 75 - 80 80 - 85
Reversibility Easily reversible Hardly reversible
Example
Myrobalan Mimosa
Type Ellagitannin Profisetinidinic
Treatment Removal of tannins 80 % 50 %
with Urea 8 M Decrease of Ts (°C) 10 -20 4-5
131
12. Other tannages
Other tannages
132
66
12. Other tannages
OIL TANNING
1) Pickled sheepskin pelt
2) Wash to get swelling
3) Split
4) Re-pickle @pH 5 with 10% NaCl
5) Optional aldehyde pretannage
6) Squeeze excess water
7) Add cod liver oil
8) Heat up @40-50°C to initiate auto-oxidation
133
12. Other tannages
9) Degrease with aqueous Na2CO3 or organic

solvent (! Moellon-degras)
10) Buff the surface
The auto-oxidation products are fixed to the

fibers in sheath-like form. High resistance to
water and solvents. ΔTs ≈ 0 °C. Ewald effect is
used to mould leather into shapes (tucking).
134
67
12. Other tannages
SULFONYL CHLORIDE
Prot-NH2 + R-SO2-Cl → Prot-NH-SO2-R + HCl
Viable substitute of oil tanning. In this case no
oxidation is required, and final Ts ≈ 80 °C
Almost abandoned due to legislative restrictions
on C10-C13 SCCP (short chain chloroparaffin),
now extending to medium (C13-C17) and longer
chains.
135
12. Other tannages

SYNTANS
Discovery of tanning action of sulfonated
phenols/naphthols polycondensated with
formaldehyde (SO2Cl2, acetone, ethylene oxide).
First patent by Stiasny, 1913.
sulfonation + condensation
condensation + sulfonation
136
68
12. Other tannages
Auxiliary syntans
I step: sulfonation of naphthalene
II step: condensation with formaldehyde
137
12. Other tannages

Auxiliary syntans
1: naphthalen-1-sulfonate
2: naphthalen-2-sulfonate
3: naphthalen-2,6 –disulfonate
n=2: dimer + isomers
n=3: trimer + isomers
Retention time (min) 138
69
12. Other tannages
Auxiliary syntans
Long chain
Medium chain
Short chain
139
Retention time (min)
12. Other tannages

Auxiliary syntans
Gel Permeation
Chromatography
Long chain
Medium chain
Short chain
140
70
12. Other tannages
Auxiliary syntans
Monomeric unit Chain extension Naphthalene/formaldehyde MW (Da)
n
3–7 Short 1,8 2500
4–9 Medium 1,3 6000
7 - 13 Long 1,0 20000
Short chain Long chain

Penetration in the cross section
Dyeing uniformity
Free formaldehyde
Free naphthalene
141
12. Other tannages

Substitution syntans – 1st route
I step: addition of formaldehyde to phenol
+ isomers
Insoluble resin
p-methylolphenol dimethylolphenol
II step: sulfitation of methylolphenols

Soluble compounds
142
71
12. Other tannages
Substitution syntans – 1st route
III step: condensation Dimethylether link
High MW polymer
143
12. Other tannages

Substitution syntans – 2nd route
I step: sulfonation of phenol
Disulfonated phenol + isomers
II step: condensation with formaldehyde
144
72
12. Other tannages
or, alternatively, with formaldehyde and urea
145
12. Other tannages

III step: further condensation with phenol/CH2O
Extension unit Neutralization
Finished product
146
73
12. Other tannages
Substitution syntans
Tanning power
Decrease of solubility
Tanning power
Tanning power
147
12. Other tannages

Phenolsulfonic acids are divided in
- 1st condensation products: generally obtained
by single condensation of phenolsulfonic acid
with formaldehyde and urea
- 2nd condensation products: condensation of
phenolsulfonic acid with formaldehyde and
urea, followed by a further treatment with
formaldehyde and urea
148
74
12. Other tannages
1st condensation syntan 2nd condensation syntan
Free phenol Low High
Free formaldehyde High Low
MW - +
Dispersibility - +
Ox
+ +
o-benzoquinone
RED p-benzoquinone
cathecol hydroquinone YELLOW 149
12. Other tannages

<monomers
>MW
150
75
12. Other tannages
Dihydroxydiphenylsulfone syntans
dihydroxydiphenylsulfone
151
12. Other tannages

152
76
12. Other tannages
Dihydroxydiphenylsulfone + phenolsulfonic acid
Mixed polymers
153
12. Other tannages

Dihydroxydiphenylsulfone + naphthalenlsulfonic
acid
154
77
12. Other tannages
Other phenolic syntans
Phenol can be replaced by bisphenol A or
chresol
X = CH2SO3H: substitution syntan
obtained by condensation of
sulfomethylated phenol-cresol
R = H, CH3
Auxiliary syntans based on

diarylether
n = 1, 2
R = H, CH3
155
12. Other tannages

As a general rule the tanning effect depends on
the position of the H-bonding groups, on the
inductive effect and on the steric hindrance.
Non tanning Tanning

Auxiliary syntans Replacement syntans
Increasing MW
Increasing phenolic OH content
Increasing sulfonate content
Increasing OH/SO3 ratio
Increasing water solubility (hydrophilicity)
156
78
12. Other tannages
Effect of molecular structure on tanning power
157
12. Other tannages
158
79
12. Other tannages
159
12. Other tannages
Effect of relative position of phenolic OH on tanning
Presence of sulfonic substituents
160
80
12. Other tannages
RESINS
Melamine-urea-formaldehyde (MUF sulphonated
resins)
R=CH2OH
R=CH2SO3H
R=H
R= CH2NH-Mel-R
R= CH2-Urea-R
pH<7 methylene bridge

pH>9 ether bridge 161
12. Other tannages

RESINS
Melamine-urea-formaldehyde (MUF sulphonated
resins)
The ratio methylene/ether is proportional to the

resistance to hydrolysis.
Rearrangement of ether bridges leads to release of
formaldehyde
162
81
12. Other tannages
RESINS
Dicyandiamidic resins: condensation products of
urea, formaldehyde and dicyandiamide.
163
12. Other tannages

RESINS
Polyacrilates
PUR
Styrene-maleic anhydride
164
82
12. Other tannages
ALDEHYDE TANNING
Formaldehyde is known to have a tanning effect.
On collagen’s side Lys is involved in the reaction.
Prot-NH2 + RCHO → Prot-NH-CH(OH)R
The N-methylol derivative can lose water and
form a Schiff base:
Prot-NH-CH(OH)R → Prot-N=CHR + H2O
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12. Other tannages
Since OH is a good leaving group, a cross-linkage

effect is also possible with another collagen
sidechain:
Prot-NH-CH(OH)R + Prot-NH2 →
Prot-NH-CHR-NH-torP + H2O
In any case, covalent bonds do form.
166
83
12. Other tannages
Nowadays almost all of aldehyde tannages are
based on glutaraldehyde.
1) Glutaraldehyde forms Schiff bases with

proteins, stabilized by other GA molecules.
2) No evidence of crosslinks
3) 3 GA are fixed per Lys amino group.
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12. Other tannages

Polymerization of glutaraldehyde
168
84
12. Other tannages
Reaction of glutaraldehyde with collagen
169
12. Other tannages

Oxazolidines were introduced in the leather
industry in the late 70’s. Formaldehyde is used in
the synthesis:
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85
12. Other tannages
OXAZOLIDINES
Type Oxazolidine A Oxazolidine E Oxazolidine T
Name 4,4-dimethyl-1- 5-Ethyl-1-aza-3,7- 5-hydroxymethyl-1-aza-
oxa-3-aza- dioxabicyclo[3.3.0] 3,7-dioxabicyclo[3,3,0]
cyclopentane octane octane
Molecular structure
CAS number 51200-87-4 7747-35-5 6542-37-6
MW (g/mol) 101.17 143.18 145.18

Appearance Yellowish liquid Yellowish liquid White powder
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12. Other tannages

Oxazolidines react with the amino residue of Lys
in two ways:
A – Breakage of C–O bond of the heterocycle
172
86
12. Other tannages
Oxazolidines react with the amino residue of Lys
in two ways:
B – Breakage of C–N bond of the heterocycle
with formation of a Schiff base. Formaldehyde?
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12. Other tannages
Formaldehyde is released by the leather due to

hydrolysis. Customers’ requirements are more
and more strict on formaldehyde:
Evolution of maximum tolerated formaldehyde
content in finished leather (values in mg/kg)
300 → 150 → 75 → 50 → 20 → ?
174
87
12. Other tannages
Phosphonium salts
Tetrakis(hydroxymethyl)phosphonium sulfate
(THPS) reacts with an aldehydic-like mechanism
(P-methylol groups)
175
12. Other tannages
Four crosslinking points are theoretically

possible – on average each molecule links 2.2
amino groups.
At pH>8 the phosphonium salt is hydrolyzed and
oxidized
-
OH
(HOCH2)4P+ (HOCH2)4POH (HOCH2)3P +
Ox
H2O + HCHO (HOCH2)3P=O
176
88
13. Miscellanous tannages
Miscellaneous tannages
177
Epoxide tanning
Stable epoxides have been prepared for tanning
applications:
Polyethyleneglycol diglycidyl ether
Glycerol triglycidyl ether
Pentaerythritol glycidyl ether
178
89
Isocyanate tannage
Water-soluble isocyanates can raise TS up to
80°C. The NCO moiety reacts with OH
(urethanes) and amines (ureas).
HMDI
IPDI
MDI
179
14. Fungicides
Typical biocidal substances used in tanning:

organo-sulfur compounds
TCMTB (2-(Thiocyanomethylthio) benzothiazole)
OIT (2-Octyl-4-isothiazolin-3-one)
180
90
14. Fungicides
Typical biocidal substances used in tanning:

phenolics
CMK (4-Chloro-3-methylphenol)
OPP (2-Phenylphenol)
181
14. Fungicides
Degradation of TCMTB
TCMTB (2-(Thiocyanomethylthio) benzothiazole)
Reduction (sulfide, sulfite, other)
MBT (2-Mercaptobenzothiazole)
182
91
15. Post tanning
Post tanning
183
15. Post tanning
WET END
After regulation of thickness by shaving the wet
material is subjected to the following
operations:
1) Retanning
2) Dyeing
3) Fatliquoring
184
92
15. Post tanning
Retanning is conducted with tanning or pseudo-
tanning agents in order to impart the final
“character” to the leather.
It is a major contributor of the fullness, the
handle (haptic) and the mechanical
performances of the finished article.
Virtually all kinds of tanning agents can be used
(metallic salts, aldehydic reagents, hydrogen-
bondable polymers, syntans, etc.)
Chemical modifications include the shift of IEP.
185
15. Post tanning
Dyeing gives the requested colour to the

substrate
Fatliquoring prevents fibre sticking during
drying. The nature and quantity of fatliquors
regulate the softness, the humidity and also
influence the mechanical properties (tear and
tensile strength). Special features (water
repellency, fire resistance, etc.) are also given in
this stage.
186
93
15. Post tanning
General formulation of fatliquors
1) Hydrophobic components: saponifiable and

unsaponifiable substances.
Fats and oils of animal/vegetal origin, mineral
oils, silicones, alkylbenzenes, polyethers, etc.
187
15. Post tanning
2) Hydrophilic substances: anionic, cationic, non-

ionic emulsifiers
Sulfonated, sulfitated, carboxylated,
phosphonated, fatty amines/amides,
polyglycolethers, etc.
188
94
15. Post tanning
3) Inorganic substances (salts)

4) Volatile substances (water, solvents)
Fatliquors are technically classified basing on the

origin of the raw fatty substance (natural,
synthetic) and the ionic charge.
189
15. Post tanning
Natural
- Animal (fish oil, lard oil, lanoline, etc.)
- Vegetal (lecithin, sunflower, rapeseed, peanut,
palm, coconut, castor oil, waxes, etc.)
Synthetic
- From oil refining: mineral oil, alkylbenzenes,
etc.
- Synthetic fatty alcohols, esters, polymers, etc.
190
95
15. Post tanning
Anionic fatliquors
- Fatty alkyl/aryl sulfonates R-SO3-

- Fatty alkyl/aryl sulfates R-OSO3-
- Fatty alkyl/aryl phosphates R-OPO(OH)2
- Fatty alkyl/aryl carboxylates (soaps, acrylic
copolymers)
191
15. Post tanning
Anionic fatliquors
Sulfosuccinates:
Esterification of maleic anhydride with fatty
alcohols, then sulfitation.
Properties
Fair stability to electrolytes, high lightfastness,
very good fixations on leather.
192
96
15. Post tanning
Sulfosuccinates
193
15. Post tanning
Anionic fatliquors
Sulfitated fatliquors:
Oxidation of unsaturated fats (air@80-90°C for
24h, or with pressurized oxygen and cataysts fo
2 h), then sulfitation with NaHSO3.
Properties
High stability to electrolytes, fair lightfastness,
fair fixation on leather.
194
97
4. Soaking
Distribution of fat in the cross section
195
15. Post tanning
196
98
15. Post tanning
197

EN 15987:2015
Leather. Terminology. Key definitions for the
leather trade
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EN 15987:2015
leather trade
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EN 15987:2015
leather trade
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100
EN 15987:2015
leather trade
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EN 15987:2015
leather trade
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EN 15987:2015
leather trade
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EN 15987:2015
leather trade
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EN 15987:2015
leather trade
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EN 15987:2015
leather trade
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EN 15987:2015
leather trade
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leather trade
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leather trade
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leather trade
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17. Some pictures
ISO 17131 – Identification of leather with microscopy
211
17. Some pictures

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17. Some pictures

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17. Some pictures
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17. Some pictures

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Tanning chemistry

1. Collagen and skin structure

Collagen and skin

1. Collagen and skin structure

• Coded at position A 64 of human genome

• Hydroxyproline is almost exclusive

1. Collagen and skin structure

TRIPLE HELIX = 2 x α(1) + 1 x α(2)

1. Collagen and skin structure

1. Collagen and skin structure

1. Collagen and skin structure

1. Collagen and skin structure

Hyp is the major responsible for collagen stability

Source Pr/Hyp residues per 1000 Shrinkage temperature (°C)

Water content Freezing point Desorption Structural function

! Properties change upon drying

1. Collagen and skin structure

Skin and its components

2. Skin and its components

AA type Elastin Collagen

2. Skin and its components

2. Skin and its components

3. Curing and preservation of hides

Curing and preservation

Conditions favoring putrefaction

3. Curing and preservation of hides

Technique Hides processed in the district

3. Curing and preservation of hides

3. Curing and preservation of hides

3. Curing and preservation of hides

3. Curing and preservation of hides

The BEAMHOUSE process prepares the hides for

1) Removal of non-collagenous components (HA

Typical beamhouse process for bovine hides

The reactor of choice is the DRUM

The reactor of choice is the DRUM

The reactor of choice is the DRUM

Mechanical action in the drum

Soaking has the aim of

• Cleaning and rehydrating the pelt

Mass exchange is regulated by transportation

sodium lauryl sulfate

Non ionic detergents

Ethoxylathed fatty alcohols

Hydrophilic - Lipophilic Balance (HLB)

Example: lauryl ether sulfate 2M (n=2)

HLB Range Water solubility Application

Cystine content of hair: 60 mmol/100g

Semi-reaction Redox potential EO (mV)

Only S2- is eﬀecUve for unhairing → pH ≥ 12

Ca(OH)2 (s) Ca(OH)2 (aq) Ca2+ + 2OH-

14-log[OH-]= 14-log(2*1.7/ Ca(OH)2)= 12,7

At such pH values the hides swell.

Hair amounts to ca. 10% of hide weight. Since Cys

0,60 x Na2S (78,04 g/mol)/purity (70%) ≈ 67 g

0,07 kg/kg x 10 % = 0,7 % on hide weight

For kinetic reasons the rate is around 2-3% wt.

Unhairing reductive agents

Name Formula E0 (mV) @pH 12

This reaction is exploited in hair saving processes

4ClO2- +2H+ 2ClO2 + ClO3- + Cl- + H2O

4 R-S-S-R + 10 ClO2 + 4 H2O 8 RSO3-+ 8 H+ + 5 Cl2

Modern processes make use of hydrogen

8 ClO2 + 5 S2- + 4 H2O 8 Cl- + 5 SO42- + 8 H+