TEPZZ 9 4Z96A_T

(19)

(11) EP 2 924 096 A1

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.:

30.09.2015 Bulletin 2015/40 C10C 3/02 (2006.01) C08L 95/00 (2006.01)
C08L 75/00 (2006.01)
(21) Application number: 15158746.6

(22) Date of filing: 12.03.2015

(84) Designated Contracting States: (72) Inventors:

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • Bhatnagar, Akhilesh Kumar
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO FARIDABAD (IN)
PL PT RO RS SE SI SK SM TR • Padhan, Rabindra Kumar
Designated Extension States: FARIDABAD (IN)
BA ME • Gupta, Anurag Ateet
Designated Validation States: 121007 FARIDABAD (IN)
MA • Raman, Naduhatty Selai
121007 FARIDABAD (IN)
(30) Priority: 26.03.2014 IN MU10492014
(74) Representative: Oficina Ponti, SLP
(71) Applicant: INDIAN OIL CORPORATION Ltd. C. Consell de Cent, 322
Mumbai 400 051 (IN) 08007 Barcelona (ES)

(54) PREPARATION OF POLYMER MODIFIED BITUMEN (PMB) FROM POLYETHYLENE

TEREPHTHALATE (PET) DERIVED POLYAMIDO AMINE

(57) The present invention relates a novel approach vides a process to utilize waste PET, which is a threat to
to prepare Polymer Modified Bitumen by using tereph- environment and is available commercially in different
thalamide additives, derived from PET, for improving bi- physical forms, for conversion into industrially useful ad-
tumen quality. Particularly, the present invention pro- ditive for bituminous product.
EP 2 924 096 A1

Printed by Jouve, 75001 PARIS (FR)

 EP 2 924 096 A1

Description

FIELD OF THE INVENTION

5 [0001] The present invention relates a novel approach to prepare Polymer Modified Bitumen by using terephthalamide
additives, derived from PET, for improving bitumen quality.

BACKGROUND OF THE INVENTION

10 [0002] Bitumen is a dark-brown to black sticky material, solid or semi-solid in consistency, in which the primary con-
stituents are a mixture of paraffinic and aromatic hydrocarbons and heterocyclic compounds containing sulfur, nitrogen
and oxygen. In view of emerging need to improve bitumen properties, the use of chemical additives, particularly Polymers,
is currently a much investigated subject.
[0003] In recent years, one of the important developments in the field of alternate application of virgin or used plas-
15 tic/rubber material (mainly SBS and EVA type), is their use in making Polymer/Rubber Modified Bitumen (PMBs/RMBs)
as value added product of Bitumen. Presently, PMBs/RMBs are used in huge quantities in making road highways
infrastructure. PMBs/RMBs offer some definitive advantages over conventional bitumen such as lower susceptibility to
daily and seasonal temperature variations, higher resistance to deformation at elevated pavement temperatures, better
age resistance properties, better adhesion, less cracking even in heavy traffic conditions etc. The use of PMBs/RMBs,
20 in India, has just begun during last decade particularly under highway development program.
[0004] Disposal of plastic material in general and PET based products like bottles for water/soft drinks etc., in particular,
is one of identified factor for current pollution. Global efforts are underway, to recycle PET through both chemical and
mechanical routes. Unfortunately, under mechanical recycling route, in particular, many prior art reported processes are
not efficient and the quality of derived product remains questionable for recycling purposes.
25 [0005] On the other hand, "chemical recycling" which includes depolymerization of PET chains has been widely men-
tioned in the prior art. Five major approaches such as Glycolysis, Alcoholysis, Hydrolysis, Saponification and Aminolysis
have been reported in several scientific literatures.
[0006] In aminolysis route our approach consisted of subjecting PET and amines such as ethanol amine, polyamine
to temperature conditions from about 100° to 200 °C both under catalytic and non-catalytic conditions. PET on decom-
30 position, as reported in our earlier patent (Application number: PCT/IB2013/050974), converts into product or product
mixtures which are mainly terephthalamide derivatives.
[0007] One of the major challenge and a desirable approach in the aminolysis reaction is to develop products that can
be used on an industrial scale. In our earlier patent (Application number: PCT/IB2013/050974) we have explored the
process for utilization of terephthalamide synthesized from PET via aminolysis reaction as an anti-stripping agent for
35 bitumen.
[0008] Lee, Sang-Yum; recently showed that the dimethylphenol (DMP) was added to the neat asphalt and polymer-
ization carried out autonomously, without adding any external catalyst for the polymerization, only with oxygen molecules
in the air. The polymer produced in the asphalt was polyphenyleneoxide (PPO) and it enhanced the mechanical properties
of the asphalt.
40 [0009] EP 0561471 A1 discloses the bituminous composition comprising, block copolymer and conjugated diene and
an acrylic monomer such as an alkyl methacrylate to form PMB. WO 2012007418 A1: discloses a Polyurethan-/Polyiso-
cyanurat polymer obtainable from the reaction of an isocyanate-terminated with POLYOL outside of bitumen and then
blend with bitumen. EP 0667886 B1 describes bituminous composition comprising a bituminous, conjugated diolefin
and an acrylic monomer of a polyfunctional amine having at least two amino groups.
45 [0010] There arise needs to provide a process to utilize waste PET, which is a threat to environment and is available
commercially in different physical forms, for conversion into industrially useful additive for bituminous product.

SUMMARY OF THE INVENTION

50 [0011] An object of the present invention is to provide a process to utilize waste PET, which is a threat to environment
and is available commercially in different physical forms, for conversion into industrially useful additive for bituminous
product. Another object of the present invention is to provide a process for effective and bulk use of aminolysed product
of PET polymers.
[0012] A further object of the invention is to provide a process for preparation of a bituminous cement mixture as per
55 Indian Standard and ASTM Standard as well as the combination of that mixture with an aggregate in a form for road
paving, i.e. a bituminous concrete, which has high temperature susceptibility (Table-3), and high temperature performance
properties (Table-2).
[0013] Yet another object of the invention is to provide a novel process comprising the reaction of terephthalamide

2
 EP 2 924 096 A1

derived from the reactions of amines such as primary, secondary and tertiary amines and PET with isocyanates and
more particularly Methylene Diphenyl Diisocyanate (MDI), in bitumen.
[0014] Another object of the invention is to provide a process for improving low temperature susceptibility properties
of bitumen with such chemical compounds.
5
BRIEF DESCRIPTION OF ACCOMPANYING DRAWING

[0015]

10 Fig-1: Shows Hot Water Stripping Test (ASTM D 3625-96 (Reapproved 2005))

(a) Neat VG-10 Bitumen Binder;

(b) Polymer Modified Bitumen Binder of the Present Invention.

15 Fig-2: IR Data of BHETA Terephthalamide (Bis (2-hydroxyethylene) terepthalamide) Derived PMB.

Fig-3: IR Data of TETA Terephthalamide derived PMB.

DETAILED DESCRIPTION OF THE INVENTION

20
[0016] The present invention discloses a method of preparation of novel polymer modified asphalt binder compositions
that are made by reacting a Poly-isocyanate with amido amine derivative.
[0017] An aspect of the present invention discloses a process for preparing modified bitumen from amido amines or
polyamido amines and isocyanate or polyisocyante.
25 [0018] In an aspect the present invention provides a process for preparing modified bitumen comprising, reacting
amido amines or polyamido amines; isocyanate or polyisocyanate; and bitumen in a solvent to obtain modified bitumen.
[0019] In another aspect of the present invention, amido amines or polyamido amines are reacted with isocyanate or
polyisocyanate, prior to reacting with bitumen.
[0020] In another aspect of the present invention, amido amines or polyamido amines; isocyanate or polyisocyanate;
30 and bitumen are reacted simultaneously.
[0021] In another aspect of the present invention, amido amines or polyamido amines and isocyanate or polyisocyanate
are reacted to obtain a polyureathane.
[0022] In another aspect of the present invention, amido amines or polyamido amines and isocyanate or polyisocyanate
are reacted to obtain a polyurea.
35 [0023] Another aspect of the present invention discloses a bituminous cement mixture comprising polyurethane or
polyurea polymers in body of bitumen.
[0024] The polyurethane or polyurea polymers are formed in the body of the bitumen matrix in the following manner:

40

45

50

where, R= (Ph-CO-NH)1-5 (CH2-CH2)1-8-(NH)0-8;

R’= Ph, Ph-CH2-Ph, Ph-CH3, (-CH2-)1-10
[0025] In an aspect of the present invention, bituminous cement mixture as described herein comprises of a statistical
55 mixture of compounds encompassed by the general structure of formula R’1NCH2CH2-(CH2CH2NH)n-CO-
C6H4-CO-(NHCH2CH 2)nCH2CH2NR"2, where N is nitrogen, R’1 and R"2 are each independently a hydrogen or alkyl
moiety and n is an independent integer lying in the range of 1 to 10.
[0026] In an embodiment of the present invention, amido amines or polyamido amines are prepared by reacting

3
 EP 2 924 096 A1

polyethylene terephthalate (PET) with amines or polyamines.

In yet another embodiment of the present invention, the terephthalamide and polyisocyanate can be reacted together
in a variety of ratios with the range of (0.05 to 30%) and under different set of reaction conditions.
[0027] In an embodiment of the present invention, amido amines or polyamido amines are present in 0.05-30% wt/wt
5 of bitumen, the isocyanates or polyisocyanates are present in 0.05-30% wt/wt of bitumen and the reaction is conducted
at a temperature of 50°C to 190°C for a period of 10 minutes to 8 hours.
[0028] In accordance with the present invention, modified bitumen is prepared by reacting amido amines or polyamido
amines with isocyanate or polyisocyante in bitumen. When the reactant components in bitumen are reacted together,
they form a statistical mixture of terephthalamide compounds encompassed by the general structural formula
10 R’1NCH2CH2-(CH2CH2NH)n-CO-C 6H4-CO-(NHCH2CH2)nCH2CH2NR"2, where N is nitrogen, R’1 and R"2 are each in-
dependently a hydrogen or alkyl moiety and n is an independent integer lying in the range of 1 to 10. R’1N and or R"2N
could also be alkyl or substituted aromatic groups or an oligomer derived from aminolysis of PET. In one embodiment,
R’1N and/or R"2N is alkyl or substituted aromatic group or an oligomer derived from aminolysis of PET.
[0029] In accordance with the present invention, amines or polyamines are selected from the group comprising ethylene
15 diamine, triethylene tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene di-
amine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamine, trimeth-
ylene diamine, pentaethylene hexamine, di(trimethylene)triamine, N-(2-aminoethyl)piperazine, 1,4-bis(2-aminoethyl)pip-
erazine, an aromatic polyamine such as phenylene and napthylene diamines or hydrazines such as hydrazine, organo-
hydrazines having hydrocarbon-based substituents of up to about 30 carbon atoms.
20 [0030] The isocyantes or polyisocyanates used in accordance with the present invention are selected from the group
comprising hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate (HMDI), ethylene diisocyanate,
ethylidene diisocyanate, propylene, butylene diisocyanate, diisocyanate dichlorohexaméthylène, furfurylidene diisocy-
anate, Cycloaliphatic polyisocyanates, like isophorone diisocyanate (IPDI), cyclopentylene-1, 3-diisocyanate, cyclohex-
ylenedimethylene 1 diisocyanate, cyclohexylene-1, 2 - diisocyanate, and mixtures thereof, aromatic polyisocyanates
25 like the 4, 4 ’-diphenyl diisocyanate (MDI) and its isomers, such as 2,4’ - and 2, 2 ’-diphenylmethane diisocyanate, toluene
diisocyanate (TDI) and isomers thereof, particularly the 2,4 - and 2,6-toluene diisocyanate, 2, 2-diphenylpropane-4’-
diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, 1, 4-naphthalene diisocyanate,
1, 5-naphthalene diisocyanate, azobenzene-4, 4’-diisocyanate, diphenyl sulfone-4, 4’-diisocyanate, 1-chlorobenzene-
2 ,4-diisocyanate, 4 4’, 4"-triisocyanatotriphériyl methane, 1, 3, 5-triisocyanato-tetraisocyanate, and mixtures thereof.
30 [0031] The polyisocyante as described herein is diisocyanates, more specifically MDI and its isomers, TDI and its
isomers, the HDI, the IPDI and derivatives thereof.
[0032] Various solvents suitable for carrying out the polymerization according to the invention include Dimethyl for-
mamide (DMF), Dimethyl sulphoxide (DMSO), Acetone, Methylethyl ketone, Tetrahydrofuran (THF), Ethyl acetate, Ben-
zene, Toluene, Chlorobenzene, Hexane, Cylohexane, Xylene and Dichloro Methane(DCM) etc.
35 [0033] In another aspect of the present invention, a bituminous concrete comprising bituminous cement mixture and
an aggregate.
Further, the process of the present invention is performed by way of two alternative processes:

1. When isocyanates are added in Bitumen:

40
[0034] Different polyamido amines/amido amines from PET were synthesized in a separate reaction vessel using
method reported in the earlier patent Application number: PCT/IB2013/050974. For the present invention bitumen,
polyamido amines/amido amines/ terephthalamide and polyisocyanate are reacted to obtain a bituminous mix.

45 2: When isocyanates are added outside Bitumen:

[0035] Polyurethanes were synthesized using a one-step polymerization reaction method. Poly amidoamine and/or
terephthalamide derivative prepared by reacting PET and ethanol amine, triethanolamine, amine or polyamine is reacted
with Polyethylene glycol (PEG) (PEG200,PEG400,PEG6000) Polyethylene glycol(PEG) suitable for use in the present
50 discloses includes, but is not restricted to, various low molecular weight PEG and also high molecular weight PEG and
Dibutyltin dilaurate (DBTDL) in a solvent. After the completion of the reaction, isocyanate/ polyisocyanate were added.
Removal of solvent was accomplished by using vacuum distillation. The above product was added to bitumen and to
form polymer modified bitumen (PMB).
[0036] Having described the basic aspects of the present invention, the following non-limiting examples illustrate
55 specific embodiment thereof.

4
 EP 2 924 096 A1

Example 1:

(When isocyanates are added in Bitumen)

5 [0037] Different polyamido amines from PET were synthesized in a separate reaction vessel using method reported
in the earlier patent Application number: PCT/IB2013/050974. For present invention, a three necked, 500 ml round-
bottom flask equipped with a heating mantle, overhead stirrer, water condenser, nitrogen gas sparging tube and a thermo
well pocket containing thermometer (40°C to 300°C range) was used. The flask was charged with bitumen, polyamido
amines in 3% Wt/Wt of bitumen, polyisocyanate in 1.5% Wt/Wt of bitumen to form modified bitumen. The temperature
10 is 140 °C and duration of reaction is 2 hours. The bituminous mix thus prepared was tested for different lab tests.

Physico-Chemical Properties:

[0038] The physicochemical properties of the modified bitumen samples during this invention indicate that it has met
15 the plastomer specification. The following were used for the experiment:

VG-10 Bitumen

[0039] Bitumen supplied from Mathura Refinery having viscosity grade-10 (i.e. 80/100 penetration grade).
20 Properties of Mathura Refinery having VG-10 Bitumen:

Properties Test values Referral specifications

Penetration 85 IS1203/1978
25 Absolute Viscosity at 60°C 1145 IS1206(PART2)
Kinematic Viscosity at 135°C 302 IS1206(PART3)
Softening Point in °C 46 IS 1205/1978
Ductility at 27°C 100+ IS 1208 : 1978 Min
30
Ductility after TFOT at 25°C in cm 100+ IS 1208 : 1978 Min

TEPA-Modified:
35
[0040] TEPA-Modified Bitumen comprising of terephthalamide [Aminolysis product synthesis of PET with tetraethyl-
enepentamine (TEPA)], isocyanate and Bitumen.

BHETA Modified:
40
[0041] BHETA -Modified Bitumen comprising of terephthalamide (synthesis of PET with ethanol amine), isocyanate
and Bitumen.

TEPA-Modified(1):
45
[0042] TEPA-Modified (1), Bitumen comprising of terephthalamide (Aminolysis product synthesis of PET with tetrae-
thylenepentamine), isocyanate and Bitumen (The Ratio of isocyante, terephthalamide and bitumen are 0.5:1:98.5 wt/wt).

TEPA-Modified(2):
50
[0043] TEPA-Modified Bitumen comprising of terephthalamide (Aminolysis product synthesis of PET with tetraethyl-
enepentamine), isocyanate and Bitumen (The Ratio of isocyante, terephthalamide and bitumen are 0.5:1.5:98 wt/wt).

BHETA Modified (1):

55
[0044] BHETA -Modified Bitumen comprising of terephthalamide (synthesis of PET with ethanol amine), isocyanate
and Bitumen (The Ratio of isocyante, terephthalamide and bitumen are 0.5:1:98.5 wt/wt).

5
 EP 2 924 096 A1

BHETA Modified (2):

[0045] BHETA -Modified Bitumen comprising of terephthalamide (synthesis of PET with ethanol amine), isocyanate
and Bitumen (The Ratio of ISOCYANTE, terephthalamide and bitumen are 0.5:1.5:98 wt/wt).
5
Table-1: Physico-Chemical Properties
Properties VG-10 TEPA-Modified BHETA PMB-grade-3 Specification
Bitumen Modified (IRC:SP:53-2010)

10 Penetration 25°C (100g, 84 67 66 60-120 IS1203/1978

5s),0.1mm
Softening Point (Ring and 46 51.5 52 50 Min IS 1205/1978
Ball), °C, Minimum

15 Ductility at 27°C (5 100 90+ 40 --- IS 1208 : 1978

Cm/Min) Min
Viscosity (150°C) Using 1.57 2.78 2.95 1-3 poise ASTM:D-4402
Rotational Viscometer
(Poise)
20
Separation Difference in --- 2 2.7 3 Max (IRC:SP
Softening Point(R&B) °C 53-2010)
Max

25 Dynamic Shear Rheometer

[0046] DSR method was determined to be the main method for measuring the deformation characteristics of road
surfaces in the future. The test procedure used to measure the G*/Sin(δ), a parameter of rutting-assistance of the original
bitumen and RTFOT test-aged bitumens. The Superpave specification states that, at the maximum pavement design
30 temperature, the G*Sin(δ) value should be at least 1.0 kPa for original bitumen and 2.2 kPa in order for RTFOT-aged
bitumen to resist rutting.

Table-2: Dynamic Shear Rheometer

Properties Test VG-10 TEPA-Modified BHETA Passing limit PMB-grade-3
35
Temperature Bitumen G*/Sin (delta) Modified of G*/Sin (IRC:SP:53-2010)
G*/Sin G*/Sin (delta)
delta) (delta) (ASTM:D
-7175)
40 DSR Neat 58°C 2.14 5.32 4.93 1.0 58°C Min Required
Temperature
64°C 0.92 2.55 2.35
70°C 0.43 1.23 1.16
76°C 0.2 0.639 0.519
45
DSR RTFO 58°C 3.99 11.34 10.67 2.20 58°C Minimum
Age Required
64°C 1.71 5.49 4.96
Temperature
70°C 0.61 2.84 2.22
50 76°C 0.27 1.27 1.01

[0047] The modified asphalt exhibiting improved stiffness values for original unaged modified bitumen binder as well
as RTFO age modified bitumen binder, which when tested with DSR at temperature ranging from 58-82 °C, exhibits
55
G*/Sin(delta) values are higher than normal bitumen. The table showed that the modified bitumen has G*/Sin(delta) are
1.23 and 1.16 kPa for unaged and 2.84 and 2.22 kPa at 70 °C for RTFO age, TEPA-Modified and BHETA Modified
bitumen respectively.

6
 EP 2 924 096 A1

Bending Beam Rheometer

[0048] In order to further examine low temperature thermal cracking properties, thin beams of modified bitumen were
tested for creep stiffness at low temperature using the Bending Beam Rheometer (BBR). The maximum stiffness criteria
5 of 300 MPa and the minimum m-value criteria of 0.300 recommended in Superpave binder specifications generally
appear to be reasonable in mitigating low-temperature cracking.

Table-3: Bending Beam Rheometer

Properties VG-10 Bitumen TEPA-Modified BHETA Modified Specification
10
Temperature Stiffness m- Stiffness m-Value Stiffness m- ASTM:D 6648 Maximum
Value Value Stiffness =300 MPa and
Minimum m-value = 0.300
-6 °C 74 0.402 41.3 0.495 35.3 0.508

15 -12 °C 147 0.362 93.3 0.432 110 0.381

-18 °C 395 0.288 256 0.326 280 0.292

[0049] The modified asphalt exhibiting improved creep stiffness and m-value were tested at low temperature from
20 -42°C to 0°C according to SHARP Bending Beam Creep Stiffness Test AASHTO TP1. The results disclose that the
modified binder in this invention were more flexible after aging process. This showed the direct effect of aging on bitumen
viscoelastic behaviors and increasing the bitumen plastic behavior. A comparative study of the BBR test data for the
modified bitumen is given in the above table. The table showed that the modified bitumen has stiffness 256 and 280
MPa and m-value 0.326 and 0.292 at -18 °C for TEPA-Modified and BHETA Modified bitumen respectively. This discloses
25 the better performance of our modified bitumen than the other PMB available in the market.

Rutting Characteristics

[0050] Wheel tracking test is a simulative laboratory method of assessing resistance to permanent deformation and
30 correlate their results with in-service pavement rutting. The modified asphalt exhibits improved rutting resistance 3.2
and 1.5 mm and 2.96 and 1.82 for different composition of TEPA-Modified and BHETA Modified bitumen respectively.

Table-4: Rutting Characteristics

Properties VG-10 TEPA- TEPA-Modified BHETA BHETA Specification
35 Bitumen Modified (2) Modified (1) Modified (2)
(1)
Rut Depth 4.8 3.2 1.5 2.96 1.82 (EN12697-22:2003+A1)

40 Marshall Stability Test

[0051] Marshall Stability test is used for evaluation of the resistance to plastic deformation of a compacted cylindrical
specimen of bituminous pavement. Marshall Stability Test has stability-flow tests. The Marshall stability of the bituminous
pavement is defined as the maximum load carried by the compacted cylindrical specimen at a standard test temperature
45 of 60°C. The flow value is the deformation that the test compacted cylindrical specimen undergoes during loading up to
the maximum load mm units. According to IRC: SP-53 specification the marshall strength and flow value for Hot Climate,
Marshall Stability is 12KN and Flow value is 2.5-4 mm and for Cold Climate the Marshall Stability is 10KN and Flow
value is 2.5-4 mm and for High Rain Fall area Marshall Stability: 12KN, Flow value is 3.0-4.5mm at 60°C, respectively.

50 Table-5: Marshall Stability Test

Binder (Marshall Strength KN / Flow in mm)* Specification
content Compaction temp:141°C
VG-10 TEPA- BHETA ASTM:D-6927
55 Bitumen Modified Modified ASTM:D-6926
5% 11.9/2.24 14.54/3.66 11.28/2.32 IRC:53-2010
5% 12.30/2.43 13.44/3.75 12.47/2.80 Hot Climate:

7
 EP 2 924 096 A1

(continued)

Binder (Marshall Strength KN / Flow in mm)* Specification

content Compaction temp:141°C
5
VG-10 TEPA- BHETA ASTM:D-6927
Bitumen Modified Modified ASTM:D-6926
5% 13.15/2.80 12.55/3.45 10.92/2.12 Marshall Stability: 12KN, Flow at 60°C = 2.5-4mm
Average of 12.45/2.49 13.51/3.62 11.55/2.41
10
5%
dosage
5.5% 13.55/2.39 17.75/3.45 14.09/3.89 Cold Climate:
5.5% 12.98/2.55 16.25/4.08 14.20/3.46 Marshall Stability: 10KN, Flow at 60°C = 3.5-5 mm
15 For High Rain Fall Marshall Stability: 12KN, Flow at
5.5% 14.59/2.52 16.8/3.67 13.89/3.21
60°C = 3.0-4.5mm
Average of 13.67/2.48 16.93/3.73 14.06/3.52
5.5%
dosage
20
6% 13.55/2.39 20.15/5.08 15.23/5.23
6% 14.58/3.59 17.71/4.35 16.82/5.03
6% 14.09/3.12 20.48/4.05 14.67/4.87

25 Average of 14.07/3. 19.44/4.49 15.57/5.04

6%
dosage

[0052] The modified asphalt exhibits improved Marshall Stability and flow value. The results indicate that stability
30 increases on all formulations meets all types of climatic condition in the IRC:53-2010.

Hot Water Stripping Test (ASTM D 3625-96 (Reapproved 2005))

[0053] The Boiling Water Test (ASTM D3625) is a subjective test for the effects of moisture of bituminous mixes. It is
35 used primarily as an initial screening test of anti-stripping agent in bituminous mixes. The results clearly demonstrate
the good antistripping behaviour of modified bituminous mixes. The results disclose that the modified binder in this
invention shows improved antistripping behavior.

Example 2:
40

(When isocyanates are added outside Bitumen)

[0054] Polyurethanes were synthesized using a one-step polymerization reaction method. BHETA 0.04155 mol, Pol-
yethylene glycol (PEG) (0.01785 mol) and DBTDL (0.001167 mol) were dissolved in 250 mL of DMSO in a two-necked
45 round bottom flask equipped with a condenser and stirrer. The temperature was raised to 110 °C. Then 1.8 mol of MDI
were added and the reaction mixer stirred vigorously. After completion of reaction, removal of solvent was accomplished
by using vacuum distillation. 3% of the above product was added to bitumen and stirred for 2h at 140°C to formed
polymer modified bitumen (PMB). Properties of resultant modified bitumen are shown below.

50 Table-6: Physico-Chemical Properties

Properties VG-10 TEPA-EXSITU BHETA-EXSITU PMB-grade-3 Specification
Bitumen PMB PMB (IRC:SP:53-2010)
Penetration 25 °C 84 71 69 60-120 IS1203/1978
55 (100g, 5s),0.1mm
Softening Point (Ring 46 50.7 51 50 Min IS 1205/1978
and Ball), °C, Minimum

8
 EP 2 924 096 A1

(continued)

Properties VG-10 TEPA-EXSITU BHETA-EXSITU PMB-grade-3 Specification

Bitumen PMB PMB (IRC:SP:53-2010)
5
Viscosity(150°C) 1.57 1.96 2.16 1-3 poise ASTM:D-4402
Using Rotational
Viscometer(Poise)
Separation Difference --- 2.5 2.7 3 Max (IRC:SP
10 in Softening 53-2010)
Point(R&B) °C Max

[0055] The results indicate that all physico-chemical properties of all polymers modified bitumen binder (made through
ex-situ polymerization) and meet all requirements according to the IRC: 53-2010.
15
Table-7: Dynamic Shear Rheometer (DSR)
Properties Test EXSITU- EXSITU BHETA Passing limit of PMB-grade-3
Temperature TEPA-PMB PMB G*/Sin(delta) (ASTM:D- (IRC:SP:53-2010)
G*/Sin(delta) G*/Sin(delta) 7175)
20
58°C 4.63 4.89 58°C Min Required
Temperature
DSR Neat 64°C 1.96 2.01 1.0
70°C 0.91 0.95
25 58°C 7.51 10.96 58°C Minimum
DSR Required
64°C 3.46 3.84 2.20
RTFO Age Temperature
70°C 1.72 1.86

30
[0056] The Superpave specification states that in alter to provide suitable resistance against rutting at the maximum
pavement design temperature of a bituminous product the G*/Sin(δ) value should be at least 1.0 kPa for neat bitumen
and 2.2 kPa for RTFOT-aged bitumen samples. DSR studies were done on samples of TEPA-Modified bitumen, BHETA-
modified bitumen. The table shows that all modified bitumen have G*/Sin(δ) values of 1.96 and 2.01 kPa for unaged
35 and 3.46 and 3.84 kPa at 64 °C for the RTFO aged TEPA-terephthalamide modified bitumen and BHETA- terephthalamide
modified bitumen, respectively. Thus, both modified bitumen samples under un-aged conditions as well as RTFO aged
conditions showed acceptable values up to a temperature of 64 °C against a lower value of 64 °C.

Table-8: Bending Beam Rheometer

40 Properties TEPA-Modified BHETA Modified Specification
Temperature Stiffness m-Value Stiffness m-Value ASTM:D 6648 Maximum Stiffness =300 MPa and
Minimum m-value = 0.300
-6 °C Not Applicable
-12 °C 103 0.466 99.7 0.448
45
-18 °C 296 0.348 250 0.346

[0057] A comparative study of BBR test data for neat and modified bitumen samples is given in the Table 4.4. The
table showed that the modified bitumen have stiffness 296, 250 MPa and m-value 0.348 and 0.346 at -18 °C for TEPA-
50
Modified and BHETA-Modified bitumen respectively. This means that, BHETA-modified and TEPA-Modified bitumen
samples are consistently matched the desired value limits at -18 °C and thus these modified bitumen binders will be
more resistant to low temperature cracking.

55
Claims

1. A process for preparing modified bitumen comprising, reacting amido amines or polyamido amines; isocyanate or

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 EP 2 924 096 A1

polyisocyanate; and bitumen in a solvent to obtain modified bitumen.

2. The process as claimed in claim 1, wherein amido amines or polyamido amines are reacted with isocyanate or
polyisocyanate, prior to reacting with bitumen.
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3. The process as claimed in claim 1, wherein amido amines or polyamido amines; isocyanate or polyisocyanate; and
bitumen are reacted simultaneously.

4. The process as claimed in claim 1, wherein amido amines or polyamido amines are prepared by reacting polyethylene
10 terephthalate (PET) with amines or polyamines.

5. The process as claimed in claim 1, wherein amido amines, terephthalamide or polyamido amines are present in
0.05-30% wt/wt of bitumen.

15 6. The process as claimed in claim 1, wherein the isocyanates or polyisocyanates are present in 0.05-30% wt/wt of
bitumen.

7. The process as claimed in claim 1, wherein the reaction is conducted at a temperature of 50°C to 190°C.

20 8. The process as claimed in claim 1, wherein the reaction is conducted for a period of 10 minutes to 8 hours.

9. The process as claimed in claim 4, wherein amines or polyamines are selected from the group comprising ethylene
diamine, triethylene tetramine, propylene diamine, trimethylene diamine, hexamethylene diamine, decamethylene
diamine, octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamine, tri-
25 methylene diamine, pentaethylene hexamine, di(trimethylene)triamine, N-(2-aminoethyl)piperazine, 1,4-bis(2-ami-
noethyl)piperazine, an aromatic polyamine selected from phenylene and napthylene diamines or hydrazines such
as hydrazine, organo-hydrazines having hydrocarbon-based substituents of up to about 30 carbon atoms.

10. The process as claimed in claim 1, wherein isocyantes or polyisocyanates are selected from the group comprising
30 hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate (HMDI), ethylene diisocyanate, ethylidene
diisocyanate, propylene, butylene diisocyanate, diisocyanate dichlorohexaméthylène, furfurylidene diisocyanate,
Cycloaliphatic polyisocyanates, like isophorone diisocyanate (IPDI), cyclopentylene-1, 3-diisocyanate, cyclohexy-
lenedimethylene-1-diisocyanate, cyclohexylene-1, 2-diisocyanate, and mixtures thereof, aromatic polyisocyanates
like the 4, 4 ’-diphenyl diisocyanate (MDI) and its isomers, such as 2,4’ - and 2, 2 ’-diphenylmethane diisocyanate,
35 toluene diisocyanate (TDI) and isomers thereof, particularly the 2,4 - and 2,6-toluene diisocyanate, 2, 2-diphenyl-
propane-4’-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, 1,4-naphtha-
lene diisocyanate, 1, 5-naphthalene diisocyanate, azobenzene-4, 4’-diisocyanate, diphenyl sulfone-4, 4’-diisocy-
anate, 1-chlorobenzene-2 ,4-diisocyanate, 4 4 ’, 4 "-triisocyanatotripheriyl methane, 1, 3, 5-triisocyanato-tetraiso-
cyanate, and mixtures thereof.
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11. The process as claimed in claim 1, wherein the solvent is selected from Dimethyl formamide (DMF), Dimethyl
sulphoxide (DMSO), acetone, Methylethyl ketone, Tetrahydrofuran (THF), Ethyl acetate, Benzene, Toluene, Chlo-
robenzene, Hexane, Cylohexane, Xylene and Dichloro Methane(DCM).

45 12. The process as claimed in claim 1, wherein the polyisocyante is diisocyanates, selected from MDI and its isomers,
TDI and its isomers, HDI, IPDI and derivatives thereof.

13. The process as claimed in claim 1, wherein amido amines, terephthalamide or polyamido amines and isocyanate
or polyisocyanate are reacted to obtain a polyureathane.
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14. The process as claimed in claim 1, wherein amido amines or polyamido amines and isocyanate or polyisocyanate
are reacted to obtain a polyurea.

15. A bituminous cement mixture comprising polyurethane or polyurea polymers as claimed in claims 13 and 14, in
55 body of bitumen.

16. A bituminous concrete comprising bituminous cement mixture of claim 1 and an aggregate.

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• EP 0561471 A1 [0009] • EP 0667886 B1 [0009]

• WO 2012007418 A1 [0009] • WO IB2013050974 W [0037]

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