FIELD OF THE INVENTION
[001] The present invention relates to anti stripping compounds for
bitumen in general, and to an environment friendly method for disposal of waste plastics through conversion of polyethylene terephthalate (PET) polymers to anti-stripping compounds in particular. The invented process is for improving anti-stripping properties of bitumen and for safe and environment friendly large scale disposal of used PET polymer through a green chemistry approach.
BACKGROUND OF THE INVENTION AND PRIOR ART
[002] In recent past, problems relating to water damage to bituminous
pavement have received attention of researchers toward a phenomena referred to
as "stripping". Stripping relates to bituminous pavements that exhibit separation
of the bitumen from the aggregate surfaces in bituminous concrete due primarily
to the action of water on the bitumen over time under various environmental
conditions. Use of antistripping chemicals in bitumen is practiced world over
since past six decades and a variety of chemistry has been examined.
[003] Bitumen is a dark-brown to black sticky material, solid or semi-
solid in consistency, in which the primary constituents are a mixture of paraffinic and aromatic hydrocarbons and heterocyclic compounds containing sulfur, nitrogen and oxygen. The particle size of mineral aggregate used in bituminous concrete composition may vary over a wide range, such as from 2×10-5 to 6×10-2 meters in diameter or the aggregate may be of a fairly uniform size. Mineral aggregates employed in bituminous compositions also range in character from hydrophilic to hydrophobic. It has long been known that mineral aggregates have a greater attraction for water than for oil or bitumen. In general siliceous and acidic minerals such as sands and gravels are highly hydrophilic, whereas calcareous and alkaline materials such as limestone are slightly hydrophilic. Due to these variations, it is difficult to obtain and maintain a satisfactory bitumen coating on the mineral aggregate particles when water is present. A poor bitumen coating on the mineral aggregate leads to break up of the bituminous concrete

and commonly results in poor pavement quality with highly reduced life span. A successful method of increasing pavement life has been to add anti-stripping additives to the bituminous compositions. Such additives increase the hydrophobicity of the aggregate, thereby strengthening and preserving the bitumen-aggregate bond. In view of emerging need to protect bituminous pavements from damage due to their exposure to moisture, improvement in bitumen properties through use of chemical additives is currently a much investigated subject.
[004] Plastics, in modern civilization, have become rather indispensable
due to certain inherent advantages they offer such as their light weight, ease of manufacture on large scale, high degree of flexibility and less consumption of energy per unit volume as compared to metals in manufacturing process. The most commonly used plastics, under the class "thermoplastic", are low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), polyproylene copolymer (PPCP), polyvinyl chloride (PVC), polystyrene (PS), polyethylene terphthalate (PET) etc and together they constitute 80% of total polymers produced worldwide. The polyester industry makes up about 18% of world polymer production and is third after polyethylene (PE) and polypropylene (PP). Because PET is an excellent barrier material, plastic bottles made from PET are widely used as drinking water/soft drinks containers. The majority of the world's PET production is for synthetic fibers (in excess of 60%) with bottle production accounting for around 30% of global demand. Over the last few years, PET use for water bottles has grown at exceptional rates, driving PET solid-state resin demand and its production in the developed regions, growing at an average annual rate of approximately 4.3% during 2009-2013. India uses about 14 MMT plastics as against US consumption of 40 MMT and China's consumption of about 38 MMT. Large scale use of these plastic materials in various forms and their poor recycle/disposal practices have made them omnipresent and are identified as a major culprit for environmental pollution. This acute problem has led to global debate on "Plastic vs. No Plastics" and placed plastics under shadow of doubt about their real usefulness.

[005] Disposal of plastic material in general and PET based products
like bottles for water/soft drinks etc. in particular, has become mainly responsible for current pollution menace on streets. This pollution, besides being health hazard, is a particularly visible eye sore, in streets, near railway tracks, market places etc all over the world and more particularly in growing economies like India. To promote the conservation and recycling of plastic materials, several countries made legal provisions e.g. US promulgated the "Resource Conservation and Recovery Act (RCRA)" in 1976 and India developed "Recycled Plastic manufacture and Usage Rule) in 1999, with further amendments in 2003. Different options which are practiced today to recycle/reuse plastics include, but not limited to, land filling, use in solid fuel briquetting, promotion of biodegradable polymers, primary and secondary recycling of waste plastics, use in blast furnace as reducing agent, use in cement industry for energy recovery, gasification to liquid and gaseous fuels/lubricants, producing value added products, such as flouro-lubricants from waste teflon, using plastics as raw material for some chemical processing such as converting PET into Bis-(hydroxyl ethylene carboxymide)-benzene, which is used as anti-corrosion additive in modern paints, etc.
[006] In recent years one of the important developments in the field of
alternate application of virgin or used plastic/rubber material 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 advantage 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 has begun in India in the last decade, particularly under highway development programme, albeit slowly due to high cost of popular polymers such as SBS, EVA etc which are recommended modifiers for bitumen.
[007] Bitumen and aggregate materials useful for building of highways
are well known. In order to obtain pavement of high quality and strength, more

effective ways are to use acidic rocks (SiO2 content of rocks > 66%) such as
granite (a silicate rock) which has high strength and provides good resistance to
wear and skid. But the acidic rocks have poor adhesion to bitumen leading to
easy stripping of the bitumen, particularly in presence of moisture. To prevent
bitumen stripping, studies have been undertaken on anti-striping chemicals
whose addition into bitumen can greatly improve the adhesion between bitumen
and acidic aggregate materials and thus increase the life of the pavement.
[008] Curtis (1990) in his review article on liquid antistripping
chemicals "SHRP-A/UIR-90-016 Strategic Highway Research Programme" covered examples of some basic additives used in the past for this purpose, which include the primary alkyl amines, e.g., lauryl amine, stearyl amine, and the alkylene diamines, particularly the alkyl-substituted alkylene diamines, e.g., N-stearyl-l,3-propylene diamine. Amides are also used in some anti-stripping formulations. Most popular chemicals in general belong to following groups
• Nitrogen containing oil soluble liquid additives, mostly fatty acid based polyamine polyamides
• Polymers such as SBS, EVA etc showing anti-stripping properties
• Cationic surfactants
• Mineral based chemicals such as lime
• Organo- compounds Silicone
[009] Carlo Gravarini and G. Rinaldi ("Development of new
Adhesion Agents for Asphalt Cement", Ind. Eng. Chen. Res. 1989, 28, 1231-36) reported good antistripping property of product derived from reaction of tetra ethylene pentamine (TEPA) and formaldehyde (CH20) or with formaldehyde (CH20) and phenol.
[010] Al-Handy et al ("Starch as a modifier for asphalt paving
material"; Const Bldg mat 25 (2011) 14-20) reported the use of starch as more
cost effective binder modifier for road pavements and more specifically for
special paving construction sites when fuel or chemical resistance is desired.
[011] Evans E.D in US patent 3246008, 1966 claimed significant
antistrip property in reaction product of ozonized fatty acids and polyamines.

[012] Sawatzky, H. (1982) (in European Patent EP0549379) reported
that nitrogen containing fraction derived from sewage sludge, improves the adhesion of asphalt to aggregate in asphalt concrete, and is an improved anti-stripping agent.
[013] Hesberger in US Patent no 2430815 (1945) reported use of Tall
Oil to increase the adhesivity of bitumen to mineral aggregates. The use of Dihydroxy aluminium sulphonates as an anti stripping agent in bitumen was described.
[014] Jack N. Dybalski, of Armak Company (in AAPT annual meeting
Kansas City, Missouri 1982) recommended treatment of aggregates with cationic type surfactants to get maximum antistrip behavior.
[015] D.N. Little & Jon A. Epps (2001) (National Lime Association
2001; "The benefits ofhydratedlime in hot mix asphalt") reported use of lime as antistrip agent which also gives certain additional advantage such as stiffening of bituminous binder, control of fracture growth at low temperature, reducing aging effect and altering plastic properties of bitumen.
[016] Firas Awaja (2005) gives a review (European Polymer Journal
41(2005)1453-1477) on recycling of PET covering process engineering in PET
thermal degradation, chain extension process, reactive extrusion process etc.
[017] Paszum D. et al (1997) (Ref: Ind Eng Res 1997,36,1373)
reviewed chemical recycling of PET and reported that methanolysis and
glycolysis of used PET has been used commercially in coating materials and as
plasticizer. Chemical degradation through aminolysis has been explored using
different amines such as allyl amines, morpholines, hydrazine, polyamines etc.
[018] Shukla (2006) (Ref. S.R.Shukla, Ajay M Harad, Polymer
Degradation and Stability 91,2006,1850-1854) reported reaction of PET with ethanolamine using acetic acid, sodium acetate and potassium sulphate as catalyst which was completed in 8 hours resulting in bis(2-hydroxyethylene) terephthalamide (BHETA). The paper reports use of PET material and amine in molar ratio of 1:6 and maximum conversion efficiency into BHETA Bis (2-Hydroxy Ethylene) Terphthalamide, in the range of 68.2 to 83.2% under different catalytic conditions and temperature range of 170°C -180°C.

[019] Magda E.T. et al (2010) (Polymer degradation and stability
95,(2010)187-194) studied chemical recycling of post consumer PET bottle using ethanolamine and Dibutyl tin oxide (DBTO), sodium acetate, cetyl trimethyl ammonium bromide as catalyst at 190°C in about 62% yields and used the reaction product in developing anticorrosion paints.
[020] Spychaj T. (2001) (J Mat cycles and waste management 3,24-
31,2001)) reported aminolysis and aminoglycolysis of waste PET in which
experiments were conducted at 200-210°C (with a molar ratio of recurrent
polymer unit to amine of 1:2). The amines used were diethylenetriamine,
triethylenetetramine and their mixtures, p-phenylenediamine or triethanolamine.
The products thus developed were tried out as hardener for liquid epoxy resin.
[021] From the prior art covered above, it becomes clear that in PET
aminolysis process to recycle waste PET, the conditions used were quite harsh and makes use of a range of catalysts, some of which are quite costly and hazardous. There are also no reports of using the product derived from PET by aminolysis for any applications in petroleum industry in general and bitumen in particular.
[022] In addition to above, some alternate chemistry based products
have been tried over the years for antistripping properties. However, prior art documents do not mention any work on antistripping chemicals which may have been derived from PET polymers.
OBJECTS OF THE INVENTION
[023] An object of the invention is to provide a process to convert PET
polymers, whether used or virgin, into chemical compounds which show excellent anti-stripping properties in bitumen.
[024] Another object of the invention is to provide a process for
improving anti-stripping properties of bitumen with such chemical compounds.
[025] Yet another object of the invention is to provide a process which
operates in relatively low temperature range of 110 to 160°C.

[026] One more object of this invention is to demonstrate that molar
ratio of costly amines to PET is significantly reduced when conditions of the
present invention, i.e. use of solvent, are met during aminolysis of PET.
[027] Another object of the invention is to provide a process which
achieves a maximum conversion efficiency of 100% into diamido diamine
products mixture and produces no effluent.
[028] Yet another object of the invention is to provide a process where
the reaction time for condensation of polyamine and PET is significantly low
when compared with the prior art.
[029] A further object of the 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 product.
[030] A still further object of the invention is to provide a process that is
a single pot reaction, energy efficient and is completed in lesser time.
[031] Yet another object of this invention is to provide a process
wherein no catalyst is required during aminolysis of PET thus obviating the need
of toxic catalysts.
[032] Another object of the invention is to provide a process for
effective and large scale disposal of PET polymers which are environmental
hazards.
[033] A further object of the invention is to provide a process for
preparation of a bituminous cement mixture per se 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 anti-stripping properties.
SUMMARY OF THE INVENTION
[034] The present invention discloses an environment friendly method
for disposal of waste plastics through conversion of polyethylene terephthalate (PET) polymers to anti-stripping compounds. It is achieved through green chemistry approach. The PET polymer is either recycled or virgin and is used as synthon. The process gives a solution for safe and environment friendly large

scale disposal of used PET polymer such as used PET bottles and containers which are discarded after use, and become a major source of environment pollution.
[035] The anti-stripping compound of the invention is the reaction
product obtained by reacting an amine with used PET polymer which is a major culprit for environmental pollution in the cities. These reactions, using PET as synthon, can be carried out with a number of different reactants (amines, polyamines) under a variety of different reaction conditions. It is reacted with a polyamine, preferably tetraethylene pentamine in xylene solution, when the polyamine undergoes aminolysis reaction with PET without any catalyst and at a relatively low temperature in the range of 110°C to 160°C. The process achieves the maximum conversion efficiency of 100% into diamino diamido mixture of compounds and produces no effluent.
[036] A process for producing a bituminous concrete having high anti-
stripping properties is also disclosed.
DETAILED DESCRD7TION OF THE INVENTION
[037] The invention will now be described in an exemplary
embodiment. There may be other embodiment of the same invention, all of which are deemed covered by this description.
[038] The present invention discloses a process to use PET polymers,
whether used or virgin, as synthon and convert them into chemical compounds
which show excellent anti-stripping properties in bitumen, and also a process for
improving the anti-stripping properties of bituminous concrete mixture by using
such chemical compounds. The method comprises adding to an asphalt cement
mixture, a compound which is produced by reacting an amine or polyamine and
PET with or without the presence of catalysts and with or without the presence of
solvent or mixture thereof. The reaction components may be reacted together
simultaneously or alternatively in a separately identified sequence.
[039] The invention represents an example of "green chemistry" since it
is a single pot reaction with atom economy of high order and converts an

environmentally hazardous material into an industrially useful product. The study, conducted in the present invention showed that synthesis, with or without solvents and without catalyst as well, had the advantages of high yields, facile reaction with small energy consumption. Moreover, the reaction produces no effluents.
[040] In laboratory experiment, anti-stripping agents for bitumen have
been obtained by condensation of several polyamines (but not limited to) such as
tetraethylenepentamine (TEPA), triethylenetetramine (TETA),
diethylenetriamine (DETA) and ethylenediamine (EDA), propanediamine (PDA), hexamethylene triamine (HMT), p-Phenylenediamine etc. It was observed that the reaction product mixture in 0.3 to 0.5% dosages, had given excellent anti-strip properties with 100% anti-strip performance in boiling water test (Table 2), both before and after TFOT test including retained Marshal Stability test (Table 3). Reaction products of synthon PET with diamines, other than polyamines, did show anti-stripping properties but only with higher dosages i.e 1% or above and were not so effective. The reaction time for condensation of polyamine and PET is significantly low in this present invention when compared with the prior art.
[041] A bituminous concrete mixture developed in the present invention
is having therein a minor amount of an anti-stripping chemical mixture, produced by the condensation reaction of a polyamine and PET in solvents with or without the presence of catalysts.
[042] Unlike what is reported in prior art, polyamines can undergo
aminolysis reactions with PET even without a catalyst and at relatively low
temperatures (110° to 160°C) when reaction is carried out in solvents like
toluene, xylene, decalin, tetralin, o-chlorobenzene or mixtures thereof.
[043] Moreover, no catalyst is required during aminolysis of PET when
a solvent like toluene, xylene, decalin, tetralin, o-chlorobenzene or mixtures
thereof etc are used, thus obviating the need of toxic and costly catalysts like lead
acetate, dibutyl tin oxide (DBTO) etc as used in the prior art.
[044] Further, molar ratio of costly amines to PET is significantly
reduced when conditions of the present invention, i.e. use of solvent, are met

during aminolysis of PET. Instead of use of a Polyamine:PET molar ratio of 1:2 as reported in prior art, the present invention reports successful completion of
reaction in ratios ranging from 1:1 to 1:6.
«
[045] The reaction is performed under green chemistry concept which
ensures that the process which is a one step reaction, is done at relatively lower
temperature, ensures atom economy, produces no effluent and uses no catalyst.
Typical reaction conditions are given in Table-1. The invention also provides
protection of the environment since it converts waste PET polymers, which are
environmental hazards, into useful antistripping chemicals for bitumen.
[046] The present invention gives an economic and practical solution to
industrially utilize used and waste PET polymer, thus minimizing a major source of concern in keeping the environment free of pollution and hazardous materials. It opens up a new avenue for effective and large scale disposal possibilities of PET polymers.
[047] The anti-stripping compounds disclosed in this invention impart
improved adhesion between the bitumen concrete and the aggregate surfaces to which the bitumen is applied. Such surfaces are less subject to deterioration caused by the stripping effects of water in combination with other environmental effects.
[048] In addition to providing a method for improving the anti-stripping
properties of bitumen, the invention provides a bituminous cement mixture per se as well as the combination of that mixture with an aggregate in a form for road paving, i.e. a bituminous concrete. The mixture is comprised of bitumen cement, having therein minor amounts of the anti-stripping agent prepared in accordance with the present invention and which is produced by the condensation of the amines/polyamines and PET. The PET and amines can be reacted together in a variety of ratios, kept within the range of (l):(l-30) but more preferably in (1):(2) ratio and in solvents and their mixtures. When the reactant components are reacted together, they form a statistical mixture of compounds which constitute the anti-stripping agent of the present invention. Specifically, the anti-stripping agent is in the form of a composition containing a statistical mixture of compounds encompassed by the general structural formula:

R'1NCH2CH2-(CH2CH2NH)n-CO-C6H4-CO-(NHCH2CH2)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. R'1N and or R"2N could also be alkyl or substituted aromatic groups or an oligomer derived from aminolysis of PET.
[049] A bituminous concrete having high anti-stripping properties is
prepared by adding minor amounts in the range of 0.1 to 5% by weight of the anti-stripping agent according to the present invention to the bitumen cement and mixing with an aggregate in the form of local granite rocks. Evaluation of Antistripping Additives:
[050] There are different performance tests, based both on laboratory
and field testing, for evaluating anti-stripping properties developed over the years but none is accepted fully as correlating with real field conditions. These tests have been classified in different categories such as Dynamic Immersion tests, Static Immersion tests, Water Boiling tests, Chemical Immersion tests, Abrasion tests, Simulated Traffic tests Quantitative Coating Evaluation tests, Non-Destructive tests, Immersion-Mechanical tests. Boiling water test, Marshall Stability test and freeze-thaw test, which are commonly practiced to quickly judge the anti-stripping properties of various chemicals and aggregates. Some of these tests are included in relevant ASTM D 3625-96 or IS.6241/71 specifications.
[051] Two performance tests, namely hot water immersion test and
retained marshal stability were used for evaluation of chemicals under this invention and a summary of the tests are as follows: Hot Water Immersion Tests
[052] Boiling Water Test is a visual rating of the extent of stripping
after the mixture is boiled. 238 grams of washed and dry aggregate and the 12.5 gm of melted bitumen is doped with the anti-stripping agent, mixed properly and are kept in oven at 85-100°C. Then a 2,000 ml beaker is filled halfway with distilled water and boiled. The mixture is placed in boiling water for 10 minutes.

Asphalt cement that is floating is skimmed off from the top. The water is cooled
to room temperature and then poured off. The aggregate mixture is emptied onto
a white paper towel and graded, then visually observed for the remaining
percentage of coated area (not stripped by water). After 24 hours the aggregate
mixture is observed again. A mixture that retains 75% to 85% of the asphalt
cement is considered as acceptable for use in the field.
Retained Marshal Stability Test
[053] This method of test covers the procedures for testing bituminous
mixes to determine optimum Asphalt Content and stability characteristics,
including resistance to plastic flow and flow properties. The stability portion of
the test measures the maximum load supported by the test specimen at a loading
rate of 50.8 mm/minute. Load is applied to the specimen till failure, and the
maximum load is designated as stability. During the loading, an attached dial
gauge measures the specimen's plastic flow (deformation) as a result of the
loading. The flow value is recorded in 0.25 mm (0.01 inch) increments at the
same time when the maximum load is recorded
[054] Some of antistripping chemicals, developed under this invention
(Code named PET A, PET B, PET C and PET D and after blending with bitumen
in appropriate ratio, have been tested for Hot water immersion tests (Table 2),
Retained Marshal Stability test (Table 3) and Physico-chemical tests (Table 4).
These tests confirm acceptability of developed product mixture as antistripping
chemical for bitumen and their performance well comparable to commercial
products, currently being used by oil industry.
Experimental Procedures
Materials:
[055] Different materials used in analysis and reactants in the invention
are described in this section.
Aggregates:
[056] Aggregates are local granite rocks employed in preparing the
pavement. The stones used were regular, close to a cube in the shape, and of such
particle size that 100% passed a 19-mm sieve and were retained on a 13.2-mm

sieve. The stones are washed in distilled water to remove all fines, dried at 105 /-
5 °C to constant weight, and stored in airtight containers until required for use.
Bitumen:
[057] Experiments were carried out with commercial VG 10 grade
bitumen obtained from the Mathura refinery of the applicant, meeting BIS
specification IS 73-2006. Typical properties of bitumen used are given in Table
5.
Poly amines:
[058] The invention encompasses the use of one or more amines and
polyamines as reactant, represented by general structural formulae:
NR1 CH2CH2NH-(CH2CH2NH)n CH2CH2NR2
NR2 (CH2CH2)n NR1
NR1(CH2CH2NH CH2CH2)n NR2
where N is nitrogen, R1 and R2 are each independently a hydrogen or alkyl
moiety and n an independent integer in the range of 1 to 10. NR1 and or NR2
could singly or otherwise also be alkyl or substituted aromatic groups.
[059] Some examples of useful alkylene polyamine include ethylene
diamine, triethylene tetramine, propylene diamine, trimethylene diamine,
hexamethylene diamine, decamethylene diamine, octamethylene diamine,
di(heptamethylene)triamine, tripropylene tetramine, tetraethylene pentamine,
trimethylene diamine, pentaethylene hexamine, di(trimethylene)triamine, N-(2-
aminoethyl)piperazine, l,4-bis(2-aminoethyl)piperazine. The amino compound
can also be an aromatic polyamine such as the phenylene and napthylene
diamines or hydrazines such as hydrazine itself and organo-hydrazines having
hydrocarbon-based substituents of up to about 30 carbon atoms.
[060] Other diamines which have been experimented with and tested in
the current invention include ethylene diamine, triethylene tetramine, propylene
diamine, trimethylene diamine, hexamethylene diamine, decamethylene diamine,
octamethylene diamine, di(heptamethylene)triamine, tripropylene tetramine,
tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine,
di(trimethylene)triamine, N-(2-aminoethyl)piperazine, l,4-bis(2-
aminoethyl)piperazine, and p-phenylenediamine. The reaction product mixture of

these amines with PET under the condition specified showed varying degree of performance ranging from very good to good. The condensation products of diamines with synthon PET, which showed very good performance are tetraethylenepentamine (TEPA), triethylenetetramine (TETA) and diethylenetriamine (DETA). Polyethylene terephthalate (PET) polymer:
[061] Polyethylene terephthalate commonly abbreviated PET, PETE or
PET-P, is a thermoplastic polymer resin of the polyester family and is used in synthetic fibers; beverage, food and other liquid containers, thermoforming applications and engineering resins. The majority of the world's PET production is for synthetic fibers (in excess of 60%) with bottle production accounting for around 30% of global demand. The polyester industry makes up about 18% of world polymer production and is third after polyethylene (PE) and polypropylene (PP).
[062] PET may exist both as an amorphous (transparent) and as a semi-
crystalline polymer. The semi-crystalline material might appear transparent (particle size < 500 nm) or opaque and white (particle size up to a few microns) depending on its crystal structure and particle size. Its monomer can be synthesized by transesterification reaction between ethylene glycol and dimethyl terephthalate with methanol as a byproduct. Polymerization is through a polycondensation reaction of the monomers.
[063] PET consists of polymerized units of the monomer ethylene
terephthalate, with repeating C10H8O4 units. The PET, used as synthon in this invention, covers a wide range in terms physicochemical properties including intrinsic viscosity and application fields (Table 6). These also and specifically include used and recycled PET based products such as bottles for drinking water, soft drinks, fibers, packaging materials, and engineering plastics and its IR spectra gives major peak at 1720 cm"1 confirming the presence of ester functionality. The present invention specifically used two types of PET, namely bottle grade and fiber grade material, which were supplied by Reliance Industry Limited, India for laboratory work (Table 7).

Catalysts:
[064] Prior art for aminolysis reactions of PET with amines include use
of several catalysts such as dibutyl tinoxide (DBTO), Magnesium acetate tetra hydrate, calcium acetate monohydrate, calcium acetate hydrate, barium acetate, cobalt(II) acetate tetra hydrate, aluminum acetate, lithium acetate, sodium acetate, lead(IV) acetate, manganese(II) acetate, Tin(II)acetate and Zinc acetate dihydrates. The reaction with catalysts are generally conducted at a temperature range of 180°C to 220°C and takes about 8 hours to complete. In the present invention, an attempt was made to perform this reaction without the presence of catalyst and it was established that reaction done in a solvent helps in significant reduction in the temperature atleast by 30°C and time of reaction by about 4 hours. Solvents:
[065] It was established that the use of solvent helped in reaction
progress and in reducing the temperature requirements. Solvents such as tetralin, decalin, Dichlorobenzene, Trichlorobenzene, Sulpholane, Xylene, Toluene or mixture thereof have been used. It was found that reaction is complete even without catalysts, when used PET (bottle grade) and diamines are refluxed in certain solvents like xylene for four hours only. In other polymer grades of PET also, reaction proceeds on similar lines but time taken is more. EXAMPLE-1
[066] A three necked, 500 ml round-bottomed flask equipped with a
heating mantle, overhead stirrer, water condenser, nitrogen gas sparging tube and a thermo well pocket containing thermometer (50°C to 300°C range) was charged with 30 gms of PET (in the form of granules or powder or small cut pieces) and 60 gms of a polyamine e.g. tetraethylene pentamine in 200 ml of xylene solution. A current of dry nitrogen was constantly maintained. Slowly the mixture was heated to reflux temperature of xylene and then held there for 4 hours. At the end of reaction the solvent was distilled off and the unreacted polyamines were recovered under vacuum. The resulting product, recovered in quantitative yields, is a semi-viscous liquid at ambient temperatures. The IR spectra of the reaction product mixture showed peaks at 1632.4 cm"1, 1554.4 cm"1

confirming the formation of amide functional group in the product mixture. The residue was diluted with water (100ml) and refluxed for 5 minutes and allowed to cool for 5 hours when a yellow solid product, hygroscopic in nature, was obtained and filtered and dried (m.p 45°C-47°C). The crude product mixture or the purified solid product showed excellent anti-stripping properties when blended with bitumen in 0.3 % to 0.5% dosages and tested through hot water boiling tests both before and after thin film oxidation tests (TFOT). Marshall Stability test results are shown in Table 2 confirming full compatibility of invented product with bitumen. EXAMPLE-2
[067] A three necked, 500 ml round-bottomed flask equipped with a
heating mantle, overhead stirrer, water, condenser, nitrogen gas spurging tube and a thermo well pocket containing thermometer (50°C to 300°C range) with 30 gms of PET in the form of granules or powder or small cut pieces, 120 gms of pentaethylene hexamine and 150 ml toluene. A current of dry nitrogen is constantly maintained. Slowly mixture is heated and temperature is maintained at 130°C-140°C. The reaction was held under reflux for 8 hours. The solvent and excess polyamines were evaporated under high vacuum, resulting in a semi-viscous liquid at ambient temperature. Further processing is similar as given in example 1. EXAMPLE-3
[068] A three necked, 500 ml round-bottomed flask equipped with a
heating mantle, overhead stirrer, water condenser, nitrogen gas spurging tube and a thermo well pocket containing thermometer (50°C to 300°C range) was charged with 30 gms of PET in the form of granules or powder or small cut pieces, 60 gms of p-phenylene diamine, 0.6 gms of catalyst (Bismuth triflate) and 200 ml dichlorobenzene. A current of dry nitrogen was constantly maintained. The mixture was slowly heated. The temperature of the reaction mixture was raised to 160°C and refluxed for 4 hours while removing the water of reaction. The solvent and excess polyamines were evaporated under high vacuum, resulting in a semi-viscous liquid at ambient temperatures. Further processing was similar as described in example 1 above.

We Claim:
1. An Environment Friendly Method for disposal of waste plastics through conversion of polyethylene terephthalate (PET) polymers to anti-stripping compounds for bitumen comprising the steps of:
- treating PET and a polyamine in a solvent under dry nitrogen atmosphere;
- heating the mixture slowly;
- distilling off the solvent at the end of reaction;
- separating the solid product of the reaction;
characterized in that the polyamine undergoes aminolysis reaction with PET without any catalyst and at temperatures in the range of 110 °C to 160 °C. 2 The method as claimed in claim 1, wherein PET polymer is either recycled or virgin and is used as synthon.
3. The method as claimed in claim 1, wherein the wt by wt ratio of amine to PET is in the range of 1:1 to 1:6.
4. The method as claimed in claim 1, wherein the method achieves the maximum conversion efficiency of 100% while converting into diamino diamido product mixture.
5. The method as claimed in claim 1, wherein the solvent can be toluene, xylene, decalin, tetralin, o-chlorobenzene or a mixture thereof.
6. The method as claimed in claim 1, wherein the polyamine can be tetraethylenepentamine (TEPA), triethylenetetramine (TETA),

diethylenetriamine (DETA),ethylenediamine (EDA), propanediamine (PDA), hexamethylene triamine (HMT) or p-phenylenediamine.
7. The method as claimed in claim 1, wherein the method achieves reduction in temperature reflecting a major drop by about 30°C.
8. The method as claimed in claim 1, wherein reaction time of condensation of polyamine and PET has been reduced by 3-5 hours.
9. A method for preparing a bituminous concrete having high anti-stripping properties, comprising the steps of adding minor amounts in the range of 0.1 to 5% by weight of the anti-stripping compound, prepared as claimed in claims 1 to 8, to the bitumen cement and mixing with an aggregate of rocks.