The invention relates to polymer modified bitumen, being modified by physical and chemical methods modified in such a way that it is stable under storage at high-temperature and method for its preparation. The invention relates to a modifying agent for bitumen, in the form of the complex - oil-rubber composition, being prepared from a mixture of rubber granulate and castor oil, the mixture further being cross-linked during the process of bitumen modification by compounds containing in their structure reactive isocyanate groups, such as diisocyanates, polyisocyanates, and urethane prepolymers.

The popular way of improving performance and quality of bitumen is its modification by using as a modifying agent - polymers. Nowadays, polymer modifiers which are used in the industrial scale include chemical modifiers (epoxy resins or compounds with reactive isocyanate groups, such as diisocyanates, polyisocyanates, and urethane prepolymers) and physical modifiers, mostly copolymer styrene-butadiene-styrene (SBS) and copolymer ethylene-vinyl acetate (EVA). Due to economic reasons, bitumen manufacturers also use as bitumen modifiers waste polymers from the recycling process. Mainly, these are waste rubber from the recycling of car tires.

US4069182, US4021393, US4085078, US3919148 and US3844668 disclose polymer modified bitumen, that is obtained by blending heated to a temperature in the range 150-260°C bitumen with various types of rubber granulate, produced by shredding of postconsumer car tires, used in the amount variable in the range 2-15% wt. Bituminous pavements prepared from polymer modified bitumens obtained according to the methods are characterized by improved physical-mechanical properties, increased elasticity, abrasion resistance, improved rutting and low-temperature cracking resistance, compared to neat bitumen. Major disadvantages of this binders are high viscosity, which with addition of waste rubber in the amount above 15% wt. exceed 1 Pas at l80°C and lack of high-temperature storage stability (above 180°C).

Document W02007068990 discloses method of bitumen modification by shredded waste rubber, makes it possible to obtain bitumen-rubber binders characterized by reduced viscosity and hot storage stability. The method of preparation stable bitumen binders modified by rubber granulate, according to the invention is characterized in that macromolecular polyolefins in the amount of 0,03-4,0% wt., which previously were treated with chemical conversion and contain highly polar groups (proton acceptors) are added to bitumen heated to 70-230°C These compounds shall act as dispersing agent, which provide dissolution of asphaltenes, resins and paraffin components of bitumen, and due to the presence of sulfur in their structure and under their influence, the formation of chemical bonds between rubber granulate and bitumen components occurs. Also, it contains 0,01% to 4% wt. of a mixture of medium molecular weight polyolefins, paraffin, and copolymer functionalized by carboxylic groups, whose task is a reduction of bitumen binder viscosity and causing its crosslinking. Moreover, bitumen binder prepared according to the invention may contain at least 2% wt. of antioxidants and anti- corrosive agents. After mixing these compounds with bitumen, 3% to 40% wt. of rubber granulate (size of grains 1-4 mm) are added and composition is blending for 0,5-8 hours in high- temperature between l90-270°C, in order to allow carrying out the process of rubber degradation. Then obtained composition is cooled to a temperature between 160-190° and is mixed by a shearing mixer for 0,25-4 hours and after that, it is diluted with pure bitumen, so as to amount of rubber granulate in composition was 2-30% wt. In the final stage obtained polymer modified bitumen is blending for another 0,25-2 hours. The main drawback of this solution is a preparation of polyolefin modifiers in very complex and high-temperature process. Moreover, to obtain stable polymer modified bitumen long time (at least a few hours) and very high temperature (above 200°C) of modification is required.

The method of production of devulcanized rubber with using an extruder and other mixing devices such as Z-blade mixers or ball mills is disclosed in document W02009019684. In presented solution mineral oils (engine oils) or waste from the processing of vegetable and animal oils (mainly in the form of fatty acids obtained in the process of hydrolysis of these oils) were used as a swelling agents, plasticizers and devulcanization promoting agents. Devulcanization process is carried out in the presence of inhibitors of radical reaction (bis- phenols) and metal oxides, used to neutralize sulfur released in the rubber devulcanization process. In accordance with data presented, devulcanized obtained with this method may be used as a bitumen modifier, however, their influence on bitumen properties are not disclosed.

Polish patent application 408012 discloses a method of "soft" devulcanization of rubber granulate, which runs in a controlled way and enables the use of obtained devulcanized rubber in bitumen modification. Described“soft” devulcanization of rubber granulate rely on mixing of rubber granulate ( size of grains 1-1,5 mm) in the amount of 15-15% wt. with rapeseed oil in the amount of 0,5-5% wt. (these amounts were calculated on the weight of bitumen-rubber binder), obtained a modifying agent. This oil-rubber composition is left for 18-26 hours at temperature l5-30°C for swelling rubber with oil and after that this composition is added to bitumen used in the amount of 70-90% wt. at a temperature in the range of 180-200°C and the mixture is blended at this temperature for 1 hour. Bitumen binders obtained according to this invention are characterized by lower penetration, higher softening point compared to neat bitumen and relatively low viscosity, which is a result of the use of rubber swelled with vegetable oil. The patent description doesn’t provide information about the stability of this type bitumen-rubber binder.

Use of devulcanized rubber in bitumen modification was also disclosed in documents WOl 994014896 and EP2987820. Described compositions made of bitumen and devulcanized rubber, obtained by thermo-mechanical devulcanization of shredded waste tires in a twin screw extruder. This composition may also contain thermoplastic elastomers (polystyrene copolymers, mainly copolymer SBS) and plastomers (polyolefins and copolymers ethylene-acrylate or ethylene and poly(vinyl acetate)), and softeners and plasticizers such as oils (mineral, synthetic, natural). Due to mixing of these modifiers with bitumen, obtained bitumen binders are characterized by resistance to low-temperature cracking (to about -40°C ) and a high softening poinftfo about 130°C) and also high viscosity (5,2-22,0 Pas at 185°C), which allows to their application in the production of roofing membranes, hydro isolations and sealant. The major drawback of this invention is very high viscosity of bitumen-rubber binders, which practically makes it impossible to use these binders in road and bridge pavements.

Document US6271305 discloses chemical cured, elastomeric polyurethane-bitumen composition, in the form of interconnected networks of bitumen (naphthenic bitumen, coal tar, bitumen modified by waste rubber, polyethylene, polypropylene, polystyrene or rubbers) and polyurethane, synthesized in situ in bitumen material. A number of polyurethane-bitumen compositions are disclosed, which are obtained for example from bitumen with penetration grade in the range 16-195 [0,1 mm], which at temperature 90-l80°C is mixed with polymeric 4,4’- diphenylmethane diisocyanate (PMDI) and various types of mixtures made up of amino-low molecular weight chain extenders and oligo(oxypropylene)diol (PPG), oligo(oxyethylene)diol (POE), oligo(oxytetramethylene)diol (PTMG), hydroxytelechelic oligobutanediol or oligodiol synthesized from castor oil and other vegetable oils. However, it should be underlined that castor oil in this invention is a component used to a synthesis of oligodiol, which in next stage is used to a synthesis of the urethane prepolymer, which acts as a bitumen modifier. In case of bitumen modified by polyurethanes and shredded waste rubber, a method of its production according to this invention in the first stage is to preparation reactive mixture of B-component including selected oligodiols, chain extenders and catalysts and C-component which is a polymeric 4,4’- diphenylmethane diisocyanate (PMDI). Reactive compositions so obtained are added to A- component, which contains bitumen and shredded waste rubber in the form of rubber granulate and immediately applied on roofs or building walls, on which take place hardening of polyurethane-bitumen compositions. According to the guidance of the author the best processing properties and performance and shortest time of gelation and hardening at 50 seconds, exhbits composition prepared with 50% wt. of bitumen modified by rubber granulate (Bitumer Inc), 30% wt. polymeric PMDI (BASF) and 36% wt. oligo(oxypropylene)diol (BASF) mixed with 0,07% wt. dibutyltin dilaurate (Air Products). As crosslinking agents are used 4% wt. equimolar mixture of 3,5-dimethylthio-2,4-toluenediamine and 3,5-dimethylthio-2,6-toluenediamine (Albemarle Corporation). The main advantage of this material is the possibility of wide application in the form of elastomeric-bitumen roof covering or materials for impregnation of the walls and foundations of the buildings. The process of bitumen modification takes place by using a modifying agent in the form of multi-component polymer and rubber-bitumen systems, which have to be mixed directly before application, in well-defined weight proportions, which in industrial scale requires using complicated, expensive and mobile devices, which provide mixing and dosing and also professional service is needed. Getting a binder with complex physicomechanical properties also requires additional use of amine crosslinking agent for urethane prepolymers, which are corrosive and pose a threat to the natural environment. Another drawback is getting a crosslinked binder as a result of mixing all of the components, which has short application time (gelation and initial hardening occurs within 50 s. of mixing all components). Therefore, polyurethane-bitumen binder after mixing all of the components and mixing this with mineral aggregate has a very short time of use. This completely limits its use in the construction of road pavements, except for minor repairs of cavities in bitumen pavements, using a dosing-mixing mobile device. Moreover shall be indicated that content of polyurethane in binders with the best properties, must reach 50% of its weight, which significantly increases the cost of its production, in relation to other known polymer-bitumen binders, in which rubber granulate and other types of polymers (SBS, EVA) are used as a bitumen modifiers. In this invention, as a bitumen modifier, unprocessed rubber granulate is used, which significantly limits its mixing with bitumen. Unprocessed rubber granulate cause also high-viscosity of obtained binders, which significantly limits the range of its use and possibility of storage and transport.

Document US7732510 discloses method of preparation humidity crosslinked polymer- bitumen binder, obtained as a result of bitumen modification by elastomers in the form of butadiene-styrene rubber SBR or copolymer SBS, or rubber granulate, and then mixing modified binder with phenol-formaldehyde resin (use as an activator), mineral or soybean oil (use as a activator carrier and viscosity reducing agent) and crosslinking agent in the form of air humidity hardening polyurethane prepolymer containing bis(4-isocyanatophenyl)methane. According to the disclosed method of modification process, in the first stage is to mixing of bitumen modified by elastomer (SBR, SBS or rubber granulate) with activator. Then to this binder, heated to 25- 220°C with continuous mixing, compounds with free isocyanate groups (NCO) are added. The binders obtained this way, after mixing with mineral aggregate and applications on the road surface are crosslinked by air humidity. Because of it, bitumen binder is showing a high degree of hardening and good resistance to fuels and aromatic solvents. Therefore this binder is dedicated to the construction of pavements in a gas station and fuel warehouses. It should be underlined that the essence of this invention is method of preparation polymer-bitumen binder with a high degree of crosslinking, which results in good fuel resistance. While the use of waste rubber as a bitumen modifier is optional, and most importantly they are used in the form of unprocessed rubber granulate, which considerably increases the viscosity of the binders and thus these type binders are unstable under hot storage and transport at a temperature above 160°C. Moreover, in these binders, phenol-formaldehyde resins as an activator are used, which react with compounds containing NCO groups. Crosslinking process of these binders begins at the stage of their preparation and activator structure encourages the formation of the high-density polymer network in the bitumen matrix, which causes an increase of binder viscosity. Moreover, storage and transport of this binder at room temperature require its protection against moisture. While storage of this binder at high-temperature (about l60-200°C) it is difficult, due to the possibility of uncontrolled increase of its viscosity under the influence of crosslinking reaction, occurring between compounds containing NCO groups and phenol-formaldehyde activator. Therefore the application of this binder must take place after its preparation.

Well known are polymer modified binders with waste rubber, including reclaimed rubber obtained as a result of thermal or thermo-mechanical devulcanization of waste rubber. Bitumen modification by rubber granulate enables to obtain a binder with enhanced elasticity properties, however, these binders are unstable and show high viscosity. While bitumen modification by reclaimed rubbers or reclaimed rubbers, which additionally were plasticized with aromatic, naphthenic or natural oils lead to preparation of polymer modified binders which show stability during hot storage and transport at high-temperature (abovel60°C), however this type of modification results in only slight improvement of bitumen properties or even their deterioration for example increased of penetration, decreased of softening point, weaker elastic and rheological properties. It is the result of loosening the cross-linked rubber structure in the devulcanization process, and thus loss of elastic properties.

On the other hand, the method of bitumen modification according to the invention, enables physicomechanical, elastic and rheological properties of bitumen modified by oil-rubber compositions to be improved, due to additional crosslinking process provided just during the method of modification and being caused by compounds containing in their structure isocyanate groups, which react with reactive groups NH ₂ , NH, OH, SH i COOH present in bitumen components, but also with reactive groups present in waste rubber and with hydroxyl groups present in castor oil, used in the process of obtaining oil-rubber compositions.

The invention relates to a modifying agent i.e. modifier for bitumen as well as a final product - polymer modified bitumen so bitumen modified by the mentioned modifying agent. Taking into account the method steps, the direct modifier, according to the invention, is separately oil-rubber composition, a mixture, and crosslinking component with NCO groups in its structure, which is added directly to bitumen to crosslinking its structure and bond it chemically with bitumen. The modifying agent for bitumen is accordingly three-components system / kit comprises: 1. castor oil 2. rubber particle - granulate while 1. And 2. Is in the form of the oil-rubber composition, which is prepared as a mixture directly added to bitumen in the method. 3. The third component is diisocyanate or urethane prepolymer - the crosslinking component - crosslinking agent, which has in its structure NCO groups and the component is not mixed with the oil-rubber composition directly, but only added in the bitumen matrix where it is mixed with the oil-rubber composition. Each of the components of the system modifies some of the bitumen properties, and moreover, a crosslinking agent through urethane, urea and isocyanurate groups connect all of the polymer modified binder components, forming homogenous network bitumen-isocyanate-oil-rubber, and thus hot storage stability is obtained. The modification takes place in conjunction with crosslinking process in situ during polymer modified bitumen preparation. The composition may be added to bitumen in the first stage of the method, before adding crosslinking component that contains NCO groups, or in another embodiment of the invention, crosslinking agent with NCO groups is added to bitumen as a first and then the oil-rubber composition. Components modifying agent comprising oil-rubber composition, obtained from rubber particle e.g. shredded waste rubber, according to the invention contains from 80,3% wt. to 98,0% wt. oil-rubber composition with castor oil. Content of waste rubber in composition is from 80% wt. to 95% wt. while content of castor oil in the composition is from 5% wt. to 20% wt. The modifying agent also contain from 2,0% wt. to 19,7% wt. of crosslinking component - agent in the form of compound containing in its structure reactive isocyanate groups (NCO). Crosslinking component - crosslinking agent, is added directly to bitumen, so mixing with the oil-rubber composition takes place within bitumen.

Preferably, as a crosslinking component with reactive isocyanate groups, the modifying agent comprises bis(4-isocyanatophenyl)methane modified by carbodiimide or urethane prepolymer, which contains free isocyanate groups in the amount 10% wt or more.

Preferably, a modifying agent comprises waste rubber particles e.g. shredded waste rubber, obtained from the recycling of postconsumer car tires.

Preferably, a modifying agent comprises particles e.g. shredded waste rubber, in the form of rubber granulate with grain sizes 1 mm or below 1 mm.

Polymer modified bitumen modified by the physical and chemical methods, according to the invention, comprises bitumen and oil-rubber composition, obtained by mixing waste rubber particle e.g. in shredded form with castor oil. The polymer modified bitumen also contains crosslinking component with reactive isocyanate groups NCO in its structure. Polymer modified bitumen contains (calculated on weight of polymer modified bitumen) from 77% wt. to 95% wt. of bitumen and from 4% wt. to 20% wt. of oil-rubber composition, wherein content of shredded waste rubber in composition (calculated on weight of polymer modified bitumen) is from 4% wt. to 18% wt., while castor oil is from 0,25% wt. to 3% wt. Polymer modified bitumen also contains from 0,25% wt. to 3% wt. of a crosslinking component - crosslinking agent in the form of compound with free isocyanate groups (NCO). The amount for the three ingredients is provided on weight of polymer modified bitumen.

Preferably, polymer modified bitumen comprises waste rubber particles - shredded waste rubber, obtained from the recycling of postconsumer car tires.

Preferably, , polymer modified bitumen comprises waste rubber particles e.g. in shredded form, in the form of rubber granulate, with grain sizes equal or below 1 mm.

Preferably, polymer modified bitumen comprises crosslinking component in the form of bis(4-isocyanatophenyl)methane modified by carbodiimide. Favorably, contains a crosslinking agent in the form of an urethane prepolymer with free isocyanate groups (NCO) equal or more than 10% - which contains free isocyanate groups in the amount above 10% wt. or above 10%. It is preferably used commercially available ether-, ester-, ether-ester-urethane prepolymer,

The method for preparation of polymer-bitumen binder modified by waste rubber is based on blending of bitumen with a modifying agent at high-temperature and according to the invention the methods includes the following steps:

In first step, on component of the bitumen modifier, in the form of oil-rubber composition is obtained by mixing castor oil with shredded waste rubber (particle - grain sizes 1 mm or below 1 mm), wherein the amount of waste rubber in a composition is from 80% wt. to 95% wt. , while the amount of oil in a composition is from 5% wt. to 20% wt.

In the step, oil-rubber composition (obtained in the first stage) in the amount from 4% wt. to 20% wt. (calculated on the weight of polymer modified bitumen), is blended using known mixing devices with bitumen in the amount from 77% wt. to 95% wt. (calculated on the weight of polymer modified bitumen), at temperature 175-185°C.

In the third step, mixture of bitumen and oil-rubber modifier (obtained in the second stage) in the amount from 77% wt. to 95% wt. (calculated on the weight of polymer modified bitumen) is blended using known mixing devices with a crosslinking agent, containing in its structure free isocyanate groups, used in the amount from 0,25% wt. to 3,0% wt. (calculated on the weight of polymer modified bitumen), at temperature 175-185°C.

The method for preparation polymer-bitumen binder modified by waste rubber is based on blending of bitumen with a modifying agent at high-temperature according to another variant of the invention is based on the following steps:

In the first stage, which may be also the second stage according to the invention, component of bitumen modifier in the form of oil-rubber composition is obtained by mixing oil with waste rubber particle - shredded waste rubber (grain sizes 1 mm or below 1 mm), wherein the amount of waste rubber in a composition is 90% wt., while the amount of oil in a composition is 10% wt. In the second stage, which may be also the first stage according to the invention, bitumen in the amount from 70% wt. to 90% wt. is blended using known mixing devices with a crosslinking component in the amount from 1% wt. to 3% wt. (calculated on the weight of polymer modified bitumen), which contains in its structure free isocyanate groups, at temperature 180±5°C

In the third stage, obtained oil-rubber composition in the amount from 9% wt. to 20% wt. (calculated on the weight of polymer modified bitumen), is blended using known mixing devices with the mixture obtained in the second stage used in the amount from 80% wt. to 90% wt. (calculated on the weight of polymer modified bitumen), at temperature l80±5°C. Preferably, in both variants of the methods according to the invention, prepared oil- rubber composition may be converted by thermal or thermo-mechanical methods at temperature l60-200°C, obtaining oil-rubber composition in the form of plasticized mass, which preferably is cooled to get final bitumen modifier.

According to the embodiment, in both variants of the invention oil-rubber composition is converted by using a periodic method, favorably with oil-heated Z-blade mixer, at the rotational speed of the mixing rotors in the range of 140-150 rpm. and maintain the temperature of 175- l85°C in the mixing chamber, while the time of mixing is from 10 to 60 minutes, favorably 30 minutes.

Preferably, in both variants of the methods, oil-rubber composition is converted by using a continuous method, in the extrusion process with single or twin screw extruder with maintaining the temperature of l60°C - 200°C on head and plastification zones.

Preferably, in both variants of the invention oil-rubber composition is converted by a periodic static method, in the process of its heating, in time no longer than 60 minutes and temperature no higher than l80°C.

Preferably, in both variants of the invention oil-rubber composition is cooled to room temperature.

Preferably, in both variants of the invention, bitumen with oil-rubber composition or with the crosslinking agent is blended using homogenizer, enabling shear mixing at a maximum level 4000 rpm., favorably 2000-4000 rpm.

Preferably, in both variants of the invention, bitumen with oil-rubber composition or with the crosslinking agent is blended for minimum 5 minutes, preferably 15 minutes.

Preferably, in both variants of the invention, mixture of bitumen and oil-rubber composition is blended with crosslinking agent or mixture of bitumen and crosslinking agent is blended with oil-rubber composition for a maximum of 55 minutes, preferably the total bitumen modification time, should not exceed 60 minutes, with mixing speed at maximum level 4000 rpm., favorably 2000-4000 rpm.

According to the invention, the method of preparation stable polymer-bitumen binder modified by waste rubber, which is characterized by low viscosity, is based on three stages. In the first stage oil-rubber composition is prepared by mixing for 5 to 60 minutes, castor oil in the amount from 2-20% wt. with waste rubber particles in the amount from 80% wt. to 98% wt. (especially with the shredded postconsumer car tires, which size of grains is below 1 mm) The method of mixing rubber particles - granulates with castor oil, at the stage of preparation of oil-rubber composition is carried out on the basis of well-known methods, according to one of three ways:

^■ Periodic method, using oil-heated Z-blade mixer, at the rotational speed of the mixing rotors in the range of 50-150 rpm. and maintain the temperature of l80°C in the mixing chamber, while the time of mixing is from 10 to 60 minutes.

^■ Continuous method, using extruder heated to a temperature of l60-200°C, favorably to l80°C +/- 5, at the rotational speed of screw in the range from 50 to 150 rpm,

^■ Periodic static method, which is based on mixing of castor oil with rubber granulate using paddle mixer in time from 5 to 10 minutes, in order to obtain complete wetting of rubber granulate by oil and heating prepared mixture in time below 60 minutes and at temperature not more than l80°C.

In the second stage, in another variant of the invention a third stage of bitumen modification, oil-rubber composition prepared in the first stage, used in the amount of 10-20% wt. are blended at 180±5°C with bitumem, used in the amount of 80-90% wt. The process of blending bitumen with oil-rubber composition, using high-speed mixing devices, at rotational speed of mixing rotor in the range from 500-10000 rpm, generating high shearing forces when bitumen is mixed with modifier for example homogenizer or colloidal mills. The time of mixing oil-rubber composition should be no more than 60 minutes, since the addition of modifier to bitumen, which is favorable due to the fact that bitumen modification by unprocessed rubber granulate in industrial practice last above 120 minutes.

In the third stage, in another variant of the invention the second stage of bitumen modification, to mixture of bitumen and oil-rubber composition, third component - crosslinking agent in the form of the compound with free isocyanate groups in their structure (such as diisocyanate, polyisocyanate or urethane prepolymers) is added. These compounds are able to create polymer network in bitumen, through the reaction with reactive groups NH ₂ , NH, OH, SH and COOH present in bitumen components, and also with reactive groups present in rubber granulate and hydroxyl groups present in castor oil. Moreover, isocyanate crosslinking agent, after addition to bitumen may adjusted viscosity of binders, and due to formation of polymer network connected with bitumen, provide hot storage stability of bitumen-rubber binders at temperature below l85°C. Crosslinking agents containing isocyanate groups are added to bitumen 5 minutes after adding oil-rubber composition to bitumen or in the favorable variant of the invention crosslinking agent is added as first and after that oil-rubber composition is added. Crosslinking process of the bitumen modified by oil-rubber composition is proceed using diisocyanate, polyisocyanate and urethane prepolymers, favorably with stable at modification temperature liquid bis(4-isocyanatophenyl)methane modified by carbodiimide (liquid-MDI, trade name Ongronat 3800, manufacturer Borsodchem) used in the amount below 3% wt. (calculated on the weight of oil-rubber modified bitumen). Blending process of the crosslinking agent with bitumen and oil-rubber composition is proceed using high-speed mixing devices, at rotational speed in the range from 500 to 8000 rpm, generating high shearing forces when bitumen is mixed with modifier, for example homogenizer or colloidal mills. Total time of mixing bitumen with oil-rubber composition and compounds with isocyanate groups, is no longer than 60 minutes. In favorable variant of the invention as the crosslinking agent also ether- urethane or ester-urethane prepolymer with amount of free isocyanate groups above 10% wt. may be used.

The subject of the invention is using to selected modifying agent for bitumen modification - modifier or modifying agent in the form of kit - 3 -components system, in the form of oil-rubber composition and crosslinking component - crosslinking agent containing free isocyanate groups, which chemically react with each other in bitumen. The components in the modifying agent have strictly defined tasks: oil-rubber composition gives bitumen elastic properties, and due to its preparation by thermal or thermo-mechanical devulcanization of waste rubber softening by castor oil, are characterized by better mixability with bitumen, in comparison with rubber granulate. Moreover, oil-rubber composition does not cause rapid growth of the binder viscosity, when the amount of waste rubber in bitumen increases, thereby it is possible to use above 15% wt. of waste rubber in bitumen modification.

Castor oil is used as a rubber granulate plasticizer and to decrease bitumen viscosity at the stage of its mixing with oil-rubber composition, moreover, due to present in its structure hydroxyl groups, reactive to isocyanate groups is chemically bonded with crosslinking agent, containing in its structure isocyanate groups (NCO).

Crosslinking component, containing in their structure free isocyanate groups (such as diisocyanate, polyisocyanate and urethane prepolymers), which due to high reactivity are able to form in the bitumen polymer network, through their reaction with reactive groups: NH ₂ , NH, OH, SH and COOH present in bitumen components, and with reactive groups present in rubber modifier and with hydroxyl groups present in castor oil. Moreover, isocyanate crosslinking agents have the function to adjust binder viscosity, and also by formation of the polymer network, bonded with bitumen structure, they provide stability of the rubber-bitumen binders, in storage at a temperature no higher than 180°C. It is very important to use as a crosslinking agents diisocyanate, polyisocyanate and urethane prepolymers stable at modification temperature i.e. l80°C.

According to the invention, bitumen modification by waste rubber is to formation in situ in bitumen modification process, polymer network combining bitumen components with waste rubber. Chemical bonding of rubber waste swelled with castor oil with bitumen according to the invention, occurs via extremely reactive isocyanate groups, present in compounds such as: diisocyanate, polyisocyante and urethane prepolymers, which react with amino (NH ₂ , NH), thiol (SH), carboxyl (COOH) and hydroxyl (OH) groups present in bitumen components and with reactive groups present in waste rubber (NH ₂ , NH, SH and COOH) and also with hydroxyl groups (-OH) present in castor oil.

Polymer modified bitumen obtained as a result of bitumen modification by modifier - oil- rubber composition and crosslinking by diisocyanate, according to the invention are characterized by improved properties, compared with neat bitumen and bitumen modified by un processed rubber granulate such as: low viscosity, high elasticity, resistance to high-temperature and reduced sensitivity to temperature, reduced tendency to permanent deformation and most importantly hot storage stability at temperature l80°C, improved physico-mechanical and rheological properties and better performance, compared with known bitumen modified by shredded waste rubber or reclaimed rubber. Polymer modified bitumen obtained according to the invention may be used as binder in bitumen- aggregate mixture, intended for road construction with high durability and elasticity, also may be used for roofing membranes, sealant and insulating materials.

The invention is presented in the embodiments described below: Example 1

In example 1. bitumen modified with oil-rubber composition and crosslinked by diisocyanate was obtained by using:

- bitumen 70/100, which penetration at 25°C is in the range 70-100 [0,1 mm], for example manufacturer LOTOS Asfalt Sp. z o. o.,

- rubber granulate, obtained by shredding of post-consumer rubber products, especially car tires, with grain size equal or below 1 mm, for example manufacturer Gumeko Sp. z o.o.,

- castor oil, characterized by viscosity at 20°C in the range 950-1100 mPas, acid value equals 1,23 mgKOH/g, hydroxyl value equals 163,9 mgKOH/g, iodine value equals 85,7 g I ₂ /100g, for example manufacturer Brenntag Polska Sp. z o.o.

- liquid at room temperature bis(4-isocyanatophenyl)methane modified by carbodiimide (liquid- MDI) for example trade name Ongronat 3800, manufacturer Borsodchem, containing free isocyanate groups in the range 27-28% wt,

The method for preparation of bitumen modified by oil-rubber composition (obtained by periodic method) and crosslinked by diisocyanate, according to example 1, included three stages:

In the first stage bitumen modifier in the form of oil-rubber composition is obtained. Oil-rubber composition in the amount of 250 g. was obtained by periodic method, using Z- blade mixer Brabender with capacity of mixing chamber about 200 cm ³ . In order to obtain this composition a conventional mechanical mixer was used, e.g. a paddle mixer, a mixture consisting of 225g of a rubber granulate, which was 90% wt. of mixture and 25 g. of a castor oil, which was 10% wt. of mixture, was made first. Mixing process of rubber granulate with oil continued until complete wetting of rubber granulate by oil, which lasted less than 10 minutes. Next this mixture was dosed to mixing chamber of oil-heated Z-blade mixer and everything was mixed at rotational speed of the mixing rotors in the range from 40 to 150 rpm and maintaining the temperature of 180±5°C, and the time of mixing was 30 minutes. Oil-rubber composition obtained in this stage was in the form of plasticized mass and was characterized by density equals l,03g/cm ³ and contant of parts insoluble in toluene of 70 % wt.

In the second stage obtained oil-rubber composition in the amount of 49, 5g, which was 9,9% wt. (calculated on the weight of polymer modified bitumen) was mixed with heated to 180°C liquid bitumen used in the amount of 445,5 g, which was 89,1% of final weight of polymer modified bitumen. Process of blending bitumen with oil-rubber composition was carried out at a temperature 180±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M). Time of blending oil-rubber composition with bitumen, in the second stage was no more than 5 minutes from adding modifier to the bitumen, at rotational speed of mixing rotors of 4000 rpm.

In the third stage of bitumen modification, according to the invention, to mixture of oil-rubber composition and bitumen heated to l80±5°C, third component of modifier, in the form of crosslinking agent - bis(4-isocyanatophenyl)methane modified by carbodiimide (liquid MDI) was added. Diisocyanate was added in the amount of 5g, which was 1,0% wt. (calculated on the weight of polymer modified bitumen), after 5 minutes from adding oil-rubber composition to bitumen. Adding of crosslinking agent to bitumen took place with intense mixing at temperature 180±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M), at rotational speed of mixing rotors of 4000 rpm.

Mixing was carried out for another 55 minutes, so total time of bitumen modification by oil- rubber composition and diisocyanate did not exceed 60 minutes.

Binder obtained in this way, may be used in the process of production bituminous mixtures for road construction or may be used for roofing membranes, sealants and insulating materials. Properties and test results of hot storage stability of the binder obtained in the example 1. are presented in table 1.

Example 2

The method for preparation of the polymer modified bitumen, according to example 2 was carried out in the same manner, in three stages and using the same materials as described in example 1 , except that, in the first stage, the time of mixing castor oil with rubber granulate in Z- blade mixer Brabender was 60 minutes. While in the second stage of bitumen modification oil- rubber composition from example 1. was used in the amount of 74 g, which was 14,8% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 420 g, which was 84,0% wt. of polymer modified bitumen. The process of bitumen modification was carried out in the same way as in the example 1., except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 6g., which was 1,2% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 1. Properties and test results of hot storage stability of the binder obtained in the example 2. are presented in table 1.

Example 3

The method for preparation of the polymer modified bitumen, according to example 3 was carried out in the same manner, in three stages and using the same materials as described in example 1 , except that, in the first stage, the time of mixing castor oil with rubber granulate in Z-blade mixer Brabender was 10 minutes, at temperaturel80±5°C. While in the second stage of bitumen modification oil-rubber composition from example 1. was used in the amount of 98,5 g, which was 19,7% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 393,5g, which was 78,7% wt. of polymer modified bitumen. The process of bitumen modification was carried out in the same way as in the Example 1., except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 8g., which was 1,6% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 1. Properties and test results of hot storage stability of the binder obtained in the example 3. are presented in table 1.

Example 4

The method for preparation of the polymer modified bitumen, according to example 4 was carried out in the same manner, in three stages and using the same materials as described in example 1, except that in the second stage of bitumen modification oil-rubber composition from example 1. was used in the amount of 97 g, which was 19,4% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to 180±5°C, used in the amount of 388, 5g, which was 77,7% wt. of polymer modified bitumen. The process of bitumen modification was carried out in the same way as in the Example 1. , except that bis(4- isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of l4,5g., which was 2,9% wt. of polymer modified bitumen, was added to mixture of bitumen and oil- rubber composition. The process of mixing bitumen with an oil-rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in the example 1. Properties and test results of hot storage stability of the binder obtained in the example 4. are presented in table 1.

Example 5

To obtain bitumen modified by oil-rubber composition and crosslinked by diisocyanate, in the example 5, using the same materials as described in the example 1., however the method for its preparation in the second and third stages was different. The method for preparation bitumen modified by oil-rubber composition and crosslinked by diisocyanate, according to example 5, included three stages:

In the first stage, oil-rubber composition was prepared by periodic method, in the same way as described in the example 1.

In the second stage, to bitumen heated to 180±5°C, used in the amount of 445, 5g, which was 89,1% wt. of polymer modified bitumen, crosslinking agent (liquid-MDI) for example trade name - Ongronat 3800 (Borsodchem) in the amount of 5,0g, which was l,0%wt. of polymer modified bitumen, was added. Adding of crosslinking agent to bitumen took place with intense mixing, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M). Mixing of the bitumen with liquid crosslinking agent was carried out at temperature l80±5°C, no longer than 5 minutes from adding crosslinking agent to bitumen, at rotational speed of mixing rotor of 4000 rpm.

In the third stage of bitumen modification in example 5, to mixture of bitumen and crosslinking agent (liquid-MDI) at temperature l80±5°C oil-rubber composition in the amount of 49, 5g, which was 9,9% wt. of polymer modified bitumen, was added. Oil-rubber modifier was added after 5 minutes of mixing bitumen with crosslinking agent (liquid-MDI). Adding of oil-rubber composition to bitumen took place with intense mixing at temperature l80±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA- TURRAX, with mixing rotor type Ml (S 50 N - G 45 M). Mixing was carried out at rotational speed of mixing rotor of 4000 rpm, for another 55 minutes, so total time of bitumen modification by oil-rubber composition and diisocyanate did not exceed 60 minutes.

Properties and test results of hot storage stability of the binder obtained in the example 5. are presented in table 1.

Example 6

The method for preparation of the polymer modified bitumen, according to example 6 was carried out in the same manner, in three stages and using the same materials as described in example 5, except that, in the second stage of bitumen modification, to bitumen heated to l80±5°C, used in the amount of 420 g., which was 84,0% wt. of polymer modified bitumen, crosslinking agent (liquid-MDI) for example trade name - Ongronat 3800 (Borsodchem) in the amount of 6,0 g, which was 1,2% wt. of polymer modified bitumen, was added and the whole was homogenized in the same way, at the same temperature and time, and using the same mixing device as in example 5. While in the third stage bitumen modification was carried out in the same way as in the example 5, except that to mixture of bitumen and crosslinking agent, oil- rubber composition in the amount of 74, Og, which was 14,8% wt. of polymer modified bitumen, was added. Properties and test results of hot storage stability of the binder obtained in the example 6 are presented in table 1.

Example 7

The method for preparation of the polymer modified bitumen, according to example 7 was carried out in the same manner, in three stages and using the same materials as described in example 5, except that, in the second stage of bitumen modification, to bitumen heated to l80±5°C, used in the amount of 394,5 g., which was 78,9% wt. of polymer modified bitumen, crosslinking agent (liquid-MDI) for example trade name - Ongronat 3800 (Borsodchem) in the amount of 7,0 g, which was 1 ,4% wt. of polymer modified bitumen, was added and the whole was homogenized in the same way, at the same temperature and time, and using the same mixing device as in example 5. While in the third stage bitumen modification was carried out in the same way as in the example 5, except that to mixture of bitumen and crosslinking agent, oil- rubber composition in the amount of 98,5 g, which was 19,7% wt. of polymer modified bitumen, was added. Properties and test results of hot storage stability of the binder obtained in the example 7 are presented in table 1.

Example 8

The method for preparation of the polymer modified bitumen, according to example 8 was carried out in the same manner, in three stages and using the same materials as described in example 5, except that, in the second stage of bitumen modification, to bitumen heated to l80±5°C, used in the amount of 388,5 g., which was 77,7% wt. of polymer modified bitumen, heated to l80±5°C, crosslinking agent (liquid-MDl) for example trade name - Ongronat 3800 (Borsodchem) in the amount of 14,5 g, which was 2,9% wt. of polymer modified bitumen, was added and the whole was homogenized in the same way, at the same temperature and time, and using the same mixing device as in example 5. While in the third stage bitumen modification was carried out in the same way as in the example 5, except that to mixture of bitumen and crosslinking agent, oil-rubber composition in the amount of 97 g, which was 19,4% wt. of polymer modified bitumen, was added. Properties and test results of hot storage stability of the binder obtained in the example 8. are presented in table 1.

Example 9

Testing properties of bitumens, obtained according to examples 1-8

Bitumens, obtained according to examples 1-8, were tested for their penetration according to PN-EN 1426, softening temperatures according to PN-EN 1427, stability tests according to PN-EN 13399 and viscosity tests at 180 ° C, and the results are shown in table 1 (for comparision also results for neat bitumen (70/100) and bitumen modified by un-processed rubber granulate (polymer modified bitumen type Bitumen/CR) and bitumen modified only by oil-rubber composition without crosslinking agent (polymer modified bitumen type Bitumen/ORC) are presented in the table 1.) Based on the results, it was found that the binders obtained in Examples 1-8 may be used in the production of bituminous mixtures for road construction, or may be used in roofing membranes, sealants and insulating materials.

Results presented in the table 1. for polymer modified bitumens, obtained according to examples 1-8 indicate that they are characterized by a higher softening point and lower penetration compared to neat bitumen 70/100. It is noticeable that used modifiers had significant impact on changing bitumen properties. However, used modifiers also caused increase of bitumen viscosity, compared with neat bitumen, but its value is for most of the polymers at the level which allows for trouble-free pumping and transport of polymer modified bitumen with pipelines. The use of a crosslinking agent in the form of liquid MDI also has a significant effect on improving the properties and stability of polymer modified bitumen. Compared to bitumen modified only by an oil-rubber composition (polymer modified bitumen type Bitumen/ORC), modified bitumen obtained according to the examples 1-8, are characterized by higher softening point and lower penetration, which indicate the fact that polymer network was formed in bitumen structure.

Polymer modified binder from examples 1-4 are characterized by storage stability according to 13399 (exeptions are polymer modified bitumens crosslinking by liquid MDI in the amount of 2,9 % wt.), which means that these materials after heating at temperature 180°C, for 72 hours do not show phase separation, because the difference in the softening point and penetration between the top and bottom part of the sample, after the tube test do not exceed 5°C and 9 [0,1 mm]. This proves that these binders may be stored and transported without fear of changing their properties and separating the polymer phase from the bitumen phase.

While polymer modified bitumens from examples 5-8 are stable only in case, when te oil- rubber composition is used in the amount not exceed 9,9% wt. (calculated on the weight of polymer modified bitumen). This indicates that the order in which the oil-rubber composition and diisocyanate are added, has a significant influence on the storage stability of the polymer modified bitumens, obtained according to the invention.

Table 1 Properties of neat bitumen 70/100 (used for modification), bitumen modified by un- processed rubber granulate (Bitumen/CR), bitumen modified by oil-rubber composition, obtained by using periodic method (Bitumen/ORC) and polymer modified bitumen obtained according to examples 1-8.

x - unstable sample, no possibility to determine the storage stability parameter Example 10

To prepare bitumen modified by oil-rubber composition (obtained by continuous method) and crosslinked by diisocyanate in the example 10, the same materials as in examples 1-8 were used. The method for its preparation included three stages:

In the first stage, using continuous method with extruder, oil-rubber composition was obtained. In order to obtain this composition using conventional mechanical mixer e.g. paddle mixer, mixture consisting of 950 g. of rubber granulate, which was 95% wt. of mixture and

50g. of castor oil, which was 5% wt. of mixture, was prepared. Mixing process of rubber granulate with oil continued until complete wetting of rubber granulate by oil, which lasted 5 minutes. Next this mixture was dosed to hopper of single-screw extruder for example Brabender- Duisburg, with a screw diameter equals 20 mm and ratio L/D equals 8, and in the next step, it was extruded with efficiency 120 g/min, maintaining a constant temperature in the heating zone of the plasticizing system and the extruder head on the level l80°C. Oil-rubber composition obtained in this stage was in the form of plastic extrudate after leaving the extruder head, was cooled to room temperature and shredded to the form of granulate with grain size below 1mm. Oil-rubber composition was characterized by density equals l,08g/cm ³ and contant of parts insoluble in toluene of 78 % wt.

In the second stage obtained oil-rubber composition in the amount of 25g, which was 5,0% wt. (calculated on the weight of polymer modified bitumen) was mixed with liquid bitumen, heated to l80°C, used in the amount of 473,75 g, which was 94,75 % of polymer modified bitumen. Process of blending bitumen with oil-rubber composition was carried out at a temperature l80±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M). Time of blending oil- rubber composition with bitumen, in the second stage was no more than 15 minutes, since the modifier was added to the bitumen, at rotational speed of mixing rotors of 4000 rpm.

In the third stage of bitumen modification, according to the invention, to mixture of oil -rubber composition and bitumen, heated to l80±5°C, third component of modifier, in the form of crosslinking agent - bis(4-isocyanatophenyl)methane modified by carbodiimide (liquid MDI) was added. Diisocyanate was added in the amount of l,25g, which was 0,25% wt. (calculated on the weight of polymer modified bitumen), after 15 minutes from adding oil-rubber composition to bitumen. Adding of crosslinking agent to bitumen took place with intense mixing at temperature 180±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M), at rotational speed of mixing rotors of 4000 rpm.

Mixing was carried out for another 45 minutes, so total time of bitumen modification by oil- rubber composition and diisocyanate did not exceed 60 minutes.

Binder obtained in this way, may be used in the process of production bituminous mixtures for road construction or may be used for roofing membranes, sealants and insulating materials. Properties and test results of hot storage stability of the binder obtained in the example 10. are presented in table 2.

Example 11

The method for preparation of the polymer modified bitumen, according to example 11 was carried out in the same manner, in three stages and using the same materials as described in example 10, except that in the first stage of bitumen modification, the temperature in the heating zone of the plasticizing system and the extruder head was maintained at 200°C.

While in the second stage of bitumen modification oil-rubber composition from example 10. was used in the amount of 24,75 g, which was 4,95% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 470, 25g, which was 94,05% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 10. , except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 5g., which was 1% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 10. Properties and test results of hot storage stability of the binder obtained in the example 11. are presented in table 2.

Example 12

The method for preparation of the polymer modified bitumen, according to example 12 was carried out in the same manner, in three stages and using the same materials as described in example 10., except that in the first stage of bitumen modification, the temperature in the heating zone of the plasticizing system and the extruder head was maintained at 160°C. While in the second stage of bitumen modification oil-rubber composition from example 10. was used in the amount of 50 g, which was 10% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 448, 75g, which was 89,75% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 10., except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of l,25g., which was 0,25% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 10. Properties and test results of hot storage stability of the binder obtained in the example 12. are presented in table 2.

Example 13

The method for preparation of the polymer modified bitumen, according to example 13 was carried out in the same manner, in three stages and using the same materials as described in example 10., except that in the second stage of bitumen modification oil-rubber composition from example 10. was used in the amount of 49,5 g, which was 9,9% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 445, 5g, which was 89,10% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 10., except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 5g., which was 1% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil- rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 10. Properties and test results of hot storage stability of the binder obtained in the example 13. are presented in table 2.

Example 14

Testing properties of bitumens, obtained according to examples 10-13

Bitumens, obtained according to examples 10-13, were tested for their penetration according to PN-EN 1426, softening temperatures according to PN-EN 1427, stability tests according to PN-EN 13399 and viscosity tests at 180 ° C, and the results are shown in table 2 (for comparision also results for neat bitumen (70/100) and bitumen modified by un-processed rubber granulate (polymer modified bitumen type Bitumen/CR) and bitumen modified only by oil-rubber composition (obtained by continuous method) without crosslinking agent (polymer modified bitumen type Bitumen/ORC) are presented in the table 2.) Based on the results, it was found that the binders obtained in Examples 10-13, are characterized by improved stability, compared with bitumen modified by un-processed rubber granulate and compositions obtained using continuous method and their physico-mechanical and rheological properties indicates that these binders may be used in the production of bituminous mixtures for road construction, or may be used in roofing membranes, sealants and insulating materials.

Table 2 Properties of neat bitumen 70/100 (used for modification), bitumen modified by un processed rubber granulate (Bitumen/CR), bitumen modified by oil-rubber composition, obtained by using continuous method (Bitumen/ORC) and polymer modified bitumen obtained according to examples 10-13.

Example 15.

To prepare bitumen modified by oil-rubber composition (obtained by continuous method) and crosslinked by urethane prepolymer in the example 15, following materials were used:

- bitumen 70/100, which penetration at 25°C is in the range 70-100 [0,1 mm], manufacturer for example LOTOS Asfalt Sp. z o. o.,

- rubber granulate, obtained by shredding of post-consumer car tires, with grain size below 1 mm, for example manufacturer Orzel Sp. z o.o.,

- castor oil characterized by viscosity at 20°C in the range 950-1100 mPas, acid value equals 1,23 mgKOH/g, hydroxyl value equals 163,9 mgKOH/g, iodine value equals 85,7 g I ₂ /l00g, for example manufacturer Brenntag Polska Sp. z o.o.

- liquid at room temperature bis(4-isocyanatophenyl)methane modified by carbodiimide (liquid- MDI) for example trade name Ongronat 3800, manufacturer Borsodchem, containing free isocyanate groups in the range 27-28% wt., which has thermal stability at bitumen modification temperature i.e. 180°C. - urethane prepolymer (PRE), containing 10% wt. free isocyanate groups (NCO), synthesized using bis(4-isocyanatophenyl)methane (Ongronat 3800, manufacturer Borsodchem) and a,w- dihydroxy[oligo(oxyteramethylene)] (for example PolyTHF2000 Polyether, manufacturer BASF) with molecular weight equals 2000 Da.

Method of preparation polymer modified bitumen according to example 15, included three stages:

In the first stage, oil-rubber composition was obtained by continuous method, in the same way as described in the example 10.

In the second stage, oil-rubber composition obtained in the first stage, in the amount of 49,75g, which was 9,95% wt. (calculated on the weight of polymer modified bitumen) was mixed with liquid bitumen, heated to l80°C, used in the amount of 447,75 g, which was 89,55 % of polymer modified bitumen. Process of blending bitumen with oil-rubber composition was carried out at a temperature 180±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M). Time of blending oil -rubber composition with bitumen, in the second stage was no more than 15 minutes from adding modifier to bitumen, at rotational speed of mixing rotors of 4000 rpm.

In the third stage of bitumen modification, to mixture of oil-rubber composition and bitumen, heated to 180±5°C, third component of modifier, in the form of crosslinking agent - urethane prepolymer was added. Prepolymer was added in the amount of 2,5g, which was 0,5% wt. (calculated on the weight of polymer modified bitumen), after 15 minutes from adding oil-rubber composition to bitumen. Adding of crosslinking agent to bitumen took place with intense mixing at temperature 180±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M), at rotational speed of mixing rotors of 4000 rpm.

Mixing was carried out for another 45 minutes, so total time of bitumen modification by oil- rubber composition and diisocyanate did not exceed 60 minutes.

Binder obtained in this way, may be used in the process of production bituminous mixtures for road construction or may be used for roofing membranes, sealants and insulating materials. Properties and test results of hot storage stability of the binder obtained in the example 15 are presented in table 3.

Example 16

The method for preparation of the polymer modified bitumen, according to example 16 was carried out in the same manner, in three stages and using the same materials as described in example 15., except that in the second stage of bitumen modification oil-rubber composition from example 15. was used in the amount of 49,5 g, which was 9,9% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 445, 5g, which was 89,1% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 15., except that urethane prepolymer in the amount of 5g., which was 1% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and urethane prepolymer was carried out in the same way, at the same temperature and using the same mixing device as in example 15. Properties and test results of hot storage stability of the binder obtained in the example 16 are presented in table 3.

Example 17

The method for preparation of the polymer modified bitumen, according to example 17 was carried out in the same manner, in three stages and using the same materials as described in example 15., except that in the second stage of bitumen modification oil-rubber composition from example 15. was used in the amount of 49 g, which was 9,8% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 441g, which was 88,2% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 15., except that urethane prepolymer in the amount of 10 g., which was 2% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and urethane prepolymer was carried out in the same way, at the same temperature and using the same mixing device as in example 15. Properties and test results of hot storage stability of the binder obtained in the example 17 are presented in table 3.

Example 18

Testing properties of bitumens, obtained according to examples 15-17

Bitumens, obtained according to examples 15-17, were tested for their penetration according to PN-EN 1426, softening temperatures according to PN-EN 1427, stability tests according to PN- EN 13399 and viscosity tests at l80°C, and the results are shown in tabic 3 (for comparision also results for neat bitumen (70/100) and bitumen modified by un-processed rubber granulate (polymer modified bitumen type Bitumen/CR) and bitumen modified only by oil-rubber composition (obtained by continuous method) without crosslinking agent (polymer modified bitumen type Bitumen/ORC) are presented in the table 3. Based on the results, it was found that the binders obtained in examples 15-17 may be used in the production of bituminous mixtures for road construction, or may be used in roofing membranes, sealants and insulating materials. Table 3 Properties of polymer modified bitumens, obtained according to examples 15-17.

Results presented in the table 3. for polymer modified bitumens, obtained according to examples 15-17 indicate that these binders are characterized by improved hot storage stability, compared to bitumen modified by un-processed rubber granulate (tabel 1.) and bitumen modified with oil-rubber composition (obtained by using continuous method - tabel 2.) and also physico- mechanical and rheological properties indicate that it is possible to use these binders in the production of bituminous mixtures for road construction, or may be used in roofing membranes, sealants and insulating materials.

Example 19

The method for preparation of the bitumen modified by oil-rubber composition, obtained by using periodic static method, and crosslinkied by diisocyanate, according to example 19 the same materials as described in examples 1-8 were used. Method of preparation these polymer modified bitumens included three stages: In first stage bitumen modifier in the form of oil-rubber composition was obtained using periodic static method. In order to obtain this composition using conventional paddle mechanical mixer in steel containers with capacity 2 dm ³ , mixture consisting of 950 g. of rubber granulate, which was 95% wt. of mixture and 50g. of castor oil, which was 5% wt. of mixture, was prepared. Mixing process of rubber granulate with oil was continued until complete wetting of rubber granulate by oil, which lasted 5 minutes. Next this mixture was heated at temperature l80°C for 60 minutes, mixing for about. 1 minutes at intervals of 10 minutes. Mixing was carried out with a paddle mixer at the rotational speed of the mixing rotor in the range 20-100 rpm. The oil-rubber composition obtained in this way was in the form of an oil-softened granulate.

In the second stage obtained oil-rubber composition in the amount of 74, 5g, which was 14,9% wt. (calculated on the weight of polymer modified bitumen) was mixed with heated to 180±5°C liquid bitumen used in the amount of 423,5 g, which was 84,7% wt. of polymer modified bitumen. Process of blending bitumen with oil-rubber composition was carried out at a temperature l80±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M). Time of blending oil-rubber composition with bitumen, in the second stage was no more than 15 minutes from adding modifier to the bitumen, at rotational speed of mixing rotors of 4000 rpm.

In the third stage of bitumen modification, according to example 19, to mixture of oil-rubber composition and bitumen, heated to l80±5°C, third component of modifier, in the form of crosslinking agent - bis(4-isocyanatophenyl)methane modified by carbodiimide (liquid MDI) was added. Diisocyanate was added in the amount of 2 g, which was 0,4% wt. (calculated on the weight of polymer modified bitumen), after 15 minutes from adding oil-rubber composition to bitumen. Adding of crosslinking agent to bitumen took place with intense mixing at temperature 180±5°C, using a laboratory homogenizer, which allowed shear mixing for example IKA T50 basic ULTRA-TURRAX, with mixing rotor type Ml (S 50 N - G 45 M), at rotational speed of mixing rotors of 4000 rpm.

Mixing was carried out for another 45 minutes, so total time of bitumen modification by oil- rubber composition and diisocyanate did not exceed 60 minutes.

Binder obtained in this way, may be used in the process of production bituminous mixtures for road construction or may be used for roofing membranes, sealants and insulating materials. Properties and test results of hot storage stability of the binder obtained in the example 19 are presented in table 4.

Example 20 The method for preparation of the polymer modified bitumen, according to example 20 was carried out in the same manner, in three stages and using the same materials as described in example 19., except that in the second stage of bitumen modification oil-rubber composition from example 19. was used in the amount of 74,0 g, which was 14,8% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to 180±5°C, used in the amount of 420, 5g, which was 84,1% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 19., except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 5,5g., which was 1,1% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil- rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 19. Properties and test results of hot storage stability of the binder obtained in the example 20. are presented in table 4.

Example 21

The method for preparation of the polymer modified bitumen, according to example 21 was carried out in the same manner, in three stages and using the same materials as described in example 19., except that in the first stage of modification, oil-rubber composition was prepared from mixture consisting of lOOg castor oil and 900g rubber granulate, which were 10% wt. and 90% wt. of the composition.

While in second stage of bitumen modification oil-rubber composition from example 19. was used in the amount of 74,5 g, which was 14,9% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to 180±5°C, used in the amount of 422g, which was 84,4% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 19., except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 3,5g., which was 0,7% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 19. Properties and test results of hot storage stability of the binder obtained in the example 21. are presented in table 4.

Example 22

The method for preparation of the polymer modified bitumen, according to example 22 was carried out in the same manner, in three stages and using the same materials as described in example 19., except that in the second stage of bitumen modification oil-rubber composition from example 19. was used in the amount of 74,0 g, which was 14,8% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 419, 5g, which was 83,9% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 19., except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 6,5g., which was 1,3% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil- rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 19. Properties and test results of hot storage stability of the binder obtained in the example 22. are presented in table 4.

Example 23

The method for preparation of the polymer modified bitumen, according to example 23 was carried out in the same manner, in three stages and using the same materials as described in example 19., except that in the first stage of modification, oil-rubber composition was prepared from mixture consisting of 150g castor oil and 850g rubber granulate, which were 15% wt. and 85% wt. of the composition.

While in second stage of bitumen modification oil-rubber composition from example 19. was used in the amount of 74 g, which was 14,8% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to l80±5°C, used in the amount of 42 lg, which was 84,2% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 19., except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 5g., which was 1% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 19. Properties and test results of hot storage stability of the binder obtained in the example 23 are presented in table 4.

Example 24

The method for preparation of the polymer modified bitumen, according to example 24 was carried out in the same manner, in three stages and using the same materials as described in example 19., except that in the first stage of modification, oil-rubber composition was prepared from mixture consisting of 200g castor oil and 800g rubber granulate, which were respectively 20% wt. and 80% wt. of the composition.

While in second stage of bitumen modification oil-rubber composition from example 19. was used in the amount of 74 g, which was 14,8% wt. of polymer modified bitumen. In the second stage, this composition was mixed with the liquid bitumen heated to 180±5°C, used in the amount of 419,5 g, which was 83,9% wt. of polymer modified bitumen. In the third stage the process of bitumen modification was carried out in the same way as in the example 19. , except that bis(4-isocyanatophenyl)methane modified by carbodiimide (Ongronat 3800) in the amount of 5g., which was 1,3% wt. of polymer modified bitumen, was added to mixture of bitumen and oil-rubber composition. The process of mixing bitumen with an oil-rubber composition and diisocyanate was carried out in the same way, at the same temperature and using the same mixing device as in example 19. Properties and test results of hot storage stability of the binder obtained in the example 24. are presented in table 4.

Example 25

Testing properties of bitumens, obtained according to examples 19-24

Bitumens, obtained according to examples 19-24, were tested for their penetration according to PN-EN 1426, softening temperatures according to PN-EN 1427, stability tests according to PN- EN 13399 and viscosity tests at l80°C, and the results are shown in table 4.

Based on the results, it was found that the binders obtained in examples 19-20 may be used in the production of bituminous mixtures for road construction, or may be used in roofing membranes, sealants and insulating materials.

Table 4 Properties of neat bitumen 70/100 (used for modification), bitumen modified by un- processed rubber granulate (Bitumen/CR), bitumen modified by oil-rubber composition, obtained by using periodic static method (Bitumen/ORC) and polymer modified bitumens obtained according to examples 19-24.

Polymer modified bitumens, which were obtained according to examples 19-24 are characterized by viscosity in the range 0,1 -1,9 Pas, at temperature 180°C, and storage stability compared with bitumens modified by un-processed rubber granulate (Bitumen/CR) and bitumens modified only by oil-rubber composition (obtained using static method) and also physico-mechanical and rheological properties indicate that it is possible to use these binders in the production of bituminous mixtures for road construction, or may be used in roofing membranes, sealants and insulating materials.