Abstract:
The aim of this invention is to synthesize new polymers which can be used for bitumen modification, oil absorption and other purposes. It was done by synthesizing styrene-modified maleic anhydride complex (SMMA) which has ability to react with all types of polymers and forms nano particles inside them. Indeed it is the formation of nano particles inside the polymers which cause such a great changes in physical, chemical, thermal and mechanical properties. None of the known derivatives of natural rubber or EPDM for examples shows the properties which have seen in this invention. The nature of the polymer determines the end use of the novel products. If the polymer is natural rubber (NR), the resulting novel polymer can be used for bitumen modification. They are compatible with bitumen, melt, react and disperse in bitumen readily without needing to special equipments for blending. The resulting composition is homogenous and demonstrates improved settling and rheological properties at high and low temperatures. If the polymer is ethylene-propylene diene monomer (EPDM), the produced novel polymer behaves like a smart particle and absorbs contaminates like oil selectively from a mixture of oil and water.

Description:
BACKGROUND OF THE INVENTION  
       [0001]     Until now, the main groups of polymers which have been used as bitumen modifiers are the followings:  
         [0000]     Thermosetting polymers, thermoplastic polymers, natural (NR) &amp; synthetic rubbers, thermoplastic elastomer (TPE) and elvaloy (RET).  
         [0002]     Each of the above groups has disadvantages which can not be called as ideal one, for example: thermoplastic polymers are characterized by softening on heating and hardening on cooling. Polyethylene (PE), atactic and isotactic polypropylene (APP, IPP), polyvinylchloride (PVC), polystyrene (PS) . . . , etc, are the main polymers of this group. Thermoplastic polymers associate at room temperature with bitumen, increasing its viscosity, however they do not significantly confer any element of elastic deformation to bitumen and can separate when heated.  
         [0003]     Thermosetting polymers are not widely used, due to the high cost and special method of application.  
         [0004]     Natural rubber (NR) and synthetic rubbers such as polybutadiene, styrene-butadiene rubber (SBR), etc, are sensitive to decomposition and oxygen absorption. They have a molecular weight too high to be directly dissolved in the bitumen and must be partially decomposed and mechanically homogenized.  
         [0005]     Thermoplastic elastomers (TPE) such as SBS and SIS are physically dispersed in bitumen, but do not chemically react with the bitumen. Keeping a consistent dispersion often requires extra care and attention, this can be especially difficult if there is any project delay in using of the material. Also the butadiene mid block in SBS is unsaturated which means it will oxidize in the pavement.  
         [0006]     Elvaloy (RET) is a random terpolymer comprising ethylene, normal butyl acrylate and glycidyl methacrylate (GMA). GMA copolymers chemically react with asphalt to form a polymer linked-asphalt system. Elvaloy (RET) can only be used for asphalt (not bitumen alone) which means it has no mechanical strength by itself.  
         [0007]     Thus, a need exist for new bitumen modifier which avoid the above disadvantages.  
       SUMMARY OF THE INVENTION  
       [0008]     Briefly, the present invention is to synthesize new reactive polymers by reacting styrene-modified maleic anhydride complex (SMMA) with all types of polymers. Maleic anhydride reacts with free radical generating polymerization catalyst, i.e. benzoyl peroxide in a suitable solvent and forms compound with an active ingredient, which is called as modified maleic anhydride in the context of the present invention (MMA). The styrene monomer forms a complex (SMMA) with the MMA when mixed with it at room temperature for one hour.  
         [0009]     By incremental addition of this complex to all types of polymers, i.e. Natural rubber (NR), two reactions happen, first some SMMA reacts chemically with functional groups present in the NR, so viscosity of solution decreases, and second some of the SMMA form new copolymer of styrene-modified maleic anhydride and disperses through polymer in nano size.  
     
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS  
       [0010]     New polymers which are synthesized by the method of present invention are reactive terpolymers with the chemical designation of SMMAX (styrene/modified maleic anhydride/X), where X can be all type of polymers (natural rubber (NR), synthetic rubbers, crumb rubber, thermoplastic elastomers (TPE), thermoplastics, elvaloy (RET) and a combination of different or the same type of polymers) or nothing, which means styrene-modified maleic anhydride copolymer by itself can also be used for bitumen modification in some cases. They are named as new reactive polymers (NRPs) in the context of this patent.  
         [0011]     The reaction of maleic anhydride with natural rubber is of interest because they impart polarity to the non polar natural rubber. Pure maleic anhydride reacts with natural rubber under different conditions to give different derivatives but gelation is always a serious problem. Gelation takes place because of formation of chemical structure which is shown in  FIG. 1 . This structure is very susceptible to crosslink.  
         [0012]      FIG. 1 . Schematic of chemical structure which is susceptible to crosslink.  
         [0013]     Modification of maleic anhydride according to our present invention, prevents formation of gel during the reaction of maleic anhydride with natural rubber.  
         [0014]     There are some studies about the reaction of maleic anhydride and benzoyl peroxide when amount of benzoyl peroxide is low (0.1-0.5 weight percent of maleic anhydride). Braun and co-workers (Braun. D.,  Aziz El Sayed. I. A., Pomakis. J., Makromol. Chem.,  124, 249 (1969) claimed that the free radical polymerization of maleic anhydride (MA) proceeds with carbon dioxide cleavage. He studied the proton magnetic resonance spectrum of a benzoyl peroxide initiated polymer, concluded that the polymer does not have the expected poly (maleic anhydride)(PMA) structure; he claimed that it consists mainly of cyclopentanone repeating units ( FIG. 2 ). However, Bacskai (Bacskai. R.,  Journal of Polymer Science: Polymer Chemistry Edition.,  14., 1797-1807 (1976)) reported that products of the reaction between benzoyl peroxide and maleic anhydride are unrearranged poly maleic anhydride ( FIG. 3 ).  
         [0015]      FIG. 2 . Chemical structure of cyclopentanone.  
         [0016]      FIG. 3 . Chemical structure of poly maleic anhydride.  
         [0017]     Both of them used low concentration of benzoyl peroxide, There are no reports about the reaction of maleic anhydride with high concentration of benzoyl peroxide. In our present invention, amounts of benzoyl peroxide is very high (fifty weight percent of maleic anhydride or more). It is very hard to identify the nature of the products clearly and it is not the main aim of this invention. The most important thing is that resulting product is able to form complex with styrene, interacts with natural rubber ( FIG. 4 ) and also forms particles in nano size inside of natural rubber. The transition electron microscopy (TEM) which was taken from novel polymer (made from natural rubber) shows the existing of nano particles inside the natural rubber ( FIG. 5 ). The particles as small as one nanometer is clearly observed inside the natural rubber ( FIG. 5 ). This new derivative of natural rubber has unique properties; it melts while its thermal stability is the same as that of pure natural rubber, has almost the same glass transition temperature (T g ) as that of pure natural rubber, soluble in toluene, precipitate in alcohol, they are compatible with bitumen, easily be dissolved in bitumen (mixing at 150° C. for 30 minutes is enough) and they react with some functional groups which are present in bitumen. Carboxyl group in the modified maleic anhydride is responsible for the reaction with bitumen. Actually it can be claimed that NRPs act like elvay (RET) polymers but at the same time has noticeable mechanical strength or it is possible to be claimed that NRPs are similar to TPE polymer but at the same time has the ability to react chemically with bitumen because of carboxyl group present in modified maleic anhydride. The carboxyl group is responsible for the chemical reaction and compatibility between bitumen and NRPs. There are no further problems regarding to maintaining compatibility during storage and uses, since the chemical reaction occurs and also because of presence of nano particles of new styrene-modified maleic anhydride copolymer inside the rubber. Actually it is supposed that such great and excellent changes in properties of natural rubber can only be only due to formation of nano particles in natural rubber ( FIG. 5 ). In fact, the presence of nano particles which are disperses through the natural rubber prevent settling and agglomeration of natural rubber in the bitumen. Until now none of the known derivatives of natural rubber show all these properties together.  
         [0018]      FIG. 4 . Schematic representation of reaction between styrene-modified maleic anhydride complex and natural rubber.  
         [0019]      FIG. 5 . TEM of nano particle&#39;s distribution (SMMA copolymers) through the natural rubber.  
         [0020]     The presence of nano particles inside EPDM cause extra percent of elongation at break which have never been reported (4000%), It melts easier than pure EPDM, also modified EPDM is able to absorb contaminate from water.  
         [0021]     The type of the products which are obtained from the reaction between maleic anhydride and benzoyl peroxide depend on amount&#39;s of benzoyl peroxide and also on time of the reaction. It seems that for definite amount of benzoyl peroxide, products change from time to time. There is an optimum time for each initiator type and concentration, for example for 50% of benzoyl peroxide (weight percent with respect to maleic anhydride), optimum time is five hours.  
         [0022]     The optimum time is defined as the time that is sufficient to produce suitable products which are able to form complex with styrene (SMMA), the complex behaves as a single particle and react chemically with natural rubber ( FIG. 4 ) and enter the propagation step as a single particle. Gelation does not take place because the structure which are susceptible to crosslink never have been formed ( FIG. 1 ). If the time is insufficient, natural rubber will be crosslinked and gelation occurs.  
         [0023]     Required amount of MMA depends on the type of X component (s) and on desired properties. For a single X compound (s), there is a minimum amount of MMA which cause X compound (s) be able to readily dispersed in bitumen and do the necessary chemical interactions. There is also a maximum amount of MMA, beyond that crosslinked polymers will be produced.  
         [0024]     Rolling of pure natural rubber is a key parameter, if modified natural rubber is wanted to be used for bitumen modification. Rolling lowers molecular weight of natural rubber and causes better melting of natural rubber in bitumen. Thirty minutes at 50° C. is sufficient for pale creep natural rubber.  
         [0025]     Great changes in properties of NRPs can be created by using different X compound (s) and changing the weight ratio of components with respect to each others. NRPs may be very rigid, tough or highly elastic. Various new thermoplastic elastomers can also be synthesized by the method of the present invention.  
         [0026]     Modification of maleic anhydride requires a free radical generating catalyst. Suitable catalyst in accordance with the process include many organic peroxides, for example, dilauryl peroxide, ditertiary butyl peroxide, diacetyl peroxide, acetyl benzoyl peroxide, tertiary butyl hydroperoxide, cumene hydrogen peroxide, etc., may be used as well as other free-radical generating catalysts such as azo compounds illustrated by catalysts such as acetone peroxide which provide free-radical reactivity and stability at high temperatures may be used effectively.  
         [0027]     Various maleic anhydride compounds such as methyl maleic anhydride, Phenyl maleic anhydride, di-methyl maleic anhydride and chloromaleic anhydride are particularly contemplated. Maleic anhydride is preferred.  
         [0028]     Formation of styrene-modified maleic anhydride complex (SMMA) was done by mixing styrene with MMA for one hour at room temperature. Various vinyl aromatic monomers may be used, especially styrene and vinyl toluene, but other substituted styrene may be used such as ring-alkylated styrene compounds such as the vinyl xylenes, and p-isopropyl styrene, these being illustrative of C 1 -C 4  alkyl-substituted products. Halogen-substituted styrene may also be used in which up to five of the nuclear hydrogen atoms are replaced by chlorine, fluorine, or other halogen, while the invention is primarily directed to styrene and ring-substituted styrene, other noethlenically unsaturated compounds having a strong tendency to heteropolymerize with maleic compound, especially maleic anhydride, may be used, such as vinyl alkyl ethers illustrated by vinyl ether and vinyl butyl ether, vinyl acetate, and acrylate and methacrylate ester such as ethyl acrylate and methyl methacrylate, and olefins such as ethylene and propylene.  
         [0029]     The reaction between SMMA &amp; X compound(s) was carried out in the presence of a chain transfer agent. Variety of chain transfer agents, for example polyhallide, disulfide compounds and mercaptans can be used. While various mercaptans are known to regulate molecular weight distribution efficiently producing uniform products, mercaptans possess an undesired strong odor which most often remains with the polymerized end-product. In order to avoid the odor problem created by short chain mercaptans, larger quantities of less efficient long chain mercaptans such as 3-mercaptopropionic acid or 3-mercaptopropionate are used. Required amount of chain transfer Agent depends on the type of X compound (s), temperature of the reaction and total weights of monomers and X compound (s).  
       Example 1  
       [0030]     A mixture of 1 gram of maleic anhydride, 0.5 gram of benzoyl peroxide and 100 gram of Toluene were charged to a 250 cc multiple-neck round bottom flask equipped with a stirrer, thermometer, condenser and nitrogen inlet. With constant agitation, the mixture was heated to 120° C. under nitrogen sweeping. The mixture was held at this temperature for five hours. Then it is cooled to room temperature and 20 grams of styrene was added to the flask and the mixing was continued for one hour. At the end, 0.1 gram of 3-mercaptopropionic acid was added and mixed for further one hour at room temperature. This solution is called as “Solution A”.  
         [0031]     100 grams of natural rubber (pale creep) which were rolled for 30 minutes at 50° C. was dissolved in 200 grams of toluene at 60° C. in a one liter reactor which was equipped with a mechanical stirrer, thermometer, reflux condenser, addition funnels. The “Solution A” was added over two hours to the reactor and mixed with rubber. The mixture was held at 60° C. for two days after addition. A clear brown polymer solution was obtained and the toluene was removed by any desired methods.  
         [0032]     Thermal stability of the novel polymer 1 was evaluated by thermal gravimetry analysis (TGA). As it can be seen from the  FIG. 6 , it has lost only 10% of its initial weight at 336° C.  
         [0033]      FIG. 6 . TGA thermogram of the novel polymer 1.  
         [0034]     Differential scaning calorometry (DSC) of the novel polymer 1 was studied. Its melting point and glass transition temperature (T g ) are 90° C. ( FIG. 7 ) and −60° C. ( FIG. 8 ), respectively.  
         [0035]      FIG. 7 . DSC of the novel polymer 1, in temperature range of zero to 200° C.  
         [0036]      FIG. 8 . DSC of the novel polymer 1, in temperature range of −100 to zero C.  
         [0037]     Heat stability of the novel polymer 1 is better than pure natural rubber ( FIG. 9 ), while novel polymer 1 can melts but pure natural rubber can not ( FIG. 10 ). The glass transition temperature of novel polymer 1 is almost the same as pure natural rubber ( FIG. 11 ).  
         [0038]      FIG. 9 . TGA thermogram of the novel polymer 1 &amp; pure natural rubber.  
         [0039]      FIG. 10 . DSC of the novel polymer 1 &amp; pure natural rubber, in temperature range of zero to 250° C.  
         [0040]      FIG. 11 . DSC of the novel polymer 1 &amp; pure natural rubber, in temperature range of −100 to 50° C.  
         [0041]     The stress-strain curve of the novel polymer 1 is shown in  FIG. 12 . It has tensile strength of 0.2 MPa and its strain at break point is 635%. The low tensile strength is a key parameter which causes the novel polymer 1 to be dispersed through bitumen easily.  
         [0042]      FIG. 12 . Stress (MPa) vs strain (%) of the novel polymer, at test speed of 50 mm/min.  
         [0043]     Six grams of the novel polymer 1 mixed with 94 grams of Iranian Bitumen 60/70 at 150° C., for one hour, while stirrer speed is 1000 rpm. The most important properties of the pure bitumen 60/70 and bitumen containing 6% novel polymer is compared and shown in table 1.  
                                                   TABLE 1                           The most important properties of pure bitumen       and that containing 6% of novel polymer 1.                Softening point   Penetration 25   F.B.P           (° C.)   (° C.) (.1 mm)   (° C.)       Materials   ASTM-D36   ASTM-D5   IP 80/89                    Iranian Bitumen 60/70   58   70   −5       Novel Polymer 1   72   30   −13                  
 
         [0044]     The novel polymer 1 is compatible with bitumen, melts, chemically reacts and disperses in it very well, as it can be seen from  FIG. 13 .  
         [0045]      FIG. 13 . Photograph of mixture of bitumen &amp; novel polymer 1.  
       Example 2  
       [0046]     The same as example 1, but ethylene-propylene-diene monomer (EPDM) was used instead of natural rubber. The resulting polymer can be used for absorption of contaminate like oil from water. It behaves like a smart particle when immersed in a mixture of oil and water, it absorbs oil and remains on the surface of the water. Also they can be used whenever EPDM with low meting point and low tensile strength is required.  
         [0047]     The TGA of the resulting polymer shows that it lost only 5% of its weight at 300° C. ( FIG. 14 ) and shows better heat stability compare to the pure EPDM ( FIG. 15 ).  
         [0048]      FIG. 14 . TGA of the novel polymer 2.  
         [0049]      FIG. 15 . TGA of the novel polymer 2 &amp; pure EPDM.  
         [0050]     Novel polymer 2 has melting point of 90° C. ( FIG. 16 ) and its glass transition temperature (T g ) is −45.57° C. ( FIG. 17 ).  
         [0051]      FIG. 16 . DSC of the novel polymer 2, in temperature range of zero to 200° C.  
         [0052]      FIG. 17 . DSC of the novel polymer 2, in temperature range of −100 to zero C.  
         [0053]     DSC of the novel polymer 2 with pure EPDM rubber was compared in temperature range of zero to 250° C. and was shown in  FIG. 18 . It can be seen that novel polymer 2 melts easier than pure EPDM.  
         [0054]      FIG. 18 . DSC of the novel polymer 2 &amp; EPDM rubber, in temperature range of zero to 200° C.  
         [0055]     Novel polymer 2 has tensile strength of 0.65 MPa and its strain at break point is 4192% ( FIG. 19 ). Its very high strain at break point and low tensile strength enables it to absorb large amount of oil.  
         [0056]      FIG. 19 . Stress (MPa) vs strain (%) of the novel polymer 2, at test speed of 50 mm/min.  
       LEGANDS OF THE FIGURES  
       [0000]    
       
           1 .  FIG. 1 . Schematic of chemical structure which is susceptible to crosslink.  
           2 .  FIG. 2 . Chemical structure of cyclopentanone.  
           3 .  FIG. 3 . Chemical structure of poly maleic anhydride.  
           4 .  FIG. 4 . Schematic representation of reaction between styrene-modified maleic anhydride complex and natural rubber.  
           5 .  FIG. 5 . TEM of nano particle&#39;s distribution (SMMA copolymers) through the natural rubber.  
           6 .  FIG. 6 . TGA thermograms of the novel polymer 1.  
           7 .  FIG. 7 . DSC of the novel polymer 1, in temperature range of zero to 200° C.  
           8 .  FIG. 8 . DSC of the novel polymer 1 in temperature range of −100 to zero ° C.  
           9 .  FIG. 9 . TGA thermogram of the novel polymer 1 &amp; pure natural rubber.  
           10 .  FIG. 10 . DSC of the novel polymer 1 &amp; pure natural rubber, in temperature range of zero to 250° C.  
           11 .  FIG. 11 . DSC of the novel polymer 1 &amp; pure natural rubber, in temperature range of −100 to 50° C.  
           12 .  FIG. 12 . Stress (MPa) vs strain (%) of the novel polymer 1, at test speed of 50 mm/min.  
           13 .  FIG. 13 . Photographs of mixture of the novel polymer 1 with the bitumen.  
           14 .  FIG. 14 . TGA thermograms of the novel polymer 2.  
           15 .  FIG. 15 . TGA of the novel polymer 2 &amp; pure EPDM.  
           16 .  FIG. 16 . DSC of the novel polymer 2, in temperature range of zero to 200° C.  
           17 .  FIG. 17 . DSC of the novel polymer 2, in temperature range of −100 to zero ° C.  
           18 .  FIG. 18 . DSC of the novel polymer 2 &amp; EPDM rubber, in temperature range of zero to 200° C.  
           19 .  FIG. 19 . Stress (MPa) vs strain (%) of the novel polymer 2, at test speed of 50 mm/min.