WO2005056666A1

WO2005056666A1 - Polimeric compound including rubber particles, obtaining procedure, it's applyance and resulting coating using this material

Info

Publication number: WO2005056666A1
Application number: PCT/RO2003/000017
Authority: WO
Inventors: Laurentiu Daniel Tigau; Constantin Ciobanu
Original assignee: Laurentiu Daniel Tigau; Constantin Ciobanu
Priority date: 2003-12-11
Filing date: 2003-12-11
Publication date: 2005-06-23
Also published as: AU2003304598A1

Abstract

The invention 'Polimeric compound including rubber particles, obtaining procedure, it's applyance and resulting coating using this material' refers to a polymeric compound including rubber particles, used for coating different surfaces in order to assure mechanical and anticorrosive protection, such as metallic, wooden, glass, ceramics, textiles, floors, especially designed for gas and oil transporting pipes, for thermo insulating plates, industrial halls flooring, sport grounds, playgrounds, paddocks, level crossings, fittings, shoes flange, different sportive articles, obtaining procedure and appliance, as well as resulting coating using this compound. Rubber particles polymeric compound is costituted of vulcanized rubber particles treated with esthers of fat unsaturated with inferior's alcohol acids and activated with UV radiations and 2 … 20%, preferable 8 … 17% a reactive polymer with, double polymerisable compounds to a proportion of 0,2 … 10 molls/10000g, preferable 0,4 8 molls/10000 g, 1 … 20%, preferable 1,1 … 13% free isocianic compound, 0,01....18%, preferable 0,1 … 15% epoxy compound, 0,1 … 150 parts, preferable 2 … 50 parts of an aliphatic or aromatic hydroxiurethane or a compound of its with a concentration of the urethane's compound of 4 … 15 molls -NH-COO-/1000 g, preferable 5 … 12 molls -NH-COO-/1000 g, 001 … 3 parts, preferable 0,1 0,25 parts of catalysts chosen between stanium dioctate or dilaurated stanium dibuthyl, 0,1 … 3 parts, preferable 0,2....1,3 antioxidant parts chosen between imino imidazoline bethaine, alchiimino imidazoline amphoterisated or alchil amidoimine amphoterisated, 2 … 8 parts, preferable 4 … 6 parts of microfibriles chosen between polyamidic, polyesteric, cellulosic microfibriles or a composite of those mentioned, 0,1 … 60 parts, preferable 2 … 20 parts an inorganic product under powder form with a particle keenness under 2 microns chosen between limestone, bentonite, silicium dioxide, barium sulfate, copper sulfate, zinc oxide, titanium dioxide, talc, iron oxide, chrome oxide or 0,01 … 10%, preferable 0,2 … 6% metallic powder chosen between aluminum, zinc, copper or its composit, 0 … 90 parts, preferable 0,1....70 solvent parts.

Description

POLIMERIC COMPOUND INCLUDING RUBBER PARTICLES, OBTAINING PROCEDURE, IT'S APPLYANCE AND RESULTING COATING USING THIS MATERIAL

The invention refers to a polymeric compound including rubber particles, used for coating different surfaces in order to assure mechanical and anticorrosive protection, such as metallic, wooden, glass, ceramics, textiles, floors, especially designed for gas and oil transporting pipes, for thermo insulating plates, industrial halls flooring, sport grounds, playgrounds, paddocks, level crossings, fittings, shoes flange, different sportive articles, obtaining procedure and appliance, as well as resulting coating using this compound. There are well known polymeric compounds obtained from a polymer matrix and rubber vulcanized particles used for various articles, such as heels, shoes flange, various technical pieces or slings for industrial conveyors. The use of vulcanized rubber particles for obtaining useful compounds is now of great importance in solving pollution problems, considering the increased used car tires quantities. Also, the use of rubber waist materials for polymeric compounds obtaining with large appliance range it's an attractive subject from economical point of view. Generally, such compounds involves a polymer matrix more or less compatible with rubber particles, the chemical connection between the polymer and the rubber hydro carbonated chains being weak, especially the type of connections p-ll realised by the un

participating electrons of oxygen from polymer carbonyl groups and π electrons from

rubber macromolecules double connections. In this regard have been realized compounds for various purposes, starting from urethane pre polymers with free isocyanic groups and fine rubber particles. In US 4112176, in particular, are being described etheric pre polimer compounds with free isocyanic groups and vulcanized rubber particles with reduced water content. The water in the atmosphere reacts with the prepolymer leading to a reticulated polyuretha ureic matrix in which the rubber particles are included. The disadvantage of these composites is the fact that only the fin rubber particles may be used, thus limiting the area of applicability of the present solution. In any case, the prepolymers proposed so far to be used in obtaining such composites, either for special use, or general one, have all presented one or more disadvantages. For example, US 5385953 describes the way you could control the water in the system by mixing the rubber particles with molecular sieves, but this stage of work leads to a much harder method and a more expensive product. In WO 00/75231 A1 and WO 2004/067870 A1 the interactions inside the composite's matrix - and by that I am referring to the interactions between the polyurethane containing free isocyanic groups and the rubber particles - aren't mentioned and are treated as simple fillers; in dynamic or even static conditions, if the composite's components do not interact and do not form chemical links, the properties change in time, with fase separation which forms the respective compound. Other documents presents the use of binder substances between rubber and polymer, so called primer. Thus in WO 95/25076 as binder is used the organo aminosilane in distorted alcohol consiting of methylate alcohol. The disadvantage of this solution consists in the fact that the water inside the filling can not be controled, fact that leads to a weak adherence to the polymer, and in the GB 2364708 A and US 6565918 patents the connection betwen rubber and polymer is carried thrue by poly butadiene diol (polibutadiene with hidroxyl terminal groups). In both cases, the synthesis methods of the prepolymer as well as the method of obtaining of the composite are relatively complicated and there has been no development in the field of industrial exploitation of this proceedings with a proper build installation. In US 4771110, EP 0558023 A1, WO 97/23515, US 5382635, US 5506283, WO 97/31955, US 5693714, US 5969053, are presented the composites obtained with polyurethanic elastomers, epoxy resins or unsaturated polyesters in which the rubber particles are included. For an increased adherence, the rubber particles are treated either with chloride that has been diluted with air, either by nitrogen or any other inert gas, or with chloride and a small quantity of fluoride, that increases the gas mix power of oxidation. Through this method you obtain rubber particles with different halogen concentrations connected, considering the treatment period of rubber particles with chlorine. The result are compounds with high level modules, with a wide a rea of use, but the residual chlorine a nd especially the fluoride are potential pollution and corrosion sources, which raises environmental issues, problems with the corrosion of the equipment and the protection of the workers responsible of the chlorination operation. None of the documents quoted above suggests the way the binding substance ties itself to the rubber particles macromolecule, thus assuring a higher compatibility of the composite, nor the types of polar structures that are formed in the redox process of halogenation, that can react with the reactive groups within the polymer matrix, especially since we know that, for example, the polyurethanes are less compatible with the chlorinated polymers. So even if the compound has a high hardness, its resistance to repeated flexions is limited. The problem that the inventions group are solving, consists in obtaining and achieving a more efficient way of activating the rubber particles, as well as its proportion along with other components that together form a polymeric composition from which it can result composite products with physical-chemical and superior physical-mechanical properties. According to the invention, the polymeric composition is made up from the particles of vulcanized rubber treated with 0,005...20%, preferably 0,01...8% unsaturated fat acids esthers that came from vegetal oils and inferior alcohols and activated by UV radiations, in a fluidized air bed, 2...20%, preferably 8...17% a reactive polymer with double polymerisable connections in a proportion of 0,2...10 mols/10000g, preferably 8...15% epoxi groups, 2...150 parts, preferably 8...50 parts of a hydroxiurethane aliphatic or aromatic or a mixture between these two with the concentration in urethanes groups between 4...15 mols -NH-COO-/1000g, preferably 5...12 mols -NH-COO-/1000g, 001...3 parts, preferably 0,1...0,25 parts catalysts chosen between stanium dioctate and dilauraurated stanium dibutil, 0,1...3 parts, preferably 0,2...1,3 parts antioxidants chosen between imino imidazoline betaine, alchi imino imidazoline amphoterisated or alchil amidoimine amphoterisated, 2...8 parts, preferably 4...6 microfibriles parts chosen from polyamidic, polyestheric, celulosic or a mixture of these microfibriles, 0,1...60 parts, preferably 2...20 parts of an anorganic product powder form with particles smaller then 2 microns chosen from clacium carbonate, bentonite, silicium dioxide, barium sulphate, cooper sulphate, zinc oxide, titanium dioxide, talc, iron oxide, chrom oxide or, 0,01...10%, preferably 0,2...6% metallic powders chosen from aluminium, zinc, cooper or a mixture of those, 0...90 parts, preferably 0,1...70 parts of one of these solvents: methilene chloride, diclormethane, tetraclorethilene or dimethilformamide, dimethilsulphoxide, N- methilpirolidone, acetones, methil ethil cetone, ethil acetate, butyl acetate, gas, toluene or xilene or toluene gasoline or a mixture of some of the above, at a temperature of 0...120 C, preferably 15...80 C, for 0,5...72 hours, preferably 1...24 hours. The proportions have been established considering the weight parts. According to one aspect of the invention, I propose particles of vulcanized rubber obtained from used automobiles rubber tires with dimensions up to 2 mm on which is deposed a film of unsaturated fat acids esthers that come from vegetal oils with units containing an unsaturated hydrocarbonated group and in some cases groups of free OH with the general structure RCOORi. Where R represents the radical with 8 up to 22 carbon atoms, with one or more unsaturated links, of the acid that finds its origins in the triglycerides of an oily plant or a mixture of triglycerides of two or more oily plants, and R1 is a hidrocarbonated radical type CH₃-(CH₂)n- , where n could have one of the following values: 0,1 ,2,3,4; also, radical R can contain reactive functions toward structure (I) isocianats: -CH2-CH-CH₂-(I) OH From the esthers tied at the surface of the rubber particles, I have emphasized the OH group and the carbonile(C=O) through ATR-FTIR (Attenuated Total Reflection Fourier Transform Infrared Spectroscopy) spectroscopy at 3380 cm^"1 symetrical strech vibration of the connection between oxygen and hydrogen, v(O-H) and 1715 cm^"1 symetrical strech vibration of the double connection between carbon and oxygen, v(C=O) from the COO group of the esther. On the list of oily plants from which we can extract triglycerides there are corn (Zea mays), soybean (Glycine max), mustard (Brasica alba), linseed (Linum ustiatissimum), sunflower (Helianhtus annuus), rapeseed (Brassica napus), olive tree (Olea europaea), castor bean ( Ricinus communis), coconut (Cocos nucifera), palm tree (Elaeis guinmeensis), cardui mariae fructus (Silybum marianum) etc. The term of unsaturated links refers to double unconjugated connections in trans or cis positioned double conjugated links. Some of these connections can polymerize with the formation of polymeric networks. So the activation consists of chemically linking of the radical R to the macromolecules at the surface of the rubber particle in the right proportion. The esthers of the fat acids used in the invention can be obtained, through trans estherification in a basic environment, with the proper alcohol, after known synthetic methods as presented by let's say Gerhard Knothe, in J. Am. Oil Chem. Soc.76: 75-800(1999), J. Am. Oil Chem. Soc. 77:489-493(2000). The rubber particles activated with UV radiations and esthers of unsaturated fat acids, in an air fluidised bed, according to the invention, in a profitably manner, presents a bigger reactivity towards the functions inside the polymer. Also, the compatibility of the rubber crumb activated with the polymeric matrix has improved. The treatment of activating the rubber crumb with the use of UV radiations, according to the invention, is made on a band length of 200...450 nm and an intensity of 170...220mW/cm², so that the radical polymerization and the forming of the rubber-unsaturated fat acid or the rubber-polymer networks would take place in a technologically convenient time of 120 seconds tops. In the terms of this particular invention, air fluidised bed refers to the continuos mixing of the rubber particles with a flow of air. The G quantity of fat acids esthers appropriate to the rubber crumb, according to the invention, is being deducted by using formula (1): G=2,6p (1) Where G represents the quantity of fat acids esthers per 100g of rubber particles, calculated in grams and 2,6 represents a coefficient calculated in cm³ and p is the volumetric density of the rubber partiles, g/cm³. The polymers that have been used in the composite according to the invention, in a profitably manner, can have a relatively low molecular mass, so that it can contribute at the formation of polymer-rubber particles networks as well as at the spreading of the composite's components during the mixing process. For this particular invention, the term polymer defines those substances with a low molecular mass such as prepolymers. The polymers that have been used for this invention can be presented as units containing functional groups represented by the formula (II): (OOCNH-R₂-NCO)n / / A - -(OOC-R₅)m (II) \

\ (OOC-R₃-COO-R₄-CH-CH₂)w \ / O Where R₂,R₃ and R₄ each represent an aromatic type of group, aliphatic or olenifinic attached to nitrogen or carbon. When groups R₂ and R₄ represent an aromatic group, it can contain one or more aromatic cores conjugated or separated by saturated or unsaturated aliphatic groups or by heteroatoms selected between O, S. The aliphatic groups inside aromatic cores can be either liniar or ramificated. R5 can be a saturated or unsaturated aliphatic group with one or more double connections containing at least 12 carbon atoms within the molecule. A represents oligomere structures containing hidrocarbonated catenas composed of at least 20 carbon atoms or polyetheric catenas, etheric-polyesther or polyestherics saturated or unsaturated, liniar or ramificated, with molecular masses between 1000 and 4000, and n,m and w , which can be either different or identical, represent a number between 0 and 6. In order to achieve the purpose of the invention, polymers containing hidrocarbonated structures have been utilized, using the (II) formula, where A represents a ramified structure, and since the hydrocarbonated structure with more then 15 carbon atoms is a polyolephine, such polymers are radically and by addition reticulants. In particular, the parts that are interesting about (II) are olephine functions, isocyanate, epoxide, (III): -HC=CH-, -NCO, -CH - CH₂-. (Ill) \ / O

Polymers based on formula (II) containing free -NCO groups are obtained using the already known technique of the addition reactions of an isocianate in contact with -OH in such a manner so that the molar proportion between -NCO/ -OH will be bigger then 1 ,5. In particular, according to the invention, the suited radicals on which two or more isioianic formations should be attached to may be diphenil metane, dibenzyl, difenil oxide, stilbene, isoforone, toluene, tetramexil xilien, tetra-, penta-, hexamethilene, diciclohexametane, naphtilene or a mixture of some of these radicals. The epoxidic function can be introduced on an unlimited bases with any type of mono-, di- or polifunctional epoxidic resin with the sole condition that its molar mass would be smaller than 4000. The polymers used for this invention, which have functional groups and double connections, can serve as matrix when covalently linking polar substances with a high level of adherence on activated rubber particles and different types of organic and non organic fillers such as polyethers or polyesthers or liniar polyolephines and especially the branched ones. Depending on the structures A, R₂, R₃, R₄, R₅₎ and on the values n,m and w in the polymer existing in formula (II), you can obtain compositions containing various activated rubber particles, depending on the result we're looking for. Generallly, it has been noticed that in no long term period the composition subject of the current invention strengthens at room temperature without the use of catalysts, as a result of some functions being both reactants and catalysts for other functions, which confers advantages when putting the invention into practice. In particular, according to the aspects of the invention, the urethanic formation can be a catalyst for the addition reactions of the isocianats together with the polyopols and in the mean time is also a reactant for the -NCO formations. According to the invention, hydroxiurethanes can be represented through the formula (IV): HO-R₆-OOCHN-R₇-NHCOO- R₆-OH (IV) Where radicals Re, R₇ may be identical or different, radical Re may have two aliphatic carbon atoms or can contain two lateral aliphatic catenas with more then just one carbon atom. R₇ may be an aliphatic formation containing 2 up to 6 carbon atoms or it may be an aromatic with aliphatic structures placed on the core on which the functional formations have been attached. Also, R₆, R₇ may have a diverse molecular structure: etheric, estheric or hydrocarbonated. The polymers used for this invention can be prepared through any conventional way, such as the one I am about to present.

(a) The synthesis of a polymer in which component (A) from structure (II) has one of these forms: (R-CHOH-R^"-COO)rR^" (V) (HO-P-COO)Rr (VI) in which R may have a hydrocarbonated structure containing a number between 1 and 5 carbon atoms, R may be an olephinic or polyolephinic containing 5 up to 15 carbon atoms, R^" can be a diol, triol or poliol radical containing a number between 2 and 8 carbon atoms in the molecule, of different types: ethilene, buthilene, pentamethilene, hexamethilene, octamethilene, neopenthilene, trimethilene propan, tetramethilene methan. Inside the structure of the R radical the methilen formations can be separated by heteroatoms such as O and S or by aromatic structures such as benzene and benzenile metall; P represents a polymeric catena with a polyesteric structure, saturated or nonsaturated polyetheric or polybutadienic with molecular masses between 500 and 4000, the nonsaturated structure inside P can come from a nonsaturated acid or mixture of nonsaturated acids such as maleic, fumaric, itaconic or their anhidrides or polybutadiene while r can have values between 1 and 4.

(b) The process of polymerization that is necessary in obtaining the above mentioned polymers and which represents a part of the composition according to the invention, takes place in the presence of a hvdroxiurethan (IV) combined with the water in the atmosphere and can take place at room temperature, without catalysers and for a period of a few hours or even a few minutes in an accelerated manner, the process takes place in the presence of the catalysers. The catalysers that should be used in order to accelerate the reaction between - NCO and -OH are the known organometalcs compounds, intensely used in the polyurethane industry, and they are: stanium dioctate and dilaurated stanium dibutyl in proportions of 0,2...0,8%. In time, the composite strengthens, based on the reaction between the epoxidic formation and the aliphatic urethania, thus creating an advantage for the actual application of the invention because the composite material can be mold into different shapes and within reasonable time limits, allowing you to achieve the right quality of the materials.

The double connections inside the nonsaturated structures, according to the invention, allow the composite material a glassy, low transition temperature Tg , under -30C and in the mean time, very resistant to high level oxidation. However, in some particular cases, antioxidants- such as the composites alchil imino imidazoline betaine, alchil imino imidazoline amphoterisated or alchil amino amidoimina amphoterisated or a mixture of those in a maximum proportion of 2 procents- could be added; the alchil formation has 16...22 carbon atoms, one or more nonsaturations or terpenic formations.

It would be better if the organic materials used for the filling-microfibriles- which are smaller then 10μm, were made from the wastes that usually remain from producing and processing of natural or synthetic fibers. Together with the conventional non-organic fillers, mentioned above, the wastes are mixed with the activated rubber particles and the suitable reactive polymer. The filler' humidity, as related to the invention, shouldn't be higher than 20 ppm; by h umidity m eaning the water a bsorbed by the filling, and n ot the water we u se to

hydrate it. The non-organic products used as a component of the composite that is subject of this invention are salts or metallic oxides such as: copper sulphate, zinc oxide, which also serve as pigments. In addition, the copper sulphate also has an antifungus function.

According to the invention, the composite can be made in adequate industrial installations or even on the spot by simply mixing it's components with the use of usual instruments such as ballast mixer or it can be sprayed on in successive layers of activated rubber particles together with the connecting polymer on a suitable surface.

By suitable surface I'm referring to any kind of surface, some of those being metall, wood, glass, asphalt.

The solvents used according to the invention have the role of shrinking the viscosity of the polymer being used in making the composite, especially when dealing with working temperatures a slightly over 15C, situations that we often come across with especially during spring or autumn. According to the invention, the composite's suited viscosity in these cases is to be measured with the Brookfield viscosity apparatus, rotor no. 4, and can variate between 2000...6000cP. The most appropriate solvents are mostly mixtures of ethil acetate or butyl acetate with toluene or xilene_and gasoline or DMF and a chlorine derivate such as dichloride methane methilene chlorine, tetrachlorethilene.

The right concentration of polymers subject of this invention mixed with a solvent or a mixture of solvents as shown above, can be established based on the structure of the polymer, of the solvent and on the purpose of the composite. All these together can lead to a number of advantages, such as:

-the composition allows you to obtain a more flexible and controllable cover and better adherence to different surfaces;

-very easy to apply without requiring special surface preparations, besides the usual one;

-the parts that are coated according to the invention have a higher chemical resistance to hydrolysis, oxidation, petrol derivates and fungus;

-mechanical endurance when it comes to bending it and vibrations;

- low temperature Tg glassy transition;

-it uses the wastes which raise significant environmental issues, the waste material rubber crumb, once activated with UV radiations doesn't corrode the instruments, doesn't pollute the environment anymore, its very easy to approach from a technological angle and is not a danger for the operating personnel;

-the microfibriles obtained from fiber wastes are also being used;

-the materials incorporated in the composition as well as the obtaining conditions are accessible from the technical and economical point of view;

-the method is being achieved without leaving any wastes behind.

And here there are 22 examples of achieving the invention. Example 1

(a) Obtaining the activated rubber

In a mixer of 8 dm3, that contains heating and stirring devices, air holes for mixing the powders, device for mist like spreading of liquid products, 2 UV lamps that together contain the radiation spectrum of 200^50 nm, with an intensity of 200mW/cm² each, we introduce 2000 parts rubber particles with the volumetric density of 0.35g/cm³ and the sizes as written below:

2mm 60%

1mm 22%

0,5mm 15%

under θ.5 3%

total 100

After introducing the rubber, the top of the mixer is closed and the air is allowed to circulate so that it can stir. The volume of air entering on each noozle is of 30001/hour. While stirring, at room temperature, it is pulverized in a mist like form for 20 min, 18,2 methil castor oil-plant o leat, t hen t he U V I amps a re c oupled for 60 s econds. T he U V I amps a nd t he a ir stirring are turned off and the product is left to mature for another two hours.

(b) Obtaining the reactive polymer In a reactor with a 5 liters capacity, that has stirring options, an inert gas line, vacuum and heating, we place 1000 parts dehydrated castor oil, with a hydroxyl number of 130 mg KOH/g, 100 parts maleic anhidrida and is heat through stirring at 120C for an hour, after which 1000 parts of polypropilene ether with a molecular mass of 1700 and the hydroxyl number 47,6 are being added and then heated for another hour in conditions of low pressure 1-2 mmHg and 140C. The reactor is brought to a low temperature with the help of nitrogen purified with oxygen and traces of water and its lowering its temperature till 110C, and then, under a strong stir, 700 parts of 4,4 -melted oxide diphenil disocianate. After adding the isocianate, the mix is continuously stirred for another hour and kept at a temperature of 100C, after which it is brought to 60C and mixed with 500 parts aromatic epoxidic resin with an epoxidic equivalent of 0,45 mEq/g and 200 ml ethil acetate and is still left for stiring for 2 more hours. The viscosity of final product measured at 20C is 2600cP (c) Obtaining the composition

In a mixer like the one used on point a), we place 1000 parts of the product we obtained in stage a) and 1100 parts of the product obtained in stage b), 3 parts hydroxiurethane, 0,2 parts imino imidasoline betaine, 5 parts polyamidic microfibers, 0,5 parts polyestheric microfibers, 0,5 parts celulosic microfibers, 2 parts calcium carbonate, one part bentonite, 0,1 parts silicium dioxide, 0,1 parts barium sulphate, 0,02 parts copper sulphate, 0,2 parts of a mixture made with equal sizes of zinc oxide, titanium oxide, talc, iron oxide and chrom oxide. Another 10 parts of formamide dimethil are being added to mixture. The components stir at room temperature for 20 minutes, after which the paste can be applied on different surfaces. The hardening period at room temperature is of 6 hours and if stanos octoate 0,04% is added, the period shrinks down till 2 hours waiting. The adhesion level on different surfaces is shown in graphic number 1. Graphic 1.

Besides a very good adhesion, the parts that were coated with the mix are very elastic and extremely resistant to mechanical shocks. Also, its thickness 4-8 mm provides a very good hydroinsulation. This composition is formed of two elements: -activated rubber crumb(1 ) -the polymer(2) Examples 2-10 These examples differ from example 1 because of the fat estheric acids that make the activation of the rubber particles possible, their quantity, the time they need to activate under UV radiations and the quantity of the rubber particles, see graphic 2 and the composite's structure obtained according to C stage, meaning 2200 parts of the product that has been obtained as s hown o n p oint B a nd u sing t he working t emperature and d uration shown o n graphic 3. GRAPHIC 2

With the activated rubber particles shown in graphic 2, 9 compositions have been formed as shown in graphic 3, using a reactive polymer obtained in b point conditions of the example 1 sintetised of: - 200 parts poly (ethilene adipat maleat fumarat) diol with a numeric molar mass of 2000, hidroxyl number 56 mg KOH/g, maleic number: fumaric acid 3:1 :1 ; - 20 castor oil parts; - 100 polybutadiene parts with terminal OH groups with a xidroxyl number of 52 mg KOH/g; - 5 dihidroxi parts diurethane; - 20 parts epoxi resin parts with an epoxi equivalent of 0,45 Eq/100 g; 50 disocianate ethilene parts; - 40 disocianate stillen parts; - 600 parts N-methil pirolidone. Results a polymer with a viscosity of 3800 cP with 1 ,7% NCO groups and 0,2% free epoxi groups. GRAPHIC III

Note - Adhesivity to : ' concrete *** plaster EXAMPLE 11 (a) Activated rubber obtaining In a mixer like the one in example 1 , 8 dm3, 2000 parts rubber particles are introduced with a volumetric density of 0,42 g/cm3 and the particles sizes as shown below: 2mm 20% 1mm 42% 0,5mm 20% under 0,5mm 18% Total 100 While stirring, the content is pulverized in a mist like manner for 30 minutes. 22g of methilic esthers contained by the fat acids come from soybean oil, sunflower oil, cardui mariae oil in a 1:1:1 gravimetric proportion and then the UV lamps are coupled for 80 seconds. T he U V I amps a re d isconnected a nd s o i s t he a ir s tirring, I eaving t he product to mature for another 4 hours. (b) Reactive polymer obtaining Using the same procedure as on example 1 , this time replacing the castor oil with 1000 parts trifunctionale polyether carrying the number OH 48 mg KOH/g, the molecular mass of 3500 and the acidity number 0,2 KOH/g. The polyether is obtained from:

One mol of propane trimethil Three mols of maleic anhidrida

Three mols of ether diol polypropilene with the properties: Molecular mass = 1000, and OH number 112 mg KOH/g, in addition to the maleic anhidrida over the propane trimethilol, combined with the condensing product that has been obtained with polyprophilene ether at 140C, and a pressure of 2-3 mm Hg, for 2 hours. The proportion between the 2 structures, cis:trans is of 1 ,2:0,8. The other components that have to be used are: 1000 parts dyol polybutadiene with molecular mass equal to 2700, and the OH number 40 mg KOH/g;

800 parts 4,4 - disocianate dibenzil;

400 parts aliphatic epoxidic resin with an epoxy index = 0,4 mEq/g;

100 parts ethane trichlorine;

100 parts toluen;

200 parts ethil acetate. The obtained polymer's viscosity is 3500 cP measured at 20C (Brookfield, number 4 rotor) (c) The compound obtaining

In a mixer, with the same capacity and equiped as the one in example 1 , 800 parts of the product obtained in stage a) are being introduced and along those, another 500 parts of the product obtained in stage b). The components are mixed at room temperature for 20 minutes after which it is ready to be applied on various surfaces. The time needed for the substance hardening, at room temperature is of 12 hours, and with a catalyser, 0,4% dilaurated stanium dibuthyl, the time is reduced to 3 hours at room temperature. The composite has an adherence to iron of 16,8 N/cm, Tg is of -37C and a very good flexibility - 20.000 repeated flexions (Bally) at -10C. This product is most suitable for pavements- industrial halls especially- sport grounds, playgrounds, paddocks and crossing levels. The composite contains: • Activated rubber • Polymer EXAMPLE 12 Proceeding as in point 11 by adding: 0,3% stanos octoat 0,01 % zinc powder finer then 4μm; 6% dioxide titanium; 2% talc; 0,8% alchil imino imidasoline amphoterised as an oxidation inhibitor

The composite had an adherence to stainless steel of 8.8N/cm and a very good flexibility, 80.000 repeated flexions (Bally) at room temperature. Also, it has proven to be a very good anticorrosive protection for the iron surface. Objects that have been protected with the composition described on example 12 do not oxide in a 20% solution of NaCI during a year.

EXAMPLE 13

The difference between this example and example 12 is the fact that this time the composition is spread directly on the surface to protect. On an iron surface with the dimensions 500x500x2 mm its being sprayed, with the use of a pulverizing instrument, 10 g of the product obtained at point b), Example 11 which also contains stanos octoat. Ten minutes later we add another 10 parts of the same polymeric component containing 5% aluminum powder and 0,02% zinc powder and 300 successively parts of the composition described on Ex.12. 24 hours later the obtained composite has an initial module of elasticity equal to 33 MPa, a breaking resistance of 8 MPa and can not be detached of the metallic surface without causing damage to the material. EXAMPLE 14 (a) Hydroxiurethane obtaining

In a glass reactor like the one described in example 1 , 800 parts of 98% pure isophorondiamine, 400 parts of 98% pure ethilene carbonate, 100 parts of polyethilene oxide with mass equal with 400 and 400 parts of polypropylene ether which mass equals 1000. Start the stirring and heating. After reaching 80°C the reaction mixing is kept under stirring for 2 more hours during this period of time inside the reactor the dihydroxi diizophoron ethylene diurethan is transforming into polyether solution, then the heating stops and the mixture is brought to the room temperature along with a cooling agent. COMPOUND OBTAINING

Using the same procedures as in example 12, the only difference being the fact that 6 more parts of composite C are added. The result is a composition with an adherence to glass of 4,6N/cm.

EXAMPLES 15-18

At the accomplishment of these composites all the other examples have been used but still they differ through the nature and quantity of the microfibriles or by the quantity and structure of the isocianate as shown in graphic IV.

Graphic IV

In graphic V it is shown the resistance to breaking in comparison to the composites achieved according to example 1 with the rubber particles activated with UV radiations and non-activated with different granulations. Graphic V

Claims

1. Rubber particles polymeric compound is costituted of vulcanized rubber particles treated with esthers of fat unsaturated with inferior's alcohol acids and activated with UV radiations and 2 20%, preferable 8 17% a reactive polymer with double polymerisable compounds to a proportion of 0,2 10 molls/10000g, p referable 0 ,4 8 molls/10000 g , 1 20%, preferable 1 ,1 13% free isocianic compound, 0,01....18%, preferable 0,1 15% epoxy compound, 0,1 150 parts, preferable 2 50 parts of an aliphatic or aromatic hydroxiurethane or a compound of its with a concentration of the urethane's compound of 4 15 molls -NH-COO- /1000 g, preferable 5 12 molls -NH-COO-/1000 g, 001 3 parts, preferable 0,1 0,25 parts of catalysts chosen between stanium dioctate or dilaurated stanium dibuthyl, 0,1 3 parts, preferable 0,2....1 ,3 antioxidant parts chosen between imino imidazoline bethaine, alchi imino imidazoline amphoterisated or alchil amidoimine amphoterisated, 2 8 parts, preferable 4 6 parts of microfibriles chosen between polyamidic, polyesteric, cellulosic microfibriles or a composite of those mentioned, 0,1 60 parts, preferable 2 20 parts an inorganic product under powder form with a particle keenness under 2 microns chosen between limestone, bentonite, silicium dioxide, barium sulfate, copper sulfate, zinc oxide, titanium dioxide, talc, iron oxide, chrome oxide or 0,01 10%, preferable 0,2 6% metallic powder chosen between aluminum, zinc, copper or its composit, 0 90 parts, preferable 0,1....70 solvent parts.

2. Composite according to claims 1 and 2, characterized by the unsaturated inferiors alcohol fat acids esthers quantity is of 0,005...20%, preferable 0,01....8% weight, reported to the rubber particles.

3. Composite according to claim 2, characterized by the use of saturated inferior alcohol CrC _.

4. Composite according to claim 2, characterized by the unsaturated fat acids which results on of one the oleginous plants triglycerides extracting, like corn (Zea mays), soybean (Glycine max), mustard (Brasica alba), linseed (Linum ustiatissimum), sunflower (Helianhtus a nnuus), rapeseed (Brassica napus), olive tree (Olea europaea), castor bean (Ricinus Communis), coconut (Cocos nucifera), palm oil (Elaeis guinmeensis), Cardui mariae fructus (Silybum marianum).

5. Composite according to claim 1 , characterized by the fat acid esther that may contain OH free groupings.

6. Composite according to claim 1 and 5, characterized by the fat acid esther that may contain polymerisable double connections.

7. Composite according to claim 1 , characterized by the reactive polymer that contains 0,2....10 molls/10000g, preferable 0,4....8 molls/10000g polymerisable double connection.

8. Composite according to claim 1 and 7, characterized by the reactive polymer content 2 20%, preferable 4 13% free isocyanine groups.

9. Composite according to claim 1 ,7 and 8, characterized by the reactive polymer content 6....18%, preferable 8 15% epoxy groups.

10. Composite according to claim 1 , characterized by the rubber particles treated with an unsaturated fat acid ester and UV radiations on the top of the rubber particles eventually contains OH free reactive groupings.

11. Composite according to claim land 10, characterized by the rubber particles treated with an unsaturated fat acid ester and UV radiations on the t op o f t he r ubber p articles e ventually c ontains p olymerizable d ouble connections.

12. Composite according to claim 1 and 10, characterized by it's content of 2 150 parts, preferable 8 50 parts aliphatic or aromatic hidroxiurethan or compounds of those two.

13. Composite according to claim 1 or 12, characterized by: the hyroxiurethane w hich c ontains a c oncentration i n u rethanique g roupings included between 4 15 molls -NH-COO-/1000g, preferable 5 12 molls -NH-COO-/1000g.

14. Composite according to previous claim, characterized through the fact that it also contain antioxidants chosen between imino imidazoline betaine alchil imino imidazoline amphoterisated or alchil amidoimina amphoterisated

15. Composite according to claims 1-14, characterized by the fact that the microfibriles are chosen between polyester, polyamidic, cellulose microfibriles or its compounds.

16. Composite according to previous claims, characterized by the fact that the inorganic product is chosen between the limestone, bentonite, silicium dioxide, barium sulfate, copper sulfate, zinc oxide, titan dioxide, talc, iron oxide, chrome oxide or metallic powder chosen between aluminum, zinc, copper or its composite with a particle size less then 2μm.

17. Composite a ccording t o c laim 1 , c haracterized t hrough t he fact t hat t he solvent is chosen between methyl chlorine, dichloromethane, tetrachlorethilene or ethyl acetate, butyl acetate, diesel oil, gasoline, toluene or xylene or one of its compound.

18. The obtain procedure of the composition defined in 1-17 claims, characterized by the fact that the rubber particles resulted from the residuum vulcanized rubber with the dimension till 2mm are mixed, then it is treated with unsaturated acid esters with inferior alcohols in quantity, at the ambient temperature, for 100 particular pats, as the following relation shows: G=2,6p Where p represents the volume density of the rubber particles in g/cm³, 2,6 the coefficient in cm³, after that it irradiates with 2 UV lamps, both having the radiation spectrum between 200-450 nm, with the intensity of 200mW/cm², in a air fluidized bed, for 40-120 sec, preferable 42-60sec, at the 15-30°C temperature and, after a minim 2 Hrs. sweep, the activated rubber it is passed into a mixer and it is mixed with a reactive polymer, as a solution, to a rubber: polymersolvent gravimetric ration between 10:40:50 till 80:10:10, for 2...30 min with the obtaining of a rubber-polymer mixture with the 20.000- 80.000cP viscosity at 20°C and a maximum 90% solid content.

19. The procedure accordingly to claim 18, characterized by the fact that to the obtained product into a mixer are added and mixed for 20-30 min. the following: antioxidants, microfibers, inorganic products, metallic powders, as they are, or in mixture of 2 or more, accordingly with the composition utilization functions.

20. The obtain procedure of the composition defined in 1 , 7, 8, 9 claims, characterized by the fact that the reactive polymer is obtained into a reactor with agitation system, inert gas, emptiness and heating line, from a ramnificated poliol choose between castor-oil plant, p olyether o r d ewatering polyester, with 56...180 hydroxyl, preferable 60-120 mg KOH/g, maleic anhydride or itaconica anhydride, a macrodiol chosen between ether polypropylene , poly diethilene maleat fumarat, diol or poly-butadiendiol, diisocianate, agitating epoxy resin at 120...140°C, for 2...4 Hrs. and 1-2mmHg low pressure.

21. The utilization of the composition defined by 1-18 claims for mechanical and anticorrosive different surfaces coating protection like metal, wood, glass, ceramics materials, textures, floors, s pecial for gas a nd petroleum products transport pipes, for thermo-insulating plates, industrial hall pavement, sport fields, playgrounds, paddocks, level crossings, fittings, footwear flanges, different sport articles.

22. Mechanical and anticorrosive coating characterized by the fact that it is obtained from the composition accordingly to 1-17 claims.

23. Mechanical and anticorrosive coating obtained from the composition accordingly to claim 22, characterized by the fact that it i s o btained by the application of one or more composition layers defined in any of the claims, through pulverization or through pressing.