HIGHLY ABSORBENT AND ABSORBENT CAPILLARY HYDROPHOBIC POLYMER AND CORRESPONDING MANUFACTURING PROCESS

Abstract

The invention relates to an adsorbent and absorbent capillary hydrophobic polymer and to the related process for producing it; more particularly, this invention relates to a polymer derived from natural and synthetic oily substances, able to contain, remove and recover oil, hydrocarbons and chemical products of non-aqueous matrix in the event of spills or leaks of them inside or outside water.

Claims

1. Adsorbent and absorbent capillary hydrophobic polymer (C), able to contain and remove oil, hydrocarbons and chemical products of non-aqueous matrix in the event of spills or leaks of the same inside or outside of the water, derived from a first component (A) comprising natural oily substances and a second component (B) comprising synthetic oily substances, said polymer (C) wherein the first component (A) is obtained from a mix of two agents (a-0, -o), respectively obtained from a mix of sub-components (a-1-a-7, -1--3), the first agent (a-0) being obtained from a mix of first sub-components (a-1-a-7): vegetable oil (a-1) containing triglycerides and fatty acids with high molecular weight including OH groups; like 12-hydroxil-9 octadecenoic acid; deionized water (a-2); low grade (from 2 to 6 moles) ethoxylation surfactant (a-3), like nonylphenol ethoxylate, ethanol 2.2 dodecyloxy ethoxy and their mixture; aminic catalyst and reaction accelerator (a-4), like dimethylcyclohexylamine, dimethylbenzylamine, pentamethyldiethylentriamine or 2.dimethylaminoethyl ether; metallic catalyst (a-5): tin octoate or dibutyltin dilaurate; mass/volume stabilizer (a-6), like vegetable wax or paraffinic oil; cream stabilizing agent (a-7): PDMS Polydimethylsiloxane; the second agent (-0) being obtained from a mix of second sub-components (-1--3); expanding agent (-1): in particular methyl formate (with low toxic grade in comparison with other expanding agents); chain extensor agent (-2) selected between 3-Aminomethyl-3,5,5-trimethylcyclohexylamine and monoethylene glycol; hydrophobic agent (-3), like amorphous synthetic silica superficially treated with polyalkylsiloxane; and wherein the second component (B) is obtained from a mix/mixture of third sub-components (b-1-b-3): polymer MDI (b-1) derived from 4.4 diphenylmethane diisocyanate, 2.4 diphenylmethane diisocyanate, 2.2 diphenylmethane diisocyanate, with average functionality between 2.5 and 3; polymer TDI (b-2): 2,4 toluene diisocyanate; flow agent (b-3), like turpentine.

2. The polymer (C) according to claim 1, wherein the first component (A) is obtained from a mix of the sub-components (a-1-a-7, -1--3), with the following weight percentage of the different ingredients: 70-90% vegetable oil (a-1) containing triglycerides and fatty acids; 2.0-5% de-ionized water (a-2); 0.1-1.5% low grade ethoxylation surfactant (a-3); 0.0-0.5% aminic catalyst and reaction accelerator (a-4); 0.2-1.5% metallic catalyst (a-5); 0.2-1.5% mass/volume stabilizer (a-6), like vegetable wax or paraffinic oil; 1.0-5% cream stabilizing agent (a-7) PDMS Polydimethylsiloxane; 1.0-6.5% expanding agent (-1); 2.0-6.0% chain extensor agent (-2); 0.5-2.5% hydrophobic agent (-3). and wherein the second component (B) is obtained from a mix/mixture of the sub-components (b-1-b-3), with the following weight percentage of the different ingredients: 57-97% polymer MDI (b-1); 0.0-43% polymer TDI (b-2); 3.0-7.5% flow agent (b-3).

3. Polymer (C) wherein it is obtained from a mix of the first component (A) and the second component (B), in the following weight percentage: 47-53% of the first component (A); 53-47% of the second component (B).

4. The polymer (C) according to claim 1, wherein the vegetable oil (a-1) is derived from plant seeds and fruits of a wide range of species without any limitation, provided that they contain in their composition triglycerides and fatty acid with high molecular weight including OH groups, like palms, coconuts, sunflowers, castor beans, linseed, passion fruit, rapeseed.

5. A process to obtain the capillary hydrophobic polymer (C), adsorbent and absorbent, characterized by a first phase, necessary to obtain a first component (A), and by a second phase, necessary to obtain a second component (B), and by a third final phase, necessary to obtain the capillary hydrophobic polymer (C) with high adsorbent and absorbent power; said first phase of the process, necessary to obtain the first component (A), comprising the following steps: in a first container (E17) rotating at 1350 (20%) RPM, all the sub-components (a-1), (a-2), (a-3), (a-4), (a-5), (a-6) and (a-7) are mixed for 20-30 minutes in order to obtain a first agent (a-0); according to the invention, the first container (E17) may also be a mixer; in a second container (E20) rotating at 1400-1700 RPM, all the sub components (1), (-2), (-3), are mixed for 10-15 minutes in order to obtain the second agent (-0); in a third container (E-24), rotating at 1/4-1/3 RPM, the mentioned first agent and second agent (-0,a-0) are mixed for 20-25 minutes in order to obtain the first component (A); it is also possible to put the content of the second container (E20) inside the first container (E17) and vice versa, lowering the rotation speed to 1/4-1/3 RPM; said second phase of the process, necessary in order to obtain the second component (B), comprising the following steps: in a fourth container (E-36), hermetically closed and isolated from the external atmosphere, rotating at 1/4-1/3 RPM, all the sub-components (b1), (b-2), (b-3) are mixed for 20-30 minutes in order to obtain the second component (B); said third final phase of the process, necessary in order to obtain the capillary hydrophobic polymer (C) with high adsorbent and absorbent power, comprising the following steps: substantially equal quantities (47-53%) of the first component (A) and of the second component (B), obtained from the previous phases, are separately conveyed into the injection chamber of an injection machine (E-14) wherein the two components (A; B), in percentage weight between 47% and 53% are mixed to produce the polymer (C).

6. The process, according to claim 5, wherein the containers (E-17, E-20, E-24, E-36) may be completely or partly replaced with mixers.

7. The process, according to claim 5, wherein the capillary hydrophobic polymer (C) leaves the injection chamber of an injection machine (E-14) through the exit nozzle of said injection chamber (as a cream), to feed the mould connected to said nozzle and start the expansion process together with the forming process, in order to give the final commercial shape to the resulting final manufactured product (D); within 20-120 minutes (depending on the mould volume), said manufactured product (D) solidifies, reaching the final mechanical proprieties, being subsequently extracted from the mould.

8. Manufactured products (D) wherein they are constituted of the polymer (C) as per claim 1.

9. Manufactured products (D) as per claim 8, wherein they are moulded and/or machined in the form of booms, carpets, floccules, pillows, powder, foils, rolls, sheets, pellets, cords, bands and bags.

10. Filters and filtering systems wherein they utilize the manufactured product (D) as per claim 8.

11. Containing, removing and recovery methods for industrial, commercial and domestic spills and leaks of oil, hydrocarbons and chemical products of non-aqueous matrix characterized in that they utilize the manufactured products (D) as per claim 8.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] FIG. 1 shows the flow chart of the process for production of a highly adsorbent and absorbent capillary hydrophobic polymer C and a manufactured product D derived from it, where: [0038] a1-a7, 1-3, b1-b3 represent sub-components of the polymer (C), which are contained in tanks; [0039] E25-E35, E42-E44 represent dosing devices for dosing the above-mentioned components; [0040] E-17 represents a first container (or mixer); [0041] E-20 represents a second container (or mixer); [0042] E-24 represents a third container (or mixer); [0043] E-36 represents a fourth container (or mixer); [0044] E-14 represent an injection machine; [0045] E-23 represents a compressed air system; [0046] E-41 represents a mould; [0047] A represents a first component of the polymer (C), derived from natural oily substances; [0048] B represents a second component of the polymer (C), derived from synthetic oily substances, such as TDI and MDI polymers.

[0049] FIG. 2 illustrates two possible embodiments of manufactured products (D) constituted of the polymer (C): a sausage-shaped floating boom and a mat.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT OF THE INVENTION

[0050] The adsorbent and absorbent capillary hydrophobic polymer (C) according to the invention comprises: [0051] a first component (A) comprising polymers derived from natural oily substances such as plant seeds and fruits of a wide range of species without any limitation, provided that they contain in their composition triglycerides and fatty acids with high molecular weight containing OH groups. Non-limiting examples of such vegetable sources are: palms, coconuts, sunflower seeds, castor beans, linseed, pomegranate seeds, rapeseed. The hydrophobic agents are derived from amorphous silica superficially treated with polyalkylsiloxane; [0052] a second component (B) comprising MDI polymers, derived from 4,4 diphenylmethane diisocyanate, 2,4 diphenylmethane diisocyanate, 2,2 diphenylmethane diisocyanate, with average functionality between 2.5 and 3 in combination with TDI 2,4 toluene diisocyanate.

[0053] The first component (A) is obtained from two agents (a-0, -0), which are respectively obtained by mixing the sub-components (a-1-a-7, -1--3).

[0054] In particular, the first agent (a-0) is obtained by mixing the first sub-components (a-1-a-7), with the following weight percentages: [0055] 70-90% vegetable oil (a-1) containing triglycerides and fatty acids; [0056] 2.0-5% de-ionized water (a-2); [0057] 0.1-1.5% low grade ethoxylation surfactant (a-3); [0058] 0.0-0.5% aminic catalyst and reaction accelerator (a-4); [0059] 0.2-1.5% metallic catalyst (a-5); [0060] 0.2-1.5% mass/volume stabilizer (a-6), like vegetable wax or paraffinic oil; [0061] 1.0-5% cream stabilizing agent (a-7) PDMS Polydimethylsiloxane.

[0062] The second agent (-0) is obtained from a mix of second sub-components (-1--3), with the following weight percentage of the different ingredients: [0063] 1.0-6.5% expanding agent (-1); [0064] 2.0-6.0% chain extensor agent (-2); [0065] 0.5-2.5% hydrophobic agent (-3).

[0066] The second component (B) is obtained from a mix of third sub-components (b-1-b-3), with the following weight percentage of the different ingredients: [0067] 57-97% polymer MDI (b-1); [0068] 0.0-43% polymer TDI (b-2); [0069] 3.0-7.5% flow agent (b-3).

Process for Obtaining the First Component (A)

[0070] In a first container (E17) rotating at 1350 (20%) RPM, the sub-components (a-1), (a-2), (a-3), (a-4), (a-5), (a6) and (a7) are mixed for 20-30 minutes in order to obtain the first agent (a-0). According to the invention, the first container (E17) may also be a mixer.

[0071] In a second container (E20) rotating at 1400-1700 RPM, the sub-components (1), (-2), (-3), are mixed for 10-15 minutes in order to obtain the second agent (-0). According to the invention, the second container (E20) may also be a mixer.

[0072] In a third container (E-24), rotating at 1/4-1/3 RPM, the mentioned first agent and second agent (-0,a-0) are mixed for 20-25 minutes in order to obtain the first component (A). According to the invention, the third container (E-24) may also be a mixer. It is also possible to put the content of the second container (E20) inside the first container (E17) and vice versa, lowering the rotation speed to 1/4-1/3 RPM.

Process for Obtaining the Second Component (B)

[0073] In a fourth container (E-36), hermetically closed and isolated from the external atmosphere, rotating at 1/4-1/3 RPM, the sub-components (b1), (b-2) and (b-3) are mixed for 20-30 minutes in order to obtain the second component (B). According to the invention, the fourth container (E-36) may also be a mixer.

Process for Obtaining the Capillary Hydrophobic Polymer (C) and the Manufactured Product (D)

[0074] Substantially equal quantities (47-53%) of the first component (A) and of the second component (B), obtained from the previous phases, are separately conveyed into the injection chamber of an injection machine (E-14) wherein the two components (A; B), in percentages of between 47% and 53%, are mixed by a flow of compressed air arriving from the compressed air system (E-23) for producing the polymer (C), which, through the exit nozzle of said injection chamber, feeds the mould connected to said nozzle, thereby starting the expansion process together with the forming process, in order to give the final commercial shape to the resulting manufactured product (D).

[0075] Within 20-120 minutes (depending on the volume of the mould), said manufactured product (D) solidifies, reaching the final mechanical properties, and is subsequently extracted from the mould so that it can be used as it is or mechanically machined to obtain other products such as sheets, powders, etc.

Role of the Main Components

[0076] Component A is responsible for the formation of the adsorption and absorption cells and for guaranteeing biodegradability.

[0077] Component B acts on the conversion of the natural oily substances into polymers, giving the polymer (C) its mechanical properties.

[0078] The function of the second agent (-0) is to improve the hydrophobic capabilities.

Detailed List of Components of the Composition

[0079] vegetable oil (a-1) containing triglycerides and fatty acids with high molecular weight including OH groups; like 12-hydroxil-9 octadecenoic acid; [0080] deionized water (a-2); [0081] low grade (from 2 to 6 moles) ethoxylation surfactant (a-3), like nonylphenol ethoxylate, ethanol 2.2 dodecyloxy ethoxy and their mixture; [0082] aminic catalyst and reaction accelerator (a-4), like dimethylcyclohexylamine, dimethylbenzylamine, pentamethyldiethylentriamine or 2.dimethylaminoethyl ether; [0083] metallic catalyst (a-5): tin octoate or dibutyltin dilaurate; [0084] mass/volume stabilizer (a-6), like vegetable wax or paraffinic oil for controlling moulded product D shrinkage; [0085] cream stabilizing agent (a-7): PMDS Polydimethylsiloxane for controlling the time for which the polymer C remains in the cream phase before expanding in the foam phase; [0086] expanding agent (-1): in particular methyl formate (with low toxic grade in comparison with other expanding agents); [0087] chain extensor agent (-2) selected between 3-Aminomethyl-3,5,5-trimethylcyclohexylamine and monoethylene glycol; [0088] hydrophobic agent (-3), like amorphous synthetic silica superficially treated with polyalkylsiloxane; [0089] polymer MDI (b-1) derived from 4.4 diphenylmethane diisocyanate, 2.4 diphenylmethane diisocyanate, 2.2 diphenylmethane diisocyanate, with average functionality between 2.5 and 3; [0090] polymer TDI (b-2): 2,4 toluene diisocyanate; [0091] flow agent (b-3), like turpentine.

Performance of the Manufactured Product (D)

[0092] The capillary hydrophobic polymer (C) may be moulded in various forms and/or machined to create new manufactured products (D), whose shapes are already known, such as floating booms, carpets, floccules, pillows, powders, sheets, rolls, pellets, cords, bands, bags, sacks, etc.

[0093] Said manufactured products have very interesting performance, as illustrated below.

[0094] The absorbent and adsorbent capacity of the manufactured products (D) disclosed is between 3 and 6 times greater, in terms of volume of oily pollutant, than the absorbent and adsorbent capacity of existing commercial products which are polyester-, polystyrene fibre- and polypropylene-based, and is between 6 and 10 times greater than natural products such as straw, sand, sawdust, vermiculite, peat, corn stalks, feathers, glass wool, volcanic ash, which are amongst those well-known in the prior art.

[0095] Said performance is due to the larger size of the cells (approximately 6 times the starting diameter of the polymer), as shown by the low specific weight of the manufactured product (between 80 and 150 grams per litre), and is also due to the higher number of re-use cycles of the manufactured product.

[0096] After each cycle of use of said manufactured product, it is wrung out to recover the oils adsorbed and absorbed, allowing a further re-use cycle.

[0097] The initial re-use efficiency is equal to 95% with a gradually decreasing rate. It is possible to reach between 10 and 20 re-use cycles, for heavy oil and light oil respectively.

[0098] The high and stable level of hydrophobic performance prevents any loss of the capacity to float of the manufactured product (D) during containing and recovering operations after spills of oil and its derivatives in the sea or in water.

[0099] The composition also allows an increase in the speed of absorption of high viscosity pollutant (30%) compared with existing products.

[0100] At the end of its useful life, the manufactured product may be used as a fuel due to its high energy content. It may also be disposed of in landfill, since it is biodegradable.

[0101] The manufactured products moulded in the form of booms are the ideal solution for containing large spills, on land or in water.

[0102] When quickly deployed, they contain spills of oil and chemical substances, preventing pollution of the environment and stopping said pollutants from entering our water supply and drainage systems.

[0103] Other forms, such as carpets, floccules, pillows, powder, foils, rolls, sheets, pellets, cords, bands and bags are more suitable for industrial and domestic spills.

[0104] Another interesting and effective application is use of the manufactured product as a filter for oily pollutant substances leaked in water.

[0105] The pollutant is retained by the manufactured product and the water, cleaned in that way, is available at the outfeed of the filter.