WO2005102956A1 - Chemical bonding of polymeric aggragate particles and/or liquid with bitumen and/or binders - Google Patents
Chemical bonding of polymeric aggragate particles and/or liquid with bitumen and/or binders Download PDFInfo
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- WO2005102956A1 WO2005102956A1 PCT/GB2004/001735 GB2004001735W WO2005102956A1 WO 2005102956 A1 WO2005102956 A1 WO 2005102956A1 GB 2004001735 W GB2004001735 W GB 2004001735W WO 2005102956 A1 WO2005102956 A1 WO 2005102956A1
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- WIPO (PCT)
- Prior art keywords
- modified
- bitumen
- polymers
- aggregates
- materials
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/26—Bituminous materials, e.g. tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to various methods of making polymeric aggregate particles-containing ionic functionalities and bitumen-containing ionic functionalities, based on using oxidising agents.
- the functionalised polymer particles and the functionalised bitumen or unmodified bitumen or binders can then be chemically bonded using a certain cross-linking agent.
- the un-functionalised polymer particles and the functionalised bitumen or unmodified bitumen or binders can then be chemically bonded using a certain cross-linking agent.
- the final product is suitable for, for example, the surfaces for city streets, highways, airfields and other construction applications.
- Polymers are chemical compounds built from large number of atoms. They are therefore of high molecular weight. Polymers can be of natural origin (e.g. cellulose, protein, natural rubber) or they may be synthetically produced ⁇ e.g. poly (ethylene), nylon, silicones ⁇ .
- Bitumen is the residual material left after the fractional distillation of crude oil. It is a mixture of hydrocarbon compounds and other chemical complexes containing nitrogen, oxygen, sulphur, carbon-carbon double bonds and metals such as nickel and vanadium. Bitumen can be subdivided into three main fractions such as carbenes, asphaltenes and maltenes.
- the ultraviolet light promotes a chemical reaction between alkali solution and the surface of plastics strips by etching the surfaces of the plastic strips and also alters the chemical make up of the surface of the plastic strips.
- the chemical reaction involves substituting hydrogen atoms in the plastic strips with cat ions from alkali solution.
- the exposure to ultraviolet light is for a short time( less than 24 hours) so that only surface portions of plastic strips are affected by this treatment.
- plastic strips Remove the plastic strips from the solution, rinsed in water and dried, vi) Use plastic strips as aggregates to replace 10 to 100 percent of the rock aggregate suitable for use in bituminous mixtures.
- the adhesives may be mixed with solvent to modify its viscosity.
- Coating the plastic particles with the coating materials can be achieved by rolling the plastic particles over the coating materials, spraying the coating over the particles or mixing the plastic particles in a container having the coating materials. Excess of the coating materials can be removed by use of a sieve. The size range of the plastic or rubber particles is between 2 to 20mm.
- the proposed solution to the weak bonding between the polymers and bitumen experienced in the mixtures produced using the above methods is generally via one of the following methods: 1. Oxidising the polymers and bitumen together and adding a cross-linking agent susequentley to the mix. 2. Oxidising the polymers and bitumen separately and then mixing them in the presence of a cross-linking agent. 3. Oxidising the polymers only and then mixing them with bitumen in the presence of a cross-linking agent. 4. Mixing the polymers and bitumen or binders in the presence of a cross- linking agent.
- bitumen and or binders have been treated as described in steps 3 or using another oxidising agents such as sulphuric acid, hydrogen peroxides or acetic acids individually or collectively.
- step (C) Bonding the functionalised polymer with the functionalised bitumen or un modified bitumen and or binder.
Abstract
The present invention relates to various methods of making polymeric materials (such as polymeric aggregate particles, polymeric liquid and or finely graded polymeric materials, etc. individually or collectively) -containing ionic functionalities and bitumen-containing ionic functionalities, based on using oxidising agents. The functionalised polymer material, particles or liquid and the functionalised bitumen can then be chemically bonded using a certain cross-linking agent. The final product is suitable for, for example, the surfaces for city streets, highways, airfields, for making base course and any layer in the structure of flexible and rigid pavements for airports, highways and other applications, waterproofing surfacing materials, school play grounds, play ground arid surfacing materials, roof surfacing materials and other construction applications. Polymers are chemical compounds built from large number of atoms. They are therefore of high and low molecular weight. Polymers can be of natural origin (e.g. cellulose, protein, natural rubber and plastic) or they may be synthetically produced (e.g. poly (ethylene), nylon, silicones). The particulate material defined above is suitable for use in construction comprising; modified polymers particles bonded to a modified or unmodified bitumen with or without the aid of curing agent (cross-linking agent), modified bitumen or binder contains modified polymeric materials with or without the aid of curing agent (cross-linking agent), unmodified bitumen or binder contains modified polymeric materials with or without the aid of curing agent (crosslinking agent), modified bitumen bonded to unmodified polymers particles or to unmodified polymeric materials (such as liquid or finely graded polymeric materials) with or with out the aid of curing agent( cross-linking agent) . Wherein said final product mixed with or bonded to pre-coated or uncoated aggregate particles (natural, artificial and crushed aggregates) or any other construction materials. The said final products also can be used in different industrial application with or with out mixed with other materials. The said modified polymers include all type of rubber and plastic materials including recycled, materials. The said modified polymers particles, modified polymeric bitumen, modified polymeric binders can be modified with the chemical mentioned in this patent application in one stage or multi stage applications prior to the mixing with other materials such as the modified or umnodified bitumen binders at both cold or hot mixing process at any temperature range between +OC° to +500C° . The modified bitumen or emulsions can be modified further as described in this application with adding 0.1 % to 30 % Sulphuric acid (or any oxidising agent or binder) by weight of bitumen and or any binder used in the process of producing the final products. The modified rubber and plastic aggregates or products can be pre-mixed with bitumen and or the binder before adding them to the rest of the bituminous mixture contents which normally consists of Asphalt binder (or any other binder with or without additives in cold or hot mixing environments), aggregates & fine materials. The modified aggregates described in this application can be used with any type of binders and emulsions, aggregates and fine materials individually or collectively by any percentages required.
Description
CHEMICAL BONDING OF POLYMERIC AGGRAGATE PARTICLES AND/OR LIQUID WITH BITUMEN AND/OR BINDERS
The present invention relates to various methods of making polymeric aggregate particles-containing ionic functionalities and bitumen-containing ionic functionalities, based on using oxidising agents. The functionalised polymer particles and the functionalised bitumen or unmodified bitumen or binders can then be chemically bonded using a certain cross-linking agent. Also, The un-functionalised polymer particles and the functionalised bitumen or unmodified bitumen or binders can then be chemically bonded using a certain cross-linking agent. The final product is suitable for, for example, the surfaces for city streets, highways, airfields and other construction applications.
Polymers are chemical compounds built from large number of atoms. They are therefore of high molecular weight. Polymers can be of natural origin (e.g. cellulose, protein, natural rubber) or they may be synthetically produced {e.g. poly (ethylene), nylon, silicones}.
Bitumen is the residual material left after the fractional distillation of crude oil. It is a mixture of hydrocarbon compounds and other chemical complexes containing nitrogen, oxygen, sulphur, carbon-carbon double bonds and metals such as nickel and vanadium. Bitumen can be subdivided into three main fractions such as carbenes, asphaltenes and maltenes.
There is a large potential market for strong and successful chemically bonded polymers and bitumen and many companies have attempted to achieve this. However so far none have been very successful.
Failure generally seems to be due to:
• Formation of weak bonding between the polymers and bitumen. • The use of several stages and costly process.
Prior to the present invention, methods for bonding polymers and bitumen involved ; A) Exposing recycled plastic aggregates to ultraviolet irradiation in the presence of strong alkali. Which can be achieved as follows; i) Collect and sort out recycled plastic to facilitate cutting. ii) Wash recycled plastic by using a heated solution of caustic soda solution such as (sodium hydroxide) in water to remove any contaminants such as labels, grease, etc.
iii) Cut recycled plastic into small particles/strips approximately no more than 12mm wide and 25mm -100mm long. Then wash the strips again in a caustic solution and rinsed with water. iv) Mix the particles into a high concentration solution of aluminium hydroxide or calcium hydroxide. Use a tank for holding the alkali solution and an agitator in tank for stirring the solution and the plastic strips so the plastic strips are all thoroughly wetted and their surfaces are evenly exposed to ultraviolet light. Use an ultraviolet lamp with a substantially continuous wavelength spectrum in the rang of 290 nm to 380 urn. The ultraviolet light promotes a chemical reaction between alkali solution and the surface of plastics strips by etching the surfaces of the plastic strips and also alters the chemical make up of the surface of the plastic strips. The chemical reaction involves substituting hydrogen atoms in the plastic strips with cat ions from alkali solution. The exposure to ultraviolet light is for a short time( less than 24 hours) so that only surface portions of plastic strips are affected by this treatment. v) Remove the plastic strips from the solution, rinsed in water and dried, vi) Use plastic strips as aggregates to replace 10 to 100 percent of the rock aggregate suitable for use in bituminous mixtures. B) Upgrading plastic particles by coating them with a coating materials such as; ethylene- vinyl acetate resin, epoxy, urethane resin, acrylic resin, polyester resin or vinyl chloride resin. The adhesives may be mixed with solvent to modify its viscosity.
Coating the plastic particles with the coating materials can be achieved by rolling the plastic particles over the coating materials, spraying the coating over the particles or mixing the plastic particles in a container having the coating materials. Excess of the coating materials can be removed by use of a sieve. The size range of the plastic or rubber particles is between 2 to 20mm.
In this invention, the proposed solution to the weak bonding between the polymers and bitumen experienced in the mixtures produced using the above methods is generally via one of the following methods: 1. Oxidising the polymers and bitumen together and adding a cross-linking agent susequentley to the mix. 2. Oxidising the polymers and bitumen separately and then mixing them in the presence of a cross-linking agent. 3. Oxidising the polymers only and then mixing them with bitumen in the presence of a cross-linking agent. 4. Mixing the polymers and bitumen or binders in the presence of a cross- linking agent.
As part of the present invention, there is provided a method for modifying the surface of polymeric particles and bitumen, comprising the steps of:
(a) Treating the polymer aggregate particles and or strips with an oxidising solution such as chromic acid ( potassium dichromate, water and sulphuric acid) of the formula, (1) K2Cr2O7 + H2O + H2SO4
Or the effect of other oxidising solution ( potassium chlorochromate and sulphuric acid) of the formula, (2) KClO3 + H2SO4
Or the effect of other oxidising solution ( potassium permanganate and sulphuric acid) of the formula, (3) KMnO4 + H2SO4 (4) Or any other inorganic or organic oxidising agent. (5) (b) The treatment of a polymeric material and or a bitumen by an oxidising agent will introduce various ionic functional groups on the
surfaces. These functional groups can then be reacted further in presence of a cross-linker such as divalent compound ( e.g. calcium chloride) or polyelectrolyte polymer (e.g. a polybase such as polyethyleneimine) to form a chemical bonded between the polymer and the bitumen.
Example
(a). Functionalisation of polymers 1. Clean the recycle polymeric materials such as plastic or rubber to remove the labels and any other contaminants. 2. The clean polymeric materials are then cut into strips approximately 2 x 8cm or any desired size. 3. Mixing the clean strips of polymers or polymers liquid with an oxidising solution such as chromic acid comprising of potassium dichromate : Water : Sulphuric acid in a ratio such as 7 : 12 : 150 by weight. The reaction time from 2 minutes -24 hours. 4. The treated polymers from step 3 are then washed thougrouly with water to remove the un-reacted oxidising solution.
(b) Functionalisation of a bitumen and or binders A bitumen and or binders has been treated as described in steps 3 or using another oxidising agents such as sulphuric acid, hydrogen peroxides or acetic acids individually or collectively.
(C) Bonding the functionalised polymer with the functionalised bitumen or un modified bitumen and or binder. Mixing the ftmctionalised polymer and bitumen from step (a) and (b) with
Claims
1. A method of bonding of modified or un modified polymers with modified or unmodified bitumen or binders, comprising the steps of : (a) functionalising the surface of one or all materials mentioned above; and (b) bonding of the functionalised materials with a cross-linking agent . (c) or bonding of the un-functionalised polymers with bitumen or binders with the aid of a cross-linking agent .
2. A method as claimed in claim 1 , wherein the said final product for use in the construction of a surface or a layer or layers comprising a
(a) modified or unmodified polymers bonded to a modified bitumen/binders with aid of a curing ( cross - linking) agent/s. (b) modified polymers bonded to unmodified bitumen binders with the aid of a curing agent (cross-linking agent/s). (c) un-modified polymers bonded to unmodified bitumen/binders with the aid of a curing agent/s( cross-linking agent).
3. A method as claimed in claims 1 and 2, wherein the curing agent comprises divalent compound or polyelectrolyte or any desired functional polymer.
4. A particulate material suitable for use in construction comprising modified polymers particles or liquid/s bonded to a modified bitumen with the aid of curing agent( cross-linking agent).
5. A particulate material suitable for use in construction comprising modified polymers particles or liquid/s bonded to a modified bitumen with the aid of curing agent( cross-linking agent), wherein said final product mixed with or bonded to pre-coated or uncoated aggregate particles or any other construction materials.
6. A particulate material suitable for use in construction comprising modified polymers particles bonded to a modified bitumen with or with out the aid of curing agent( cross-linking agent), wherein said final product mixed with or bonded to pre-coated or uncoated aggregate particles. Aggregate particles includes all types of natural, crushed, waste, recycled materials and artificial aggregates used in
construction industry, wherein the aggregates are coated or uncoated with cement mortar or any other type of coating agent and or paste.
7. A particulate material suitable for use in construction comprising modified or un modified polymers particles or liquid/s bonded to a modified bitumen or un modified bitumen or binders with the aid of curing agent/s( cross-linking agent), wherein the functionalisation of polymers and bitumen are curried out as follows; (A) Cleaning of polymers:
(i). Clean the recycle polymeric materials such as plastic or rubber to remove the labels and any other contaminants.
(ii). The clean polymeric materials are then cut into certain size strips or particles approximately 2 x 8cm. Or any other desired size such as 1 x 20mm,
20mm x 20mm, 10mm x3mm.
(B) Functionalisation of polymers Mixing the clean strips of polymers or liquid polymers with an oxidising solution such as chromic acid comprising of potassium dichromate : Water : Sulphuric acid in a ratio such as 7 : 12 : 150 by weight or any other desired ratio. The reaction time from 1 minutes to 24 hours. Use a suitable mixing temperature. The treated polymers from step iii are then washed thoughrouly with water if required to remove the un-reacted oxidising solution.
(C) Functionalisation of a bitumen, asphalt, binders A bitumen or any derivatives has been treated, if required, as described in steps (B) above at a suitable temperature, or using another oxidising
agents such as sulphuric acid, hydrogen peroxides or acidic acids individually or collectively.
8. A particulate material containing modified or un modified polymers particles bonded to a bitumen, asphalt or binder with the aid of curing agent( cross-linking agent), wherein the functionalised polymer from step (B) above.
9. A particulate material containing polymers particles or liquid( in liquid or solid states) bonded to a modified bitumen, modified asphalt or modified binder with the aid of curing agent( cross-linking agent), wherein the functionalised bitumen, asphalt or binder from step (C) above.
10. A particulate material substantially as herein before described mixed with natural aggregates such as crushed or uncrushed gravel, crushed aggregates ( rock) or any other type of aggregates including artificial aggregates to form a bonded or unbounded construction layer in pavement or any other structures wherein the aggregates size vary from 50mm to < 75μm
11. A particulate material substantially as herein before described mixed with natural aggregates such as gravel, crushed aggregates or any other type of aggregates including artificial aggregates to form a bound or unbounded construction layer in pavement or any other structures wherein the aggregates size vary from 50mm to < 75μm. Bound material includes mixing the aggregates described above with bitumen, asphalt, binder or any other suitable bonding agent to form bound layers in construction e.g. pavement layer or layers in highways
bitiiminous, rigid concrete pavement or composite materials/ structures.
12. A method of making a particulate material as defined in any one of the claims 1 to 12, comprising providing aggregate particles with a coating of modified polymer and allowing the coating to reach its initial setting.
13. A method as claimed in claiml 2, wherein the coating is provided by mixing the aggregate particles with the modified polymer at a suitable mixing temperature or temperature range i.e using hot or cold mixing techniques.
14. A method as claimed in claim 13, comprising mixing the aggregates with modified and or un modified binder, bitumen, asphalt or any bonding agent/adhesive at a suitable range of mixing temperature .
15. A method as claimed above, wherein 0. ltol2 wt.% of additional limes by weight of aggregate used are added.
16. A method as claimed in claims 14 to 15, comprising mixing the product with additional cement, microsilica and or pulverised fuel ash (PFA).
17. A method as claimed in claims 17 wherein 0.1 - 12 wt % of additional cement, microsilica and or pulverised fuel ash (PFA) by weight of dry aggregates used are added.
18. A method wherein the coated aggregates particles are separated by passing through or over one or more rotating and or vibrating sieves. Disposing the coated aggregate particles onto a conveyer before the coating reach its initial setting.
19. A method as claimed above, comprising adding dry cement and or accelerating powder to the coated aggregate particles while they are still mixing with the modified binder and or bitumen and or while they are still on the conveyor.
20. The use in construction of a particulate material as defined in the claims above.
21. The use of the coated aggregates as chippings or for surface dressing, wherein the surface comprises a road surface or an airfield surface, wherein the surface comprises bituminous pavement and or concrete pavement. Also the particulate material can be included in the surface layers and or roadbase layer/s of the pavement structure.
22. A method of modifying aggregate materials in order to improve their characteristics for use in bituminous or rigid pavement construction, wherein the aggregate material is provided with a coating as described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/GB2004/001735 WO2005102956A1 (en) | 2004-04-20 | 2004-04-20 | Chemical bonding of polymeric aggragate particles and/or liquid with bitumen and/or binders |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/GB2004/001735 WO2005102956A1 (en) | 2004-04-20 | 2004-04-20 | Chemical bonding of polymeric aggragate particles and/or liquid with bitumen and/or binders |
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| Publication Number | Publication Date |
|---|---|
| WO2005102956A1 true WO2005102956A1 (en) | 2005-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/GB2004/001735 WO2005102956A1 (en) | 2004-04-20 | 2004-04-20 | Chemical bonding of polymeric aggragate particles and/or liquid with bitumen and/or binders |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334032C (en) * | 2006-02-28 | 2007-08-29 | 武汉理工大学 | High early strength self expansion CA mortar material |
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| US5788760A (en) * | 1996-03-04 | 1998-08-04 | The Regents Of The University Of | Control of interface properties between fiber/cementitious material using plasma treatment |
| DE19728164A1 (en) * | 1997-07-02 | 1999-01-07 | Leonhardt Bau Gmbh | Hydraulic binder based building materials |
| US6069192A (en) * | 1998-10-13 | 2000-05-30 | Poly-Med, Inc. | Low fiber-loading composites with hybridized fiber/matrix interface |
| WO2002072499A2 (en) * | 2001-03-09 | 2002-09-19 | James Hardie Research Pty. Limited | Fiber reinforced cement composite materials using chemically treated fibers with improved dispersibility |
-
2004
- 2004-04-20 WO PCT/GB2004/001735 patent/WO2005102956A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5788760A (en) * | 1996-03-04 | 1998-08-04 | The Regents Of The University Of | Control of interface properties between fiber/cementitious material using plasma treatment |
| DE19728164A1 (en) * | 1997-07-02 | 1999-01-07 | Leonhardt Bau Gmbh | Hydraulic binder based building materials |
| US6069192A (en) * | 1998-10-13 | 2000-05-30 | Poly-Med, Inc. | Low fiber-loading composites with hybridized fiber/matrix interface |
| WO2002072499A2 (en) * | 2001-03-09 | 2002-09-19 | James Hardie Research Pty. Limited | Fiber reinforced cement composite materials using chemically treated fibers with improved dispersibility |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334032C (en) * | 2006-02-28 | 2007-08-29 | 武汉理工大学 | High early strength self expansion CA mortar material |
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