CA2179145A1 - Formulation and method for producing rubber vehicular impact barriers - Google Patents
Formulation and method for producing rubber vehicular impact barriersInfo
- Publication number
- CA2179145A1 CA2179145A1 CA 2179145 CA2179145A CA2179145A1 CA 2179145 A1 CA2179145 A1 CA 2179145A1 CA 2179145 CA2179145 CA 2179145 CA 2179145 A CA2179145 A CA 2179145A CA 2179145 A1 CA2179145 A1 CA 2179145A1
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- Canada
- Prior art keywords
- barrier
- weight
- polyurethane prepolymer
- formulation
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F15/00—Safety arrangements for slowing, redirecting or stopping errant vehicles, e.g. guard posts or bollards; Arrangements for reducing damage to roadside structures due to vehicular impact
- E01F15/02—Continuous barriers extending along roads or between traffic lanes
- E01F15/08—Continuous barriers extending along roads or between traffic lanes essentially made of walls or wall-like elements ; Cable-linked blocks
- E01F15/081—Continuous barriers extending along roads or between traffic lanes essentially made of walls or wall-like elements ; Cable-linked blocks characterised by the use of a specific material
- E01F15/086—Continuous barriers extending along roads or between traffic lanes essentially made of walls or wall-like elements ; Cable-linked blocks characterised by the use of a specific material using plastic, rubber or synthetic materials
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A formulation and a method are disclosed for on-site casting of rubber vehicular impact barriers, such as continuous, permanent highway median barriers. The formulation of the present invention, which preferably comprises 55-75% by weight rubber crumb, 5-12% by weight polyurethane prepolymer, 10-15% by weight polyol or glycol cross-linking agent, 10-20% by weight filler and 3-8% by weight fibrous material may be mixed and molded on-site by conventional mixing and molding equipment and produces a barrier having properties which allow it to be substituted for conventional concrete impact barriers.
Description
21 7q~ 4 ~3 FORMULATION AND METHOD FOR
PRODUCING RUBBER VEHICULAR IMPACT BARRIERS
FIELD OF THE INVENTION
The invention relates to a novel formulation for the manufacture of rubber vehicular impact barriers, for use as continuous highway medians for example, which for the first time allows on-site manufacture of rubber impact barriers.
BACKGROUND OF THE INVENTION
Highways and motor speedways are often constructed with temporary or permanent barriers to contain and direct vehicles that have lost control. Conventionally, the barriers are massive concrete walls which are either formed in situ or are prefabricated in interlocking modules. The modules may be prefabricated in a concrete manufacturing facility and transported to the erection site to be lifted into place with cranes or forklift trucks.
Modular barriers are typically used on a temporary basis to protect workers and equipment during highway construction, whereas permanent barriers to be used as highway medians are preferably continuous and therefore must be produced on-site.
U.S. Patent No. 5,336,016 to Baatz, the disclosure of which is incorporated herein by reference, teaches a rubber vehicular impact barrier comprising 80 to 90 percent by weight particles of recycled waste rubber and 10 to 20 percent by weight virgin rubber. Rubber impact barriers having this composition provide a number of advantages over conventional concrete barriers, as discussed at length in the above patent.
However, at least partly due to the use of virgin rubber in the formulation, heavy equipment is needed for mixing, extrusion and curing of barriers having the composition disclosed in the above patent. Specifically, the formulation of the above patent tends to be very viscous, requiring heavy mixing equipment and high pumping pressures. Also, the presence of virgin rubber requires that such barriers must be cured at high temperature and pressure for relatively long periods of time. The patent requires curing temperatures between 250 and 400~C at a pressure of from 500 to 1000 psi (pounds per square inch) for a period of time from 1.5 to 7.5 hours.
Because of the long curing time and heavy equipment required to manufacture barriers according to the above patent, such barriers must be manufactured in an off-site facility and subsequently transported to the erection site.
Therefore, the process of the above patent is limited to the production of barrier modules which are primarily used on a temporary basis and is impractical for use in on-site molding of continuous, permanent barriers.
On-site molding of impact barriers requires the use of simple equipment and requires that the barriers be molded and cured at temperatures and pressures as close as possible to ambient conditions. Furthermore, continuous molding of barriers requires that the curing time be relatively short, for example about 60 minutes or less, to allow the barrier to be produced at an acceptable rate.
~q~
The disadvantage exists that no formulations or processes are presently known which are acceptable for on-site molding of rubber vehicular impact barriers.
SUMMARY OF THE INVENTION
The invention overcomes the disadvantages of the prior art in a novel manner by providing a formulation which permits on-site molding of rubber vehicular impact barriers, and further provides a process for on-site manufacture of such barriers.
Impact barriers according to the present invention may be manufactured using simple equipment similar to that used for on-site manufacture of concrete barriers, without the application of external heat and at low pressure.
Furthermore, the formulation of the present invention has a shorter curing time than the prior art formulation taught in the above-discussed patent, which permits continuous production of barriers on-site at an acceptable rate.
The formulation of the present invention produces a barrier having impact strength, hardness and other properties desired in impact barriers as good or better than those of the prior art formulation discussed above.
In one aspect, the present invention provides a homogeneous molded solid rubber vehicular barrier, comprising: 55-75% by weight particles of rubber crumb; 5-12%
by weight liquid polyurethane prepolymer; 10-15% by weight of a diol or polyol cross-linking agent; 10-20% by weight filler; and 3-8~ by weight fibrous material.
PRODUCING RUBBER VEHICULAR IMPACT BARRIERS
FIELD OF THE INVENTION
The invention relates to a novel formulation for the manufacture of rubber vehicular impact barriers, for use as continuous highway medians for example, which for the first time allows on-site manufacture of rubber impact barriers.
BACKGROUND OF THE INVENTION
Highways and motor speedways are often constructed with temporary or permanent barriers to contain and direct vehicles that have lost control. Conventionally, the barriers are massive concrete walls which are either formed in situ or are prefabricated in interlocking modules. The modules may be prefabricated in a concrete manufacturing facility and transported to the erection site to be lifted into place with cranes or forklift trucks.
Modular barriers are typically used on a temporary basis to protect workers and equipment during highway construction, whereas permanent barriers to be used as highway medians are preferably continuous and therefore must be produced on-site.
U.S. Patent No. 5,336,016 to Baatz, the disclosure of which is incorporated herein by reference, teaches a rubber vehicular impact barrier comprising 80 to 90 percent by weight particles of recycled waste rubber and 10 to 20 percent by weight virgin rubber. Rubber impact barriers having this composition provide a number of advantages over conventional concrete barriers, as discussed at length in the above patent.
However, at least partly due to the use of virgin rubber in the formulation, heavy equipment is needed for mixing, extrusion and curing of barriers having the composition disclosed in the above patent. Specifically, the formulation of the above patent tends to be very viscous, requiring heavy mixing equipment and high pumping pressures. Also, the presence of virgin rubber requires that such barriers must be cured at high temperature and pressure for relatively long periods of time. The patent requires curing temperatures between 250 and 400~C at a pressure of from 500 to 1000 psi (pounds per square inch) for a period of time from 1.5 to 7.5 hours.
Because of the long curing time and heavy equipment required to manufacture barriers according to the above patent, such barriers must be manufactured in an off-site facility and subsequently transported to the erection site.
Therefore, the process of the above patent is limited to the production of barrier modules which are primarily used on a temporary basis and is impractical for use in on-site molding of continuous, permanent barriers.
On-site molding of impact barriers requires the use of simple equipment and requires that the barriers be molded and cured at temperatures and pressures as close as possible to ambient conditions. Furthermore, continuous molding of barriers requires that the curing time be relatively short, for example about 60 minutes or less, to allow the barrier to be produced at an acceptable rate.
~q~
The disadvantage exists that no formulations or processes are presently known which are acceptable for on-site molding of rubber vehicular impact barriers.
SUMMARY OF THE INVENTION
The invention overcomes the disadvantages of the prior art in a novel manner by providing a formulation which permits on-site molding of rubber vehicular impact barriers, and further provides a process for on-site manufacture of such barriers.
Impact barriers according to the present invention may be manufactured using simple equipment similar to that used for on-site manufacture of concrete barriers, without the application of external heat and at low pressure.
Furthermore, the formulation of the present invention has a shorter curing time than the prior art formulation taught in the above-discussed patent, which permits continuous production of barriers on-site at an acceptable rate.
The formulation of the present invention produces a barrier having impact strength, hardness and other properties desired in impact barriers as good or better than those of the prior art formulation discussed above.
In one aspect, the present invention provides a homogeneous molded solid rubber vehicular barrier, comprising: 55-75% by weight particles of rubber crumb; 5-12%
by weight liquid polyurethane prepolymer; 10-15% by weight of a diol or polyol cross-linking agent; 10-20% by weight filler; and 3-8~ by weight fibrous material.
2 1 7 ~
In another aspect, the present invention provides a homogeneous molded solid rubber vehicular barrier, comprising: about 60% by weight particles of rubber crumb having a size of 20 to 30 mesh; about 7.5% by weight of a liquid polyurethane prepolymer comprising a polyether based, methylene diisocyanate or methylene bis-(phenyl isocyanate) terminated polyurethane prepolymer having a percent isocyanate of from about 6 % to about 15%; about 12.5% by weight of polypropylene glycol having a molecular weight of about 6,000; about 15% by weight ground coal; and about 5% by weight chopped fiberglass having a fiber length of about 1/4 to 3/8 inches, said liquid polyurethane prepolymer and said polypropylene glycol forming a matrix in which said rubber, ground coal and chopped fiberglass are dispersed, wherein said barrier is a continuous highway median.
In yet another aspect, the present invention provides a method of manufacturing a homogeneous, solid rubber vehicular barrier, comprising the steps of: blending 55-75% by weight rubber crumb and 10-20% by weight filler; adding 10-15% by weight polyol or glycol cross-linking agent; adding 5-12%
polyurethane prepolymer; and adding 3-8% fibrous material;
forming the mixture in a mold to a selected barrier configuration; curing the mixture within the mold without application of external heat for a period of time from 45-60 minutes; and removing the cured barrier from the mold.
The impact barriers of the present invention utilizeinexpensive, readily available materials, most of which are available as recycled materials.
2 i 79 1 45 Further aspects of the invention will become apparent upon review of the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention may be readily understood, a preferred embodiment of the invention will be described by way of example with reference to the accompanying drawings in which:
Figure 1 is a sectional, perspective view of a portion of a continuous, permanent impact barrier which may be produced according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Figure 1 illustrates a portion of a preferred impact barrier 10 which may be produced using the formulation and the method of the present invention. Barrier 10 is a continuous highway median having a similar shape and size as a conventional concrete highway barrier, having two opposite, inclined side surfaces 12 and an outwardly flaring base portion 14.
Although barrier 10 is shown as a continuous highway median, it is to be understood that the formulation and method of the present invention may be used to produce impact barriers having any suitable configuration, either continuous or modular, and may for example have the shape and size of the barrier shown in Figures 1 and 2 of the above-discussed patent.
Barrier 10 is preferably produced on-site in long, ' 2~ 7~7 ~J
continuous lengths as will be described below.
Barrier 10 is shown in Figure 1 as having a pedestal 16 to be embedded in the roadway to provide increased resistance to vehicular impact loads. Alternatively, pedestal 16 may be eliminated and the barrier 10 may be simply placed on its base 14 upon the roadway surface. If pedestal 16 is eliminated, it is preferable to increase the overall dimensions of the barrier 10 in order to provide a larger inertial mass to resist vehicular impact loads.
The formulation of the present invention preferably comprises rubber crumb as the main ingredient, a low viscosity binder which sets quickly at low temperatures and pressure, a filler and a fibrous material.
Rubber crumb, the primary ingredient in the formulation, is preferably obtained as a recycled product derived from discarded automobile tires. The rubber crumb preferably comprises from about 55 to about 75 percent by weight of the formulation, and more preferably about 60 percent by weight of the formulation. The rubber crumb preferably comprises fine particles having a size of about 20 to 30 mesh.
The rubber crumb used in the formulation preferably does not contain significant amounts of steel. However, it is to be appreciated that in some cases it may be desirable that the barrier contains a minor amount of steel to improve impact strength of the barrier. In such cases, rubber crumb may be used which contains a small amount of steel derived from the metal wire reinforcement in the waste automobile tires. Although small amounts of steel in the formulation 2~143 may improve the impact strength of the barrier, barriers according to the present invention having acceptable impact strength and other properties may be manufactured with rubber crumb containing no steel.
The low viscosity binder preferably comprises a two part liquid polymer, comprising a polyurethane prepolymer and a liquid cross-linking agent. The inventor has found that the use of such a low viscosity binder permits low shear mixing of the formulation using relatively simple equipment, such as conventional "Ready Mix" cement mixing trucks. Also, the low viscosity of the binder permits the formulation to be pumped after mixing and compressed in the mold under low pressure.
Another important characteristic of the binder is that it may be cured without the application of an external heat source and is preferably cured at atmospheric pressure. Even under such mild conditions, the binder sets in about 30 to 60 minutes, which is significantly faster than the formulation of the above-discussed patent.
The preferred polyurethane prepolymers for use in the low viscosity binder are polyether based polyurethanes.
Particularly preferred polyurethane prepolymers are polyether based, methylene diisocyanate (MDI) or methylene bis-(phenyl isocyanate) terminated polyurethane prepolymers having a percent NC0 ranging from about 6% to about 15%, such as those sold under the trade marks Vibrathane RB871~ and Vibrathane RB873~ by Uniroyal Chemical.
Vibrathane RB871~ is the most preferred polyurethane prepolymer because of its low cost and ready availability.
~ 1 7 ~
However, it is to be understood that other types of polyurethane prepolymers may be equally suitable. The polyurethane prepolymer component of the binder preferably comprises from about 5 to about 12 percent by weight of the formulation, more preferably about 7.5 percent by weight of the formulation.
In preferred binders according to the present invention, a cross-linking agent (also referred to as a "chain extender") is reacted with the polyurethane prepolymer to form a matrix in which the other ingredients of the formulation are dispersed. The cross-linking agent is a hydroxyl group containing compound preferably selected from one or more members of the group comprising water, diols and polyols. Polyols are defined herein as polyhydric alcohols having three or more hydroxyl groups per molecule. A
particularly preferred diol is ethylene glycol, and a particularly preferred polyol is polypropylene glycol. The most preferred polyol is polypropylene glycol having a molecular weight of about 6000 and a hydroxyl number of 29, such as that sold under the trade mark Polyol G~. The cross-linking agent preferably comprises from about 10 to about 15 percent by weight percent of the formulation, most preferably about 12.5 percent by weight.
It is to be understood that atmospheric water and water present in the ingredients of the formulation will form at least some of the cross-links in the polyurethane prepolymer.
However, it is preferred that water is not added to the formulation as one of the ingredients.
21791~5 The filler is preferably an inexpensive material which is compatible with the other ingredients and has a hardening effect on the formulation. The most preferred filler is ground coal which, like the rubber crumb, may be a reclaimed material. The ground coal is the preferred filler because it is inexpensive, enhances the hardness and stiffness of the final product, and helps to blend the formulation by providing an interface between the polar urethane and the non-polar rubber crumb.
It is also possible in some formulations to use other conventional fillers, for example calcium carbonate, although this produces less advantageous results than ground coal.
It has been found that in the absence of a filler such as ground coal, the molded product has a hardness of only 60 to 70 Shore A and may have a poor bending modulus. The addition of a filler such as ground coal makes the molded product harder and stiffer, raising the Shore A hardness to about 80 to 90 and improving the bending modulus.
The filler is preferably contained in the formulation in an amount of from about 10 to about 20 percent by weight, and more preferably about 15 percent by weight, the most preferred filler being ground coal known as "Austin Black".
The fibrous material is preferably added to the formulation to provide the molded product with improved impact resistance and tear strength. The fibrous material is preferably selected from one or more members of the group comprising chopped fiberglass, nylon fibers, polyester fibers, aromatic polyamide fibers such as Kevlar~, chopped 2 1 7~ 1 4 j steel, and steel strands. It is to be understood that when chopped steel or steel strands are included in the formulation, it may be present in the rubber crumb, added as a separate ingredient, or a combination of both.
The most preferred fibrous material is chopped fiberglass fibers having a length of from about one-quarter to about one-half inch, preferably, about one-quarter to about three-eighths inches. The use of longer fiberglass fibers may result in tangling in the mixing equipment.
Instead of fiberglass, steel strands having a length of about one-quarter inch to about one and one-half inches may be used as the fibrous material. The use of longer steel strands is not preferred since they tend to stick out from the molded product. Also, steel is less preferred than fiberglass because of abrasion of the steel strands against metal parts in the process machinery, which may cause excessive wear of the machinery, and against metal parts of vehicles impacting the barrier, which may cause sparks.
The fibrous agent is preferably a reclaimed material, with polyester, nylon, aromatic polyamide and steel strands being preferably recovered from discarded tires. The fibrous material is preferably contained in the formulation in an amount of from about 3 to about 8 percent by weight, and more preferably about 5 percent by weight.
One or more optional ingredients may also be added to the formulation, if desired, without departing from the scope of the present invention. These additives may be added to enhance properties other than those related to the strength 2179i45 and hardness of the barrier.
For example, a catalyst may be added to the formulation to accelerate the curing of the binder, preferred catalysts being tin or amine catalysts. The most preferred catalysts for use with the polyurethane prepolymer and glycol or polyol cross-linking agent are Stannous Octoate (Stannous-2-ethylhexoate), such as that produced by Air Products DMDI, and DABCO 33LE~, produced by Texaco, which is a triethylenediamine catalyst. Amounts of catalysts added are preferably kept to a minimum since they reduce the pot life of the formulation after mixing and its ability to be poured into a mold.
Other optional ingredients include ground glass, reflective paint, fire retardants such as borates, antioxidants and W absorbers to prevent weathering of the highway impact barrier caused by exposure to W radiation and ozone, and coloring pigments such as zinc oxide or titanium oxide which may give the barrier a gray color similar to that of concrete.
The following is the most preferred formulation for a rubber impact barrier according to the present invention:
Rubber crumb, 30 mesh60.0 wt.%
Vibrathane RB871 7.5 wt.%
Polyol G (PPG 6000: 85-29) 12.5 wt.%
Ground Coal (Austin Black) 15.0 wt.%
Chopped Fiberglass (1/4") 5.0 wt.%
2179~
A preferred process for the production of an impact barrier according to the present invention is now discussed below.
The formulation is preferably mixed in a large mixer, S such as a conventional cement mixer truck, an industrial concrete mixture or a full scale "Hobart" mixer, in the following preferred sequence of steps:
1. The filler is blended with the rubber crumb (typically requiring about 3 min.);
2. The cross-linking agent is added to the mixture of rubber crumb and filler and mixed until the mixture is completely wetted (typically requiring about 3 mins.);
In another aspect, the present invention provides a homogeneous molded solid rubber vehicular barrier, comprising: about 60% by weight particles of rubber crumb having a size of 20 to 30 mesh; about 7.5% by weight of a liquid polyurethane prepolymer comprising a polyether based, methylene diisocyanate or methylene bis-(phenyl isocyanate) terminated polyurethane prepolymer having a percent isocyanate of from about 6 % to about 15%; about 12.5% by weight of polypropylene glycol having a molecular weight of about 6,000; about 15% by weight ground coal; and about 5% by weight chopped fiberglass having a fiber length of about 1/4 to 3/8 inches, said liquid polyurethane prepolymer and said polypropylene glycol forming a matrix in which said rubber, ground coal and chopped fiberglass are dispersed, wherein said barrier is a continuous highway median.
In yet another aspect, the present invention provides a method of manufacturing a homogeneous, solid rubber vehicular barrier, comprising the steps of: blending 55-75% by weight rubber crumb and 10-20% by weight filler; adding 10-15% by weight polyol or glycol cross-linking agent; adding 5-12%
polyurethane prepolymer; and adding 3-8% fibrous material;
forming the mixture in a mold to a selected barrier configuration; curing the mixture within the mold without application of external heat for a period of time from 45-60 minutes; and removing the cured barrier from the mold.
The impact barriers of the present invention utilizeinexpensive, readily available materials, most of which are available as recycled materials.
2 i 79 1 45 Further aspects of the invention will become apparent upon review of the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the invention may be readily understood, a preferred embodiment of the invention will be described by way of example with reference to the accompanying drawings in which:
Figure 1 is a sectional, perspective view of a portion of a continuous, permanent impact barrier which may be produced according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Figure 1 illustrates a portion of a preferred impact barrier 10 which may be produced using the formulation and the method of the present invention. Barrier 10 is a continuous highway median having a similar shape and size as a conventional concrete highway barrier, having two opposite, inclined side surfaces 12 and an outwardly flaring base portion 14.
Although barrier 10 is shown as a continuous highway median, it is to be understood that the formulation and method of the present invention may be used to produce impact barriers having any suitable configuration, either continuous or modular, and may for example have the shape and size of the barrier shown in Figures 1 and 2 of the above-discussed patent.
Barrier 10 is preferably produced on-site in long, ' 2~ 7~7 ~J
continuous lengths as will be described below.
Barrier 10 is shown in Figure 1 as having a pedestal 16 to be embedded in the roadway to provide increased resistance to vehicular impact loads. Alternatively, pedestal 16 may be eliminated and the barrier 10 may be simply placed on its base 14 upon the roadway surface. If pedestal 16 is eliminated, it is preferable to increase the overall dimensions of the barrier 10 in order to provide a larger inertial mass to resist vehicular impact loads.
The formulation of the present invention preferably comprises rubber crumb as the main ingredient, a low viscosity binder which sets quickly at low temperatures and pressure, a filler and a fibrous material.
Rubber crumb, the primary ingredient in the formulation, is preferably obtained as a recycled product derived from discarded automobile tires. The rubber crumb preferably comprises from about 55 to about 75 percent by weight of the formulation, and more preferably about 60 percent by weight of the formulation. The rubber crumb preferably comprises fine particles having a size of about 20 to 30 mesh.
The rubber crumb used in the formulation preferably does not contain significant amounts of steel. However, it is to be appreciated that in some cases it may be desirable that the barrier contains a minor amount of steel to improve impact strength of the barrier. In such cases, rubber crumb may be used which contains a small amount of steel derived from the metal wire reinforcement in the waste automobile tires. Although small amounts of steel in the formulation 2~143 may improve the impact strength of the barrier, barriers according to the present invention having acceptable impact strength and other properties may be manufactured with rubber crumb containing no steel.
The low viscosity binder preferably comprises a two part liquid polymer, comprising a polyurethane prepolymer and a liquid cross-linking agent. The inventor has found that the use of such a low viscosity binder permits low shear mixing of the formulation using relatively simple equipment, such as conventional "Ready Mix" cement mixing trucks. Also, the low viscosity of the binder permits the formulation to be pumped after mixing and compressed in the mold under low pressure.
Another important characteristic of the binder is that it may be cured without the application of an external heat source and is preferably cured at atmospheric pressure. Even under such mild conditions, the binder sets in about 30 to 60 minutes, which is significantly faster than the formulation of the above-discussed patent.
The preferred polyurethane prepolymers for use in the low viscosity binder are polyether based polyurethanes.
Particularly preferred polyurethane prepolymers are polyether based, methylene diisocyanate (MDI) or methylene bis-(phenyl isocyanate) terminated polyurethane prepolymers having a percent NC0 ranging from about 6% to about 15%, such as those sold under the trade marks Vibrathane RB871~ and Vibrathane RB873~ by Uniroyal Chemical.
Vibrathane RB871~ is the most preferred polyurethane prepolymer because of its low cost and ready availability.
~ 1 7 ~
However, it is to be understood that other types of polyurethane prepolymers may be equally suitable. The polyurethane prepolymer component of the binder preferably comprises from about 5 to about 12 percent by weight of the formulation, more preferably about 7.5 percent by weight of the formulation.
In preferred binders according to the present invention, a cross-linking agent (also referred to as a "chain extender") is reacted with the polyurethane prepolymer to form a matrix in which the other ingredients of the formulation are dispersed. The cross-linking agent is a hydroxyl group containing compound preferably selected from one or more members of the group comprising water, diols and polyols. Polyols are defined herein as polyhydric alcohols having three or more hydroxyl groups per molecule. A
particularly preferred diol is ethylene glycol, and a particularly preferred polyol is polypropylene glycol. The most preferred polyol is polypropylene glycol having a molecular weight of about 6000 and a hydroxyl number of 29, such as that sold under the trade mark Polyol G~. The cross-linking agent preferably comprises from about 10 to about 15 percent by weight percent of the formulation, most preferably about 12.5 percent by weight.
It is to be understood that atmospheric water and water present in the ingredients of the formulation will form at least some of the cross-links in the polyurethane prepolymer.
However, it is preferred that water is not added to the formulation as one of the ingredients.
21791~5 The filler is preferably an inexpensive material which is compatible with the other ingredients and has a hardening effect on the formulation. The most preferred filler is ground coal which, like the rubber crumb, may be a reclaimed material. The ground coal is the preferred filler because it is inexpensive, enhances the hardness and stiffness of the final product, and helps to blend the formulation by providing an interface between the polar urethane and the non-polar rubber crumb.
It is also possible in some formulations to use other conventional fillers, for example calcium carbonate, although this produces less advantageous results than ground coal.
It has been found that in the absence of a filler such as ground coal, the molded product has a hardness of only 60 to 70 Shore A and may have a poor bending modulus. The addition of a filler such as ground coal makes the molded product harder and stiffer, raising the Shore A hardness to about 80 to 90 and improving the bending modulus.
The filler is preferably contained in the formulation in an amount of from about 10 to about 20 percent by weight, and more preferably about 15 percent by weight, the most preferred filler being ground coal known as "Austin Black".
The fibrous material is preferably added to the formulation to provide the molded product with improved impact resistance and tear strength. The fibrous material is preferably selected from one or more members of the group comprising chopped fiberglass, nylon fibers, polyester fibers, aromatic polyamide fibers such as Kevlar~, chopped 2 1 7~ 1 4 j steel, and steel strands. It is to be understood that when chopped steel or steel strands are included in the formulation, it may be present in the rubber crumb, added as a separate ingredient, or a combination of both.
The most preferred fibrous material is chopped fiberglass fibers having a length of from about one-quarter to about one-half inch, preferably, about one-quarter to about three-eighths inches. The use of longer fiberglass fibers may result in tangling in the mixing equipment.
Instead of fiberglass, steel strands having a length of about one-quarter inch to about one and one-half inches may be used as the fibrous material. The use of longer steel strands is not preferred since they tend to stick out from the molded product. Also, steel is less preferred than fiberglass because of abrasion of the steel strands against metal parts in the process machinery, which may cause excessive wear of the machinery, and against metal parts of vehicles impacting the barrier, which may cause sparks.
The fibrous agent is preferably a reclaimed material, with polyester, nylon, aromatic polyamide and steel strands being preferably recovered from discarded tires. The fibrous material is preferably contained in the formulation in an amount of from about 3 to about 8 percent by weight, and more preferably about 5 percent by weight.
One or more optional ingredients may also be added to the formulation, if desired, without departing from the scope of the present invention. These additives may be added to enhance properties other than those related to the strength 2179i45 and hardness of the barrier.
For example, a catalyst may be added to the formulation to accelerate the curing of the binder, preferred catalysts being tin or amine catalysts. The most preferred catalysts for use with the polyurethane prepolymer and glycol or polyol cross-linking agent are Stannous Octoate (Stannous-2-ethylhexoate), such as that produced by Air Products DMDI, and DABCO 33LE~, produced by Texaco, which is a triethylenediamine catalyst. Amounts of catalysts added are preferably kept to a minimum since they reduce the pot life of the formulation after mixing and its ability to be poured into a mold.
Other optional ingredients include ground glass, reflective paint, fire retardants such as borates, antioxidants and W absorbers to prevent weathering of the highway impact barrier caused by exposure to W radiation and ozone, and coloring pigments such as zinc oxide or titanium oxide which may give the barrier a gray color similar to that of concrete.
The following is the most preferred formulation for a rubber impact barrier according to the present invention:
Rubber crumb, 30 mesh60.0 wt.%
Vibrathane RB871 7.5 wt.%
Polyol G (PPG 6000: 85-29) 12.5 wt.%
Ground Coal (Austin Black) 15.0 wt.%
Chopped Fiberglass (1/4") 5.0 wt.%
2179~
A preferred process for the production of an impact barrier according to the present invention is now discussed below.
The formulation is preferably mixed in a large mixer, S such as a conventional cement mixer truck, an industrial concrete mixture or a full scale "Hobart" mixer, in the following preferred sequence of steps:
1. The filler is blended with the rubber crumb (typically requiring about 3 min.);
2. The cross-linking agent is added to the mixture of rubber crumb and filler and mixed until the mixture is completely wetted (typically requiring about 3 mins.);
3. The polyurethane prepolymer is then added and mixed until it is completely dispersed throughout the mixture (typically requiring about 5-10 mins.);
4. The fibrous agent is added to the mixture and mixing is continued until all ingredients are blended homogeneously together; and 5. If desired, a suitable catalyst is added to the mixture for faster curing.
The mixing of the ingredients typically requires from about 10 to about 30 minutes, more typically from about 15 2 ~ 79 1 45 to about 20 minutes. However, these mixing times are approximate only and may vary according to the type of equipment being used and the amount of material being mixed.
Furthermore, it is to be appreciated that the above sequence of steps is merely a preferred sequence, and not essential. The sequence to be used in any given case is at least partially dependent on the particular ingredients used.
However, since rubber crumb is the primary ingredient, the other ingredients are preferably added into the rubber crumb.
Also, the catalyst is preferably the last ingredient added to prevent premature setting of the mixture.
The mixing may preferably be performed in a conventional cement mixing truck, such as a "Ready Mix" mixer, which may be driven to the molding site while at least some of the components of the formulation are being mixed by the truck.
It is preferred when using a cement mixing truck to load the mixer with at least the dry ingredients, i.e. rubber crumb, filler and fibrous material, and add at least some of the liquid ingredients on-site. However, the ingredients may be added in any order as long as the formulation does not begin to set before it is released from the mixer. Therefore, it is preferred to add at least one component of the binder and the catalyst, if required, to the mixture, after the cement mixer has reached the molding site.
Once the formulation is completely mixed, it is pumped under minimal pressure into a mold. The pressure required is only that necessary to pump the material and compact it into the mold, typically about 40 psi. Preferably, during the ~il 79~1~5 mixing and mold filling operations, the formulation has a consistency similar to that of concrete and can be mixed and pumped into a mold using the same or similar equipment as would be used to form conventional concrete highway barriers.
As discussed above, it is preferred that the mold is not pressurized and that no external heat is applied during the molding operation, in contrast to the prior art process described in the above-mentioned patent. Therefore, the mold is preferably unheated. However, the reaction of the polyurethane prepolymer with the cross-linking agent is typically exothermic and therefore the temperature of the mixture rises above ambient temperatures as the mixture sets, with the temperature inside the mold typically reaching about 100 to 120~C during setting. However, when using some formulations according to the present invention, it may be desirable to pre-heat the mold to about 80-90~C.
While the mixture is in the mold and before it has set, it may be advantageous to vibrate the mixture by known means to remove air bubbles therefrom, in the same manner as in setting concrete. When molding smaller amounts of material, as when manufacturing barrier modules in a manufacturing facility, it may be possible to vibrate the mold to remove air bubbles. However, in on-site casting of permanent, continuous barriers, it is preferred to vibrate the mixture with a vibrating pipe or the like inserted in the mold as when pouring large amounts of concrete.
The mixture typically sets within a period of about 30 to about 60 minutes without addition of a catalyst, more ~9i~ ~5 typically about 45 to about 60 minutes. After the mixture has set, it is removed from the mold and allowed to cure for a period of about 24 hours.
For on-site molding of continuous impact barriers, for use as highway medians for example, the molding process is preferably continuous, and is analogous to an extrusion. In a continuous molding process, liquid mixture comprising the formulation of the present invention is pumped or poured under gravity from a mixer and compacted into a mold or form at a first end thereof. As the mixture sets, it is gradually pushed from the first end of the mold to a second end of the mold, as for example by a piston, so that freshly mixed mixture can be pumped or poured into the first end of the mold and solidified mixture can be forced, or extruded, from the second end of the mold. The rate at which the mixture is forced through the mold is preferably such that the mixture has sufficient time to set into a solid mass and retain its shape. Preferably, the set mixture is ejected from the mold directly onto the roadway in its desired position, where it cures under ambient temperature and atmospheric pressure.
It is to be appreciated that large amounts of the mixture must be mixed and added to the molding equipment to form a continuous impact barrier. For example, one meter of highway median of conventional size molded from the formulation of the present invention requires about 500 liters of ingredients. On the other hand, the capacity of a "Ready-mix" cement mixing truck is about 30 yards to about 80 yards. Therefore, with a set time of about 45 to 2 ~ 7 ~
about 60 minutes, the limiting step in the production of barriers according to the present invention is more likely to be the delivery of materials to the molding apparatus rather than the set time of the mixture.
The following is an estimate of the amount of materials needed to make one kilometer of highway barrier from a formulation according to the present invention:
Rubber crumb (20-30 mesh)324,000 kg Vibrathane RB873 40,500 kg Ethylene Glycol 67,500 kg Ground Coal 81,000 kg Chopped Fiberglass (%")27,000 kg Total 540,000 kg It is to be understood that this formulation is not the most preferred formulation of the present invention and is used only to illustrate the amount of materials necessary to produce one kilometer of highway barrier.
The formulation according to the present invention is designed to provide a highway barrier having physical properties which meet the standards specified by government agencies for such barriers. The Standards for Highway Safety Barriers specified by the U.S. National Transportation Research Board have been adopted by many government agencies worldwide, such as the Ministry of Transportation of Ontario, and are now considered the worldwide standards for highway safety barriers. Although these specifications are geared 2 1 7 9 ~ ~ ~
towards barriers made from concrete, rubber impact barriers according to the present invention have been produced having the following properties, which meet the above-mentioned safety standards:
Hardness, Shore A 80-90 Tensile Strength, psi 1200 (minimum) Tear Strength, pli (Die C) 150 (minimum) Tear Strength, pli (D4701) 50 Bahshore Rebound 15-25 percent Impact Resistance at -40~C, G.M.9300P, Gardner-Denver Impact Test No Failure.
Although this disclosure has described and illustrated certain preferred embodiments of the invention, it is to be understood that the invention is not restricted to these particular embodiments. Rather, the invention includes all embodiments which are functional or mechanical equivalents of the specific embodiments and features that have been described herein.
The mixing of the ingredients typically requires from about 10 to about 30 minutes, more typically from about 15 2 ~ 79 1 45 to about 20 minutes. However, these mixing times are approximate only and may vary according to the type of equipment being used and the amount of material being mixed.
Furthermore, it is to be appreciated that the above sequence of steps is merely a preferred sequence, and not essential. The sequence to be used in any given case is at least partially dependent on the particular ingredients used.
However, since rubber crumb is the primary ingredient, the other ingredients are preferably added into the rubber crumb.
Also, the catalyst is preferably the last ingredient added to prevent premature setting of the mixture.
The mixing may preferably be performed in a conventional cement mixing truck, such as a "Ready Mix" mixer, which may be driven to the molding site while at least some of the components of the formulation are being mixed by the truck.
It is preferred when using a cement mixing truck to load the mixer with at least the dry ingredients, i.e. rubber crumb, filler and fibrous material, and add at least some of the liquid ingredients on-site. However, the ingredients may be added in any order as long as the formulation does not begin to set before it is released from the mixer. Therefore, it is preferred to add at least one component of the binder and the catalyst, if required, to the mixture, after the cement mixer has reached the molding site.
Once the formulation is completely mixed, it is pumped under minimal pressure into a mold. The pressure required is only that necessary to pump the material and compact it into the mold, typically about 40 psi. Preferably, during the ~il 79~1~5 mixing and mold filling operations, the formulation has a consistency similar to that of concrete and can be mixed and pumped into a mold using the same or similar equipment as would be used to form conventional concrete highway barriers.
As discussed above, it is preferred that the mold is not pressurized and that no external heat is applied during the molding operation, in contrast to the prior art process described in the above-mentioned patent. Therefore, the mold is preferably unheated. However, the reaction of the polyurethane prepolymer with the cross-linking agent is typically exothermic and therefore the temperature of the mixture rises above ambient temperatures as the mixture sets, with the temperature inside the mold typically reaching about 100 to 120~C during setting. However, when using some formulations according to the present invention, it may be desirable to pre-heat the mold to about 80-90~C.
While the mixture is in the mold and before it has set, it may be advantageous to vibrate the mixture by known means to remove air bubbles therefrom, in the same manner as in setting concrete. When molding smaller amounts of material, as when manufacturing barrier modules in a manufacturing facility, it may be possible to vibrate the mold to remove air bubbles. However, in on-site casting of permanent, continuous barriers, it is preferred to vibrate the mixture with a vibrating pipe or the like inserted in the mold as when pouring large amounts of concrete.
The mixture typically sets within a period of about 30 to about 60 minutes without addition of a catalyst, more ~9i~ ~5 typically about 45 to about 60 minutes. After the mixture has set, it is removed from the mold and allowed to cure for a period of about 24 hours.
For on-site molding of continuous impact barriers, for use as highway medians for example, the molding process is preferably continuous, and is analogous to an extrusion. In a continuous molding process, liquid mixture comprising the formulation of the present invention is pumped or poured under gravity from a mixer and compacted into a mold or form at a first end thereof. As the mixture sets, it is gradually pushed from the first end of the mold to a second end of the mold, as for example by a piston, so that freshly mixed mixture can be pumped or poured into the first end of the mold and solidified mixture can be forced, or extruded, from the second end of the mold. The rate at which the mixture is forced through the mold is preferably such that the mixture has sufficient time to set into a solid mass and retain its shape. Preferably, the set mixture is ejected from the mold directly onto the roadway in its desired position, where it cures under ambient temperature and atmospheric pressure.
It is to be appreciated that large amounts of the mixture must be mixed and added to the molding equipment to form a continuous impact barrier. For example, one meter of highway median of conventional size molded from the formulation of the present invention requires about 500 liters of ingredients. On the other hand, the capacity of a "Ready-mix" cement mixing truck is about 30 yards to about 80 yards. Therefore, with a set time of about 45 to 2 ~ 7 ~
about 60 minutes, the limiting step in the production of barriers according to the present invention is more likely to be the delivery of materials to the molding apparatus rather than the set time of the mixture.
The following is an estimate of the amount of materials needed to make one kilometer of highway barrier from a formulation according to the present invention:
Rubber crumb (20-30 mesh)324,000 kg Vibrathane RB873 40,500 kg Ethylene Glycol 67,500 kg Ground Coal 81,000 kg Chopped Fiberglass (%")27,000 kg Total 540,000 kg It is to be understood that this formulation is not the most preferred formulation of the present invention and is used only to illustrate the amount of materials necessary to produce one kilometer of highway barrier.
The formulation according to the present invention is designed to provide a highway barrier having physical properties which meet the standards specified by government agencies for such barriers. The Standards for Highway Safety Barriers specified by the U.S. National Transportation Research Board have been adopted by many government agencies worldwide, such as the Ministry of Transportation of Ontario, and are now considered the worldwide standards for highway safety barriers. Although these specifications are geared 2 1 7 9 ~ ~ ~
towards barriers made from concrete, rubber impact barriers according to the present invention have been produced having the following properties, which meet the above-mentioned safety standards:
Hardness, Shore A 80-90 Tensile Strength, psi 1200 (minimum) Tear Strength, pli (Die C) 150 (minimum) Tear Strength, pli (D4701) 50 Bahshore Rebound 15-25 percent Impact Resistance at -40~C, G.M.9300P, Gardner-Denver Impact Test No Failure.
Although this disclosure has described and illustrated certain preferred embodiments of the invention, it is to be understood that the invention is not restricted to these particular embodiments. Rather, the invention includes all embodiments which are functional or mechanical equivalents of the specific embodiments and features that have been described herein.
Claims (34)
1. A homogeneous molded solid rubber vehicular barrier, comprising:
55-75% by weight particles of rubber crumb;
5-12% by weight liquid polyurethane prepolymer;
10-15% by weight of a diol or polyol cross-linking agent;
10-20% by weight filler; and 3-8% by weight fibrous material.
55-75% by weight particles of rubber crumb;
5-12% by weight liquid polyurethane prepolymer;
10-15% by weight of a diol or polyol cross-linking agent;
10-20% by weight filler; and 3-8% by weight fibrous material.
2. A barrier according to claim 1, wherein said barrier is a continuous highway median.
3. A barrier according to claim 1, wherein said rubber crumb has a particle size of 20 to 30 mesh.
4. A barrier according to claim 1, wherein said rubber crumb comprises about 60% by weight of said barrier.
5. A barrier according to claim 1, wherein said polyurethane prepolymer comprises a polyether based, methylene diisocyanate or methylene bis-(phenyl isocyanate) terminated polyurethane prepolymer having a percent isocyanate of from about 6 % to about 15%.
6. A barrier according to claim 1, wherein said polyurethane prepolymer is contained in said barrier in an amount of about 7.5% by weight.
7. A barrier according to claim 1, wherein said cross-linking agent comprises polypropylene glycol having a molecular weight of about 6,000.
8. A barrier according to claim 1, wherein said polyol is contained in said barrier in an amount of about 12.5% by weight.
9. A barrier according to claim 1, wherein said filler comprises Austin Black ground coal.
10. A barrier according to claim 1, wherein said filler is contained in said barrier in an amount of about 15% by weight.
11. A barrier according to claim 1, wherein said fibrous material is selected from the group comprising fiberglass, nylon fibers, polyester fibers, aromatic polyamide fibers, chopped steel and steel strands.
12. A barrier according to claim 1, wherein said fibrous material is contained in said barrier in an amount of about 5% by weight.
13. A barrier according to claim 1, additionally comprising one or more ingredients selected from the group comprising catalysts, ground glass, reflective paint, fire retardants, antioxidants, UV absorbers and coloring pigments.
14. A barrier according to claim 13, wherein said catalyst is selected from the group comprising tin and amine catalysts.
15. A barrier according to claim 14, wherein said catalyst is selected from the group comprising stannous octoate and triethylenediamine.
16. A barrier according to claim 13, wherein said fire retardant is a borate.
17. A homogeneous molded solid rubber vehicular barrier, comprising:
about 60% by weight particles of rubber crumb having a size of 20 to 30 mesh;
about 7.5% by weight of a liquid polyurethane prepolymer comprising a polyether based, methylene diisocyanate or methylene bis-(phenyl isocyanate) terminated polyurethane prepolymer having a percent isocyanate of from about 6 % to about 15%;
about 12.5% by weight of polypropylene glycol having a molecular weight of about 6,000;
about 15% by weight ground coal; and about 5% by weight chopped fiberglass having a fiber length of about 1/4 to 3/8 inches, said liquid polyurethane prepolymer and said polypropylene glycol forming a matrix in which said rubber, ground coal and chopped fiberglass are dispersed, wherein said barrier is a continuous highway median.
about 60% by weight particles of rubber crumb having a size of 20 to 30 mesh;
about 7.5% by weight of a liquid polyurethane prepolymer comprising a polyether based, methylene diisocyanate or methylene bis-(phenyl isocyanate) terminated polyurethane prepolymer having a percent isocyanate of from about 6 % to about 15%;
about 12.5% by weight of polypropylene glycol having a molecular weight of about 6,000;
about 15% by weight ground coal; and about 5% by weight chopped fiberglass having a fiber length of about 1/4 to 3/8 inches, said liquid polyurethane prepolymer and said polypropylene glycol forming a matrix in which said rubber, ground coal and chopped fiberglass are dispersed, wherein said barrier is a continuous highway median.
18. A barrier according to claim 17, having the following physical properties:
Hardness, Shore A 80-90 Tensile Strength at least 1200 psi Tear Strength (Die C) at least 150 pli Tear Strength (D4701) 50 pli Bahshore Rebound 15-25 percent Impact Resistance at -40°C, G.M.9300P, Gardner-Denver Impact Test No Failure.
Hardness, Shore A 80-90 Tensile Strength at least 1200 psi Tear Strength (Die C) at least 150 pli Tear Strength (D4701) 50 pli Bahshore Rebound 15-25 percent Impact Resistance at -40°C, G.M.9300P, Gardner-Denver Impact Test No Failure.
19. A method of manufacturing a homogeneous, solid rubber vehicular barrier, comprising the steps of:
blending 55-75% by weight rubber crumb and 10-20%
by weight filler;
adding 10-15% by weight polyol or glycol cross-linking agent;
adding 5-12% polyurethane prepolymer; and adding 3-8% fibrous material;
forming the mixture in a mold to a selected barrier configuration;
curing the mixture within the mold without application of external heat for a period of time from 45-60 minutes; and removing the cured barrier from the mold.
blending 55-75% by weight rubber crumb and 10-20%
by weight filler;
adding 10-15% by weight polyol or glycol cross-linking agent;
adding 5-12% polyurethane prepolymer; and adding 3-8% fibrous material;
forming the mixture in a mold to a selected barrier configuration;
curing the mixture within the mold without application of external heat for a period of time from 45-60 minutes; and removing the cured barrier from the mold.
20. A method according to claim 19, wherein said barrier is a continuous highway median.
21. A method according to claim 19, wherein said rubber crumb has a particle size of 20 to 30 mesh.
22. A method according to claim 19, wherein said rubber crumb comprises about 60% by weight of said barrier.
23. A method according to claim 19, wherein said polyurethane prepolymer comprises a polyether based, methylene diisocyanate or methylene bis-(phenyl isocyanate) terminated polyurethane prepolymer having a percent isocyanate of from about 6 % to about 15%.
24. A method according to claim 19, wherein said polyurethane prepolymer is contained in said barrier in an amount of about 7.5% by weight.
25. A method according to claim 19, wherein said cross-linking agent comprises polypropylene glycol having a molecular weight of about 6,000.
26. A method according to claim 19, wherein said polyol is contained in said barrier in an amount of about 12.5% by weight.
27. A method according to claim 19, wherein said filler comprises Austin Black ground coal.
28. A method according to claim 19, wherein said filler is contained in said barrier in an amount of about 15% by weight.
29. A method according to claim 19, wherein said fibrous material is selected from the group comprising fiberglass, nylon fibers, polyester fibers, aromatic polyamide fibers, chopped steel and steel strands.
30. A method according to claim 19, wherein said fibrous material is contained in said barrier in an amount of about 5% by weight.
31. A method according to claim 19, additionally comprising one or more ingredients selected from the group comprising catalysts, ground glass, reflective paint, fire retardants, antioxidants, UV absorbers and coloring pigments.
32. A method according to claim 31, wherein said catalyst is selected from the group comprising tin and amine catalysts.
33. A method according to claim 32, wherein said catalyst is selected from the group comprising stannous octoate and triethylenediamine.
34. A method according to claim 31, wherein said fire retardant is a borate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2179145 CA2179145A1 (en) | 1996-06-14 | 1996-06-14 | Formulation and method for producing rubber vehicular impact barriers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2179145 CA2179145A1 (en) | 1996-06-14 | 1996-06-14 | Formulation and method for producing rubber vehicular impact barriers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2179145A1 true CA2179145A1 (en) | 1997-12-15 |
Family
ID=4158411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2179145 Abandoned CA2179145A1 (en) | 1996-06-14 | 1996-06-14 | Formulation and method for producing rubber vehicular impact barriers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2179145A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007047073A2 (en) * | 2005-10-14 | 2007-04-26 | Dow Global Technologies Inc. | A composite article and method of manufacture using an isocyanate-terminated prepolymer as binder |
| FR2918054A1 (en) * | 2007-06-29 | 2009-01-02 | Aliapur | AGGLOMER MATERIAL COMPRISING RUBBER GRANULATES, USES AND CORRESPONDING ACOUSTIC BARRIER |
| WO2011015678A3 (en) * | 2009-07-30 | 2011-07-14 | Jose Manuel Sanchez De La Cruz | Highway protection barrier |
| ES2363144A1 (en) * | 2009-11-18 | 2011-07-21 | Copebis Elements, S.L. | Valle quitamiedos. (Machine-translation by Google Translate, not legally binding) |
| WO2020068508A1 (en) | 2018-09-25 | 2020-04-02 | Lanxess Solutions Us Inc. | Rebonded polyurethane foam |
-
1996
- 1996-06-14 CA CA 2179145 patent/CA2179145A1/en not_active Abandoned
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007047073A2 (en) * | 2005-10-14 | 2007-04-26 | Dow Global Technologies Inc. | A composite article and method of manufacture using an isocyanate-terminated prepolymer as binder |
| WO2007047073A3 (en) * | 2005-10-14 | 2007-06-07 | Dow Global Technologies Inc | A composite article and method of manufacture using an isocyanate-terminated prepolymer as binder |
| FR2918054A1 (en) * | 2007-06-29 | 2009-01-02 | Aliapur | AGGLOMER MATERIAL COMPRISING RUBBER GRANULATES, USES AND CORRESPONDING ACOUSTIC BARRIER |
| EP2011772A1 (en) | 2007-06-29 | 2009-01-07 | Aliapur | Agglomerate material comprising grains of rubber, corresponding uses and sound barrier |
| WO2011015678A3 (en) * | 2009-07-30 | 2011-07-14 | Jose Manuel Sanchez De La Cruz | Highway protection barrier |
| EA022575B1 (en) * | 2009-07-30 | 2016-01-29 | Хосе Мануэль Санчес Де Ла Круз | Highway protection barrier |
| ES2363144A1 (en) * | 2009-11-18 | 2011-07-21 | Copebis Elements, S.L. | Valle quitamiedos. (Machine-translation by Google Translate, not legally binding) |
| WO2020068508A1 (en) | 2018-09-25 | 2020-04-02 | Lanxess Solutions Us Inc. | Rebonded polyurethane foam |
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