Field of Invention
The present invention relates to a resinous grouting composition useful as grouting material for underground mines and a process for the preparation thereof. The developed composition has better physico-mechanical properties and good shelf life and provides better and uniform annular properties on the bolts used in the mines. In the present invention, heat releasing chemical, fire retarding agents were added for the first time in the formulation so that it exhibits better physico-chemical as well as physico-mechanical properties and better shelf life.
Background of Invention and Description of Prior Art
Roof in underground coal mines is exposed due to extraction of the coal. The intermediate roof starts dilating and gets detached from the overlying layers of roof strata causing it to fall if not supported properly. It has become common practice in mining to reinforce the strata and to provide adequate support in the excavation to stabilize mine roofs by drilling or boring a hole into the rock strata at the roof of the mine, inserting a cement or resin capsule into the drilled hole and then inserting a specially designed steel, Fibre Reinforced Polymer (FRP) or Glass Reinforced Polymer (GRP) bolt through the capsule into the hole. It is highly desired that the roof bolts once installed should immediately start taking load of the roof strata and prevent dilation to eliminate the chances of roof fall. Cement capsules are being used as grouting material in roof bolting. However, the setting time and time to provide reinforcement in the strata is too long to arrest the roof dilation. It is also observed that during impending loading on the roof bolts due to stressing of the strata, cement grout provide less resistance in comparison to resin grouting because resin grout has higher strengths than the cement grouting.
Unsaturated resin system is predominantly used in the construction of composites which have many and varied applications. The application of resin for manufacturing of resin capsules suitable for grouting of roof bolts in underground mines is a relatively new area of research. Usually the resin system is used with catalyst and ancillary chemicals to optimize the polymerization rate and process characteristics. There are number of resin system such as

epoxy, polyurethanes and polyesters available in the market for effecting the reinforcement of the strata. But, it is observed that composition of the available resin systems do not provide proper physico-mechanical strength to the system coupled to the fact that the physico-chemical properties and shelf life of the products are very less. The resin capsules started polymerizing within 15-20 days and became hard within 30-45 days and showed very less shelf life. It is therefore, necessary to develop suitable resin matrix with easy manufacturing process to provide desired results and fulfill the objectives to provide support in the mine.
U.S. Pat. Nos. 3,324,662, 3,324,663, and 3,302,410 all describe a two-component resin composition which additionally contains 5 to 10 percent (based on final resin volume) of a water-receiver filler in one of the components, and water in the other component in at least an amount sufficient to react with a substantial portion of the water-reactive filler and also minimize shrinkage. The composition also contains a thickener such as pyrogenic silica, and an inert filler for the sole stated purpose of reducing the unit volume cost of the resin. In the preferred composition, water is emulsified in the resin using an emulsifying agent, and the peroxide catalyst is mixed with cement. The use of water in the above-mentioned compositions is associated with the presence of a water-reactive filler therein. Indeed, the amount of water indicated to be usually preferred is about that which will react with the water-reactive filler, and only half of this amount is said to give good results. When used in this manner, i.e., combined with a water-reactive filler such as cement, water is disclosed to reduce shrinkage of the resin. However, the drawbacks associated with the said compositions are flammable in nature, having less self life in varying temperature and having water reactive fillers which may affect physico-mechanical properties in humid environment.
U.S. Pat. No. 3,731,791 describes the use of a peroxide-catalyzed cross-linkable unsaturated polyester resin system in a single-compartment cartridge wherein the resin component and the catalyst component are separated. The reaction product is formed when the two components are brought into direct contact with each other. Although water is present in one of the resin components, the said patent does not disclose the use of inorganic fillers such as calcite

principally to reduce the shrinkage of their resinous mass which is said to always occur during polymerization.
An apparatus heretofore found suited and adaptable for the forming and filling of multicompartment sausage-like containers for resin and curing or hardening agent adapted for use with mine bolts is shown and described in U.S. Pat. No. 4,009,778. In the apparatus and method of this patent a film sheet of suitable packaging material is fed longitudinally, folded along one edge, and is passed through a forming head where the film sheet, with the folded edge, is rolled into a tube having a second, smaller tube therein at the folded edge. The tubes are then advanced along mandrels which shape the inner and outer tubes. The edges of the sheet are slightly overlapped and are heat sealed along the overlapped edge. The tubes are then filled through the mandrels. The filled tubes are divided into sausage-like lengths by wire wraps tightened around the tubes at prescribed lengths to gather and seal the sausage-like lengths. Closely spaced wire wraps are employed to end one length and start the next and the tubes are severed between such closely spaced wraps.
From a survey of the hitherto known prior art as detailed above, it may be seen that the above literature do not disclose a composition that contains the stability enhancer, plasticizers and light weight filler for providing the mechanical strength in the product.
U.S. Pat. 4291799 describes a parallel tube resin bolting package for use in resin bolting operations. The composite package has a generally figure 8 shape in cross-section, with one compartment containing a polyester resin while the other compartment contains a hardener composition. However, the resin bolting package is particularly useful in applications where the pre-drilled hole has a relatively small diameter.
U.S. Pat. 5993116 discloses a system for anchoring a reinforcement member or rock bolt in the hole of a rock formation or a structural body. More specifically, it is directed to a novel two-component filler-containing rock bolt anchoring system. It also relates to a method of preparing and method of using the rock bolting anchoring system. However, the drawbacks associated with the said compositions are flammable and not suitable for gassy mines (Degree-I & Degree-

II), having low self life and polymerized due to variation in environmental temperature and not cost effective.
Market survey revealed that there is a requirement of a product having good mechanical properties and shelf life, which is cheaper and safe to manufacture and use because the temperature variation in India is very high.
Therefore, the inventors of the present invention realized that there exists a dire need to provide a process that relates to the development of suitable resinous grouting compositions with improved manufacturing process with cost effective operations. The developed compositions exhibit better physico-mechanical properties and good shelf life and provide better and uniform annular properties on the bolts used in the mines.
Objects of the Invention
The main object of the present invention is thus to provide improved resinous grouting composition and their preparation process, which obviates the drawbacks as detailed above.
Another object of the present invention to provide a composition suitable for resin grouting which is not a mere admixture but a synergetic mixture having physico-mechanical and physico-chemical properties of resin matrix which are distinct and different from the aggregation of the properties of the individual ingredients.
Still another object of the present invention is to select reaction heat releasing chemicals for development of the long polymeric chain in the resin matrix after mixing of the catalyst.
Yet another object of the present invention is to provide chemical ingredients suitable for generating the fire retardency in the resin matrix.

Summary of the Invention
The composition of the present invention comprises of blend of polyester, vinyl ester and epoxy resin, reaction accelerator and fillers such as quartz powder, berytes, glass micro balloons and resin matrix stability enhancer and plasticizers to enhance the mechanical strength of the cured product and reaction temperature releasing ingredients.
Berytes powder alongwith quartz powder and glass micro balloons were used as filler material in place of lime stone powders which is used in the existing available products. Berytes powder gives better physico-mechanical properties and also cost effective.
Zinc Oxide is used for the first time in a grouting composition which acts as heat releasing agent and is responsible for the development of long polymer chain resulting in increase in physico-mechanical properties and shelf life of the product.
Further, the utilization of Sodium Pyro Antimonate/Potassium Pyro Antimonate as fire retardency agent in the filler component has also been done for the first time, which is more effective and enhances the fire retardency of the product.
Accordingly, the present invention provides a resinous grouting composition useful as grouting material for underground mines wherein the said composition comprising: a) Resin component comprising
Name of Chemical Ingredient Percentage (% by
weight)
Unsaturated Isophthallic Resin 50.00 - 60.00
Unsaturated Polyester Resin (Mallic Anhydride based) 10.00 - 20.00
Vinyl Ester Resin 8.00 -12.50
Epoxy Resin 4.00 - 6.20
Di-Methyl Aniline/Cobalt Nephthanate 0.20 - 2.00
Styrene Monomer 18.00 - 30.00
Benzoyl Peroxide (DOP + Water based)/Methyl Iso Ketone 4.00 -10.00
Peroxide (MIKP)
Chlorinated Wax 1.00- 2.50

b) Filler component comprising
Name of Chemical Ingredient Percentage (% by
weight)
Zinc Oxide 1.00-2.50
Aluminum Tri Hydrate 1.50 - 2.50
Antimony Tri/Penta Oxide 0.50-1.50
Berytes 60.00 - 75.00
Quartz Powder 2.00 -10.00
Glass Micro Balloons 15.00 - 25.00
Poly Naphthalene Sulphonic Acid Formaldehyde Condensate 1.20 - 2.00
Sodium Pyro Antimonate + Potassium Pyro Antimonate 0.01- 0.10
wherein the ratio of the resin component to the filler component is in the range of 25.0 to 40.0 : 60.0 to 75.0 [percentage by weight].
The invention further provides a process for the preparation of the said resinous grouting composition, wherein the steps comprising:
a) adding unsaturated Isophthallic Resin, mallic anhydride based resin, vinyl ester, epoxy resin and Dimethyl Aniline/Cobalt Nephthanate in the ribbon blender and agitated under continuous stirring to obtain a mixture;
b) adding Sodium Pyro Antimonate and Potassium Pyro Antimonate to the mixture of step [a] followed by stirring;
c) adding glass micro balloons and quartz powder followed by berytes powder to the mixture of step [b] to obtain a homogenous material;
d) adding zinc oxide, Aluminum Tri Hydrate and Antimony Tri/Penta Oxide to the homogenous material of step [c] under stirring followed by settling to obtain the desired resinous bubble free grouting composition.
In an embodiment of the present invention, the resinous matrix is a mixture of Styrene Monomer, Chlorinated Wax, Zinc Oxide, Aluminum Tri Hydrate, Antimony Tri/Penta Oxide,

Berytes, Glass Micro Balloons, Poly Naphthalene Sulphonic Acid Formaldehyde Condensate, Sodium Pyro Antimonate and Potassium Pyro Antimonate.
In another embodiment of the present invention, the resin used is such as Isophthallic Resin, Unsaturated Polyester Resin (Mallic Anhydride based) and Vinyl Ester Resin or mixture thereof.
In yet another embodiment of the present invention, the reaction promoter is such as Di-Methyl Aniline or Cobalt Nephthanate.
In still another embodiment of the present invention, the reaction catalyst is such as benzoyl peroxide dissolved in Di Octyl Phthalate or Di Butyl Phthalate and water and mixture thereof.
In a further embodiment of the present invention, the resin(s), fillers and ancillary chemical ingredients are of commercial grade.
Detailed Description of the Invention
Resin composition was taken in the mixing unit and stirred well with the help of mixing machine having U-Type blade at 120 RPM to decrease the viscosity of the resin. Added the fire retardant chemicals i.e. Sodium Pyro Antimonate and Potassium Pyro Antimonate in the resin and again stirred well. After few minutes, added the glass micro balloons and quartz powder followed by berytes powder. When the material became homogenous added zinc oxide, aluminum tri hydrate and antimony tri/penta oxide and stirred well. Kept the material in cool place for a period of about two hours to release the gas bubbles generated during the process of mixing the chemical ingredients. The ratio of the resin component to the filler component in the composition was in the range of 25.0 to 40.0 : 60.0 to 75.0 [percentage by weight]. The resin matrix was evaluated for the below mentioned properties before filling in the cartridges.

(Table Removed)
Catalyst Benzoyl Peroxide was dissolved in Di Octyl Phthalate or Di Butyl Phthalate and water and stirred well with the help of slow speed stirrer followed by adding glass micro balloons to increase the viscosity of the material.
One end of the double chamber poly tube was crimped with 2 mm aluminum wire using crimping machine operated pneumatically and the pressure of the air was maintained at 4 kg/cm2 suitable for proper crimping.

The paste of the catalyst Benzoyl Peroxide was filled with help of filling machine. The quantity of the catalyst was varied as per the cartridge dimension and quantity of the resin matrix.
Catalyst filled poly tubes were transferred to resin matrix filling plant wherein the polytubes are filled with the resin matrix pneumatically. The pneumatic pressure of the filling varied from 4.50 kg to 6.50 kg/cm2. The filled cartridges were sent to the crimping machine for final crimping.
The product developed by the process of the present invention had different types of fire retardant and chimerical composition and should possess the following properties:
(Table Removed)

The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention.
Example -1
Resin composition (A) consists of 51.20 unsaturated isophthallic resin, 10.20 % polyester resin (mallic anhydride based), 10.70 % vinyl ester resin, 5.05 % epoxy resin, 0.65 % Dimethyl
Aniline/Cobalt Naphthanate, 20.0 % styrene monomer and 2.20% chlorinated paraffin wax mixed at 120 RPM for 10 minutes to make uniform paste like material and kept for 30 minutes to release the bubbles generated during the agitation.
Filler composition (B) consists of 68.5 % berytes powder of 150 Mesh, 9.50 % quartz powder of 200 Mesh and 22 % glass micro balloons of 200 Mesh are mixed well in the ribbon blender.
Other chemicals (C) such as heat releasing agent 40.0 % zinc oxide, Fire retardant agent 30 % aluminium tri hydrate, antimony tri/penta oxide in 20:80 ratio, Self life enhancing chemical 5 % sodium pyro antimonite & potassium pyro antimonite in 50:50 ratio and plasticizer 25 % poly naphthalene sulphonic acid formaldehyde condensate were mixed in the ribbon blender.
For preparation of resin matrix, 17.50% resin composition (A) was taken in the ribbon blender and agitated for 5 minutes to reduce the viscosity, add 76.50 % Filler composition (B) slowly in the ribbon blender and agitated at 120 RPM for 10 minutes and 6 % add ancillary chemicals (C) in the matrix and agitate the resin matrix for 5 minutes for uniform consistency.
Before filling the cartridges, Resin matrix was evaluated for viscosity, gel time, final setting time, flammability and thermal stability. The resin matrix was also evaluated for physico-mechanical properties such as compressive strength, bond strength, system stiffness, elastic modulus and shrinkage.
Viscosity of the resin matrix was determined using Viscometer (Brrokfield, USA Model DV-II+). 3% Benzoyl Peroxide Paste was added to the resin matrix and agitated at 80 RPM for 45 second and then polymer chain development time was measured using viscometer. For flammability test, 12 mmX150 mmX5mm strip was prepared and kept in the flame for 30 second and flame from the strip should self extinguish within 10 second.
Compressive strength was measured for 50 mm X 50 mm cube and using universal testing machine.

It was found that above composition showed good physico-chemical properties such as gel time, final setting time, non-flammability and longer self life as well as physico-mechanical properties such as compressive strength, short encapsulation, bond strength, elastic modulus and having negligible shrinkage in comparison to the present available products. This composition found suitable for gassy (degree-l & degree -II) and non-gassy underground mines. The compressive strength was 40 MPa after 30 minutes and 92 MPa after 24 hours.
Example -2
Resin composition (A) consists of 55.00 unsaturated isophthallic resin, 8.50 % polyester resin (mallic anhydride based), 7.00 % vinyl ester resin, 3.00 % epoxy resin, 0.50 % Dimethyl Aniline/Cobalt Naphthanate, 23.00 % styrene monomer and 3.00% chlorinated paraffin wax mixed at 120 RPM for 10 minutes to make uniform paste like material and kept for 30 minutes to release the bubbles generated during the agitation.
Filler composition (B) consists of 60.5 % berytes powder of 150 Mesh, 20.00 % quartz powder of 200 Mesh and 19.50 % glass micro balloons of 200 Mesh are mixed well in the ribbon blender.
Other chemicals (C) such as heat releasing agent 50.0 % zinc oxide, Fire retardant agent 35 % aluminium tri hydrate, antimony tri/penta oxide in 25:75 ratio, Self life enhancing chemical 5 % sodium pyro antimonite & potassium pyro antimonite in 40:60 ratio and plasticizer 10 % poly naphthalene sulphonic acid formaldehyde condensate were mixed in the ribbon blender.
For preparation of resin matrix, 19.00% resin composition (A) was taken in the ribbon blender and agitated for 5 minutes to reduce the viscosity, add 75.00 % Filler composition (B) slowly in the ribbon blender and agitated at 120 RPM for 10 minutes and add 6 % ancillary chemicals (C) in the matrix and agitate the resin matrix for 5 minutes for uniform consistency.
Before filling the cartridges, Resin matrix was evaluated for viscosity, gel time, final setting time, flammability and thermal stability. The resin matrix was also evaluated for physico-

mechanical properties such as compressive strength, bond strength, system stiffness, elastic modulus and shrinkage.
Viscosity of the resin matrix was determined using Viscometer (Brrokfield, USA Model DV-II+). 4% Benzoyl Peroxide Paste was added to the resin matrix and agitated at 80 RPM for 45 second and then polymer chain development time was measured using viscometer. For flammability test, 12 mmX150 mmX5mm strip was prepared and kept in the flame for 30 second and flame from the strip should self extinguish within 10 second.
Compressive strength was measured for 50 mm X 50 mm cube and using universal testing machine.
Results of this composition showed that physico-chemical properties such as gel time, final setting time, non-flammability and longer self life as well as physico-mechanical properties such as compressive strength, short encapsulation, bond strength, elastic modulus were acceptable and suitable for gassy and non-gassy mines and having negligible shrinkage in comparison to the present available products. The compressive strength was 36 MPa after 30 minutes and 92 Mpa after 24 hours.
Example -3
Resin composition (A) consists of 65.00 unsaturated isophthallic resin, 3.50 % polyester resin (mallic anhydride based), 2.00 % vinyl ester resin, 3.00 % epoxy resin, 2.50 % Dimethyl Aniline/Cobalt Naphthanate, 23.00 % styrene monomer and 1.00% chlorinated paraffin wax mixed at 120 RPM for 10 minutes to make uniform paste like material and kept for 30 minutes to release the bubbles generated during the agitation.
Filler composition (B) consists of 50 % berytes powder of 150 Mesh, 30.00 % quartz powder of 200 Mesh and 20 % glass micro balloons of 200 Mesh are mixed well in the ribbon blender.

Other chemicals (C) such as heat releasing agent 5.0 % zinc oxide, Fire retardant agent 5.50 % aluminium tri hydrate, antimony tri/penta oxide in 25:75 ratio, Self life enhancing chemical 1.50 % sodium pyro antimonite & potassium pyro antimonite in 40:60 ratio, plasticizer 3.50 % poly naphthalene sulphonic acid formaldehyde condensate and 84.50 % fine sand were mixed in the ribbon blender.
For preparation of resin matrix, 40.00% resin composition (A) was taken in the ribbon blender and agitated for 5 minutes to reduce the viscosity, add 57.00 % Filler composition (B) slowly in the ribbon blender and agitated at 120 RPM for 10 minutes and add 3 % ancillary chemicals (C) in the matrix and agitate the resin matrix for 5 minutes for uniform consistency.
Before filling the cartridges, Resin matrix was evaluated for viscosity, gel time, final setting time, flammability and thermal stability. The resin matrix was also evaluated for physico-mechanical properties such as compressive strength, bond strength, system stiffness, elastic modulus and shrinkage.
Viscosity of the resin matrix was determined using Viscometer (Brrokfield, USA Model DV-II+). 10 % Benzoyl Peroxide Paste was added to the resin matrix and agitated at 80 RPM for 5 second and then polymer chain development time was measured using viscometer. For flammability test, 12 mmX150 mmX5mm strip was prepared and kept in the flame for 30 second and flame from the strip should self extinguish within 10 second.
Compressive strength was measured for 50 mm X 50 mm cube and using universal testing machine.
Results of this composition showed that resin matrix polymerized when Benzoyl Peroxide Paste mixed within the 10 second and physico-chemical properties such as gel time, final setting time, non-flammability and longer self life as well as physico-mechanical properties such as compressive strength, short encapsulation, bond strength, elastic modulus were not acceptable and suitable for gassy and non-gassy mines. Product showed brittle nature after curing and

looses their non-flammability and catches fire immediately when exposed to flame. The compressive strength comes down to 3 MPa.
Advantages of the Invention
The main advantages of the present invention are:
• The present invention provides a novel composition for manufacturing of resin capsules suitable grouting material for underground mines, which contains resin, fillers, reaction promoters, catalysts, fire retardant chemicals, strength enhancers and can play an important role for the manufacturing of good quality of product and provides safe environment to the men and machineries in the underground mines.
• The process of the present invention is safe for manufacturing of good quality of product.
• Products developed in the present invention provides non-flammable resin capsule suitable for gassy (Degree-I & Degree-ll) and non-gassy mines.
• The reaction temperature of product developed in the present invention is less due to using heat releasing chemicals which is responsible for development of long polymer chain.
• Product developed in the present invention provides shelf life upto six month at ambient temperature.
• The product developed in the present invention provides uniform layer on the bolt.
• The product having better fire retardency in comparison to the present product. Addition of Metal oxides increases the fire retardency of the product.
• The heat generation after mixing of catalyst is lower than the present product which provides the time to generate long chain of the polymer.

We claim:
1. A resinous grouting composition useful as grouting material for underground mines wherein the said composition comprising:
a) Resin component comprising
Name of Chemical Ingredient Percentage (% by
weight)
Unsaturated Isophthallic Resin 50.00 - 60.00
Unsaturated Polyester Resin (Mallic Anhydride based) 10.00 - 20.00
Vinyl Ester Resin 8.00 -12.50
Epoxy Resin 4.00 - 6.20
Di-Methyl Aniline/Cobalt Nephthanate 0.20 - 2.00
Styrene Monomer 18.00 - 30.00
Benzoyl Peroxide (DOP + Water based)/Methyl Iso Ketone 4.00 -10.00
Peroxide (MIKP)
Chlorinated Wax 1.00- 2.50
b) Filler component comprising
Name of Chemical Ingredient Percentage (% by
weight)
Zinc Oxide 1.00-2.50
Aluminum Tri Hydrate 1.50-2.50
Antimony Tri/Penta Oxide 0.50 -1.50
Berytes 60.00 - 75.00
Quartz Powder 2.00 -10.00
Glass Micro Balloons 15.00-25.00
Poly Naphthalene Sulphonic Acid Formaldehyde Condensate 1.20 - 2.00
Sodium Pyro Antimonate + Potassium Pyro Antimonate 0.02- 0.10
wherein the ratio of the resin component to the filler component is in the range of 25.0 to 40.0 : 60.0 to 75.0 [percentage by weight].
2. A composition as claimed in claim 1, wherein the ratio of the resin component to the filler component is preferably 40:60.
3. A composition as claimed in claim 1, wherein the resin component contains an unsaturated polyester resin blended with vinyl ester and epoxy resin and quinone as reaction inhibitor and Di-Methyl Aniline/Cobalt naphthenate as reaction promoter.
4. A composition as claimed in claim 1, wherein the filler component contains glass micro balloons, berytes, quartz powder, plasticizer, heat releasing and fire retardant chemicals.
5. A composition as claimed in claim 1, wherein the fire retardency agents are sodium pyro antimonate and potassium pyro antimonate.
6. A composition as claimed in claim 1, wherein heat releasing chemical is zinc oxide.
7. A composition as claimed in claim 1, wherein the zinc oxide accelerates the rate of release of heat generated during the reaction and is responsible for the development of chain length of the polymer in the resin component.
8. A composition as claimed in claim 1, wherein it exhibits better physico-mechanical properties and good shelf life and provides better and uniform annular properties on the bolts used in the mines.
9. A process for the preparation of the resinous grouting composition as claimed in claim1, wherein the steps comprising:
a) adding unsaturated Isophthallic Resin, mallic anhydride based resin, vinyl ester, epoxy resin and Dimethyl Aniline/Cobalt Nephthanate in the ribbon blender and agitated under continuous stirring to obtain a mixture;
b) adding Sodium Pyro Antimonate and Potassium Pyro Antimonate to the mixture
of step [a] followed by stirring;
c) adding glass micro balloons and quartz powder followed by berytes powder to
the mixture of step [b] to obtain a homogenous material;
d) adding zinc oxide, Aluminum Tri Hydrate and Antimony Tri/Penta Oxide to the
homogenous material of step [c] under stirring followed by settling to obtain the
desired resinous bubble free grouting composition.
10. A resinous grouting composition useful as grouting material for underground gassy and non-gassy (Degree-I & Degree-ll) mines substantially as herein described with reference to the foregoing examples.