64934A i
NEW FILL COMPOSITIONS AND METHOD FOR MAKING THE SAME
BACKGROUND OF THE INVENTION
5 1. Field of the Invention
The present invention relates to a projectile containing a fill composition which comprises an alkoxylated glycerin. The present invention also relates to various applications of the new fill composition.
2. Discussion of Background Information
10 Capsules containing appropriate marking materials for use as projectiles in applications ranging from field markers for trees to recreational "paintball" sporting activities are well known in the art (US3,861,943; US 4,634,606; US 4,656,092; US 5,393,054; US 5,885,671; US 6,530,962; EP0786641). Early fill compositions for such capsule projectiles consisted simply of dyes. But as disclosed in US 3,861,943, such
15 projectiles suffered from serious drawbacks including incompatibility of the dye with the capsule. Fill compositions based largely on polyethylene glycol (PEG) represented advancement in practical usage of such capsules due to the fact that PEGs are generally compatible with both the dye and other fill components and are also compatible with the capsule. One formulation involves using a blend of liquid PEG (below 600 molecular
20 weight) and solid PEG (above 600 molecular weight) to reach a viscosity that is optimal for this application (US 5,393,054). The drawback of this approach is that the solid PEG must be melted before blending with the liquid PEG. This results in an increase in processing time and costs. Furthermore, fill compositions produced in this manner can suffer from freezing at relatively high temperatures and resultant changes in capsule size. In US
25 5,885,671, a paintball fill composition primarily based on PEG 300 was introduced. This fill material represented an improvement over the prior art in that less processing was necessary in production of the fill. It employed viscosity modifiers or thickeners to achieve the proper fill viscosity and it also had better cold weather properties than fill compositions previously reported. Another fill formulation based primarily on soy oil was introduced in
30 order to produce a less expensive fill than PEG-based fills (US 6,530,962). But the soy oil fill composition has not gained widespread acceptance, probably due to inferior performance and biodegradation characteristics.
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Therefore, there is a need for fill materials and compositions suitable for use in projectiles that are less expensive, but capable of providing equivalent or superior performance characteristics to PEG based fill compositions.
5 SUMMARY OF THE INVENTION
The present invention relates to a projectile containing a fill composition, wherein the composition comprises an alkoxylated glycerin. The projectile may be made of gelatin, polystyrene, polyolefin, or mixture thereof. The alkoxylated glycerin may be a reaction product between glycerin and an alkylene oxide. In one embodiment, the alkoxylated 10 glycerin is a catalyzed reaction product between glycerin and an alkylene oxide. In one non-limiting example, the alkoxylated glycerin is a reaction product between glycerin and an alkylene oxide, and the reaction is catalyzed by one of NaOH, KOH, double metal cyanide, or mixture thereof.
The starting material, glycerin, may be crude or refined. In one embodiment, the 15 glycerin is obtained from a byproduct of a biodiesel process.
The other reaction starting material, alkylene oxide, may be a) one of ethylene oxide, propylene oxide, or butylene oxide, or b) a mixture of any combinations of ethylene oxide, propylene oxide, and butylene oxide.
The reaction product, the alkoxylated glycerin, has a molar ratio glycerin: alkylene 20 oxide of about 1 :1 to about 1:20. In one embodiment, the molar ratio glycerin:alkylene oxide is about 1 :1 to about 1 :10. In another embodiment, the molar ratio glycerin:alkylene oxide is about 1 :2 to about 1 :10.
In one non-limiting example, the alkoxylated glycerin is an ethoxylated glycerin with a molar ratio glycerin:ethylene oxide of about 1 :2 to about 1 :7. In another example, 25 the molar ratio glycerin:ethylene oxide is about 1:2.4 to 1:6.4. In another example, the molar ratio glycerin:ethylene oxide glycerin ethylene oxide is about 1 :4.4.
The fill composition for the projectile comprises about 15 to 100 wt. % of alkoxylated glycerin, preferably about 50 to 100 wt. % of alkoxylated glycerin, more preferably about 75 to 100 wt. % of alkoxylated glycerin, and most preferably about 90 to 30 100 wt. % of alkoxylated glycerin.
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The projectile fill composition may further comprise dyes, thickening agents, fragrances, glycerin, density builders, surfactants, fillers, polyethylene glycol or mixture thereof. In one embodiment, the fill composition comprises about 15 to 100 wt.% of alkoxylated glycerin, less than about 5 wt.% of a dye, less than about 3 wt.% of glycerin, 5 less than about 5 wt.% of water, less than about 4 wt.% of a thickening agent, less than about 85 wt.% of PEG, and less than 1 wt.% of a filler.
The alkoxylated glycerin is substantially in liquid form at a temperature higher than -40 0C. In one embodiment, the alkoxylated glycerin is substantially in liquid form at a temperature higher than -30 °C. In another embodiment, the alkoxylated glycerin is 10 substantially in liquid form at a temperature higher than -25 0C.
The pour point of the alkoxylated glycerin is usually about -20 to -40 °C. In one embodiment, the pour point of the alkoxylated glycerin is about -25 to -40 0C. In another embodiment, the pour point of the alkoxylated glycerin is about -30 to -40 °C.
The viscosity of the alkoxylated glycerin is usually about 75 to 800 centistokes at 40 15 0C. In one embodiment, the viscosity of the alkoxylated glycerin is about 75 to 150 centistokes at 40 0C. In another embodiment, the viscosity of the alkoxylated glycerin is about 85 to 140 centistokes at 40 0C.
The molecular weight of the alkoxylated glycerin is usually about 130 to 1000. In one embodiment, the molecular weight of the alkoxylated glycerin is about 130 to 600. In 20 another embodiment, the molecular weight of the alkoxylated glycerin is about 175 to 400.
In yet another embodiment, the projectile contains ethoxylated glycerin fill material which has a glycerin:ethylene oxide molar ratio of 1:2.4 to 1:6.4, and wherein the fill material has a pour point between -30 to -40 0C, a molecular weight of about 175 to about 400, and a viscosity between 85 to 140 centistokes at 40 0C.
25 The fill composition of the present invention may further comprise a pigment, a field or scent marker for use in wildlife control, and a malodor compound. It may be used as fill material for a paintball.
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In addition to being used as a fill material for paint balls, the use of alkoxylated glycerin in the new composition of the present invention may find applications in other fields. For example, alkoxylated glycerin may be used in as a humectant in cosmetic applications, as part of a drilling mud or insulating fluid in oil field applications, in pesticide 5 formulations, in cleaning products, personal care products, or as a part of an animal feed humectant. It may also be used in any equipment in war games or as a part of a non-lethal weapon.
BRIEF DESCRIPTION OF THE FIGURES
10 The present invention is further described in the detailed description which follows, in reference to the noted plurality of drawings by way of non-limiting examples of embodiments of the present invention, in which like reference numerals represent similar parts throughout the several views of the drawings, and wherein:
Figure 1 illustrates the viscosities, at 40 0C, of ethoxylated glycerins compared to 15 those of PEG of various molecular weights.
Figure 2 illustrates the viscosity of three different glycerin ethoxylates and PEG 300 at temperatures ranging from 30°C to 100°C.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
20 In the following detailed description, the specific embodiments of the present invention are described in connection with its preferred embodiments. However, to the extent that the following description is specific to a particular embodiment or a particular use of the present techniques, it is intended to be illustrative only and merely provides a concise description of the exemplary embodiments. Accordingly, the invention is not
25 limited to the specific embodiments described below, but rather; the invention includes all alternatives, modifications, and equivalents falling within the true scope of the appended claims.
As used herein:
Unless otherwise stated, all percentages, %, are by weight based on the total weight 30 of the composition.
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The "molecular weight" is measured by gel permeation chromatography (GPC) using the following conditions: The samples are prepared by dissolving them in tetrahydrofuran at room temperature. The GPC column is a Polymer Labs Mixed E and the detector is a Waters 410 Differential Refractometer. The eluent is tetrahydrofuran and the 5 flow rate is 1 mL/minute. Column temperature is 400C. Sample concentration is 0.25 weight % and injection volume is 150 μL. Calibration is performed using Polymer Laboratories PEG 10 Calibrants.
The "viscosity" is measured using ASTM Method D-7042. The "pour point" is measured using ASTM Method D-97.
10 The present invention provides new fill compositions to replace the traditional use of
PEGs in applications such as in paintballs, in non-lethal weapons, and in many other applications where a projectile is used. The new compositions comprise an alkoxylated glycerin, or triol. The molecular weight of the alkoxylated glycerin made for the present invention is typically between 130 to 1000, preferably between 130 to 600, and more
15 preferably between 175 to 400. The alkoxylated glycerin can usually be made by a reaction between glycerin and alkylene oxide. Such reaction is usually catalyzed by one of NaOH, KOH, double metal cyanide, or mixture thereof.
Both refined and crude glycerins may be used to make alkoxylated glycerins. In one embodiment of the present invention, glycerin obtained from a byproduct of a biodiesel
20 process is used to react with an alkylene oxide. The alkylene oxide can typically be a) one of ethylene oxide, propylene oxide, or butylene oxide, or b) a mixture of any combinations of ethylene oxide, propylene oxide, and butylene oxide.
Typically, the alkoxylated glycerin has a molar ratio of glycerin:alkylene oxide between about 1 :1 to about 1 :20, preferably between about 1 :1 to about 1 :10, and more 25 preferably between about 1 :2 to about 1:10.
For example, in one embodiment of the present invention, ethylene oxide ("EO") is used to react with glycerin to make ethoxylated glycerin as shown below:
In this reaction, n may be 0.3 to 6.7 depending on the viscosity and/or molecular weight desired in any particular application. The reaction may be carried out at about 130 to 14O0C. The residual catalyst can usually be neutralized by adding acetic acid or some other organic acid that produces soluble salts. The reacted residual catalyst, e.g. soluble 5 potassium acetate salts, may be left in the reaction product and no filtration is needed. Alternatively, an acid such as phosphoric or sulfuric acid can be used to form insoluble catalyst salts followed by filtration.
In one embodiment of the present invention, the ethoxylated glycerin has a molar ratio of glycerin: ethylene oxide of about 1 :2 to about 1:7. In another embodiment, the 10 molar ratio of glycerin:ethylene oxide is about 1 :2.4 to 1 :6.4. hi yet another embodiment, the molar ratio of glycerin:ethylene oxide is about 1 :4.4.
In the present invention, the fill composition typically comprises about 15 to 100 wt. %, preferably about 50 to 100 wt. %, more preferably 75 to 100 wt. %, and most preferably about 90 to 100 wt. % of alkoxylated glycerin.
15 Depending on the application, the fill composition may also contain other components such as dyes or pigments, thickening agents, fragrances, glycerin, malodor compounds, density builders, field or scent marker in wildlife control, surfactants, fillers, polyethylene glycol or a mixture thereof. Water may be added to the fill composition to further lower the cost and reduce viscosity if needed. The fill composition of the present
20 invention is also compatible with PEG and may be used as a blend with PEG material in order to reduce the amount of PEGs used in the fill material, thus reducing the overall fill material cost.
In one embodiment of the present invention, the fill composition comprises about 15 to 100 wt.% of alkoxylated glycerin, less than about 5 wt.% of a dye, less than about 3 wt.% 25 of glycerin, less than about 5 wt.% of water, less than about 4 wt.% of a thickening agent, less than about 85 wt.% of PEG, and less than 1 wt.% of a filler.
The alkoxylated glycerin used in the present invention is substantially in liquid form at a temperature higher than -40 0C. In one embodiment, it is substantially in liquid form at a temperature higher than -30 0C. In another embodiment, it is substantially in liquid form 30 at a temperature higher than -25 0C.
64934A
The alkoxylated glycerin used in the present invention has a pour point of about -20 to -40 0C. In one embodiment, the pour point is about -25 to -40 0C. In another embodiment, the pour point is about -30 to -40 0C.
The viscosity of the alkoxylated glycerin used in the present invention is usually about 75 to 800 centistokes at 40 0C. In one embodiment, the viscosity is about 75 to 150 centistokes at 40 0C. hi another embodiment, the viscosity is about 85 to 140 centistokes at 4O 0C.
The molecular weight of the alkoxylated glycerin used in the present invention is usually about 130 to 1000. In one embodiment, it is about 130 to 600. In another
10 embodiment, it is about 175 to 400.
The present invention is further demonstrated with the following non-limiting examples.
Example 1
15 Four samples of ethoxylated glycerin with different amounts (n) of EO are prepared, using refined glycerin as the starting material, to measure their properties. The samples are tested for their viscosities at 4O0C and their pour points. The same properties for PEG 300 are included for comparison. Some of the results are summarized in Table 1 :
20 Table 1. Various ethoxylated glycerins prepared and their properties.
The viscosities of the ethoxylated glycerin are greater for a given molecular weight than for a PEG of the same molecular weight, as shown in Figure 1. This is particularly true at lower molecular weights where the glycerin ethoxylates show the most economic advantage over PEG. Figure 2 shows the viscosity of the lower molecular weight glycerin 5 ethoxylates compared to PEG 300 at various temperatures. It is noted that the low temperature viscosity of the ethoxylated glycerin is significantly greater than PEG 300. Because of this, viscosity modifiers can be reduced or eliminated in ethoxylated glycerin based fill composition, hence reducing the cost. Even at these increased viscosities, the ethoxylated glycerins are substantially in liquid form. It is also significant that the 10 viscosities converge at higher temperatures, further supporting the idea that the higher viscosity ethoxylated glycerin will not present processing problems compared to PEGs at temperatures typical of storage and processing.
Example 2
15 Several ethoxylated glycerin based fill compositions of the present invention are prepared to demonstrate the feasibility of various applications discussed above. Paintballs with ethoxylated glycerin based fill compositions have been compared to commercially available fill compositions.
Sample ID. Ingredient Amount(%w/w):
A Glycerin/2.4 EO Ethoxylate 99.4
Chromatint Red (Color) 0.6
B. Glycerin/4.4 EO Ethoxylate 99.3
25 Chromatint Red (Color) 0.7
C. Glycerin/6.4 EO Ethoxylate 99.4
Chromatint Red (Color) 0.6
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It is demonstrated that paintballs with above fill compositions (Samples A, B, or C of the present invention) provide equivalent or superior performance characteristics to commercial paintball fills.
Example 3
5 The fill compositions of the present invention may include other components, including PEG, in order to achieve desired performance characteristics and/or to reduce the cost of the products. For example, alkoxylated glycerin based materials can be made using the following compositions:
10 Ingredient Amount(%w/w):
Glycerin/4.4 EO ethoxylate (hydrophilic carrier) 85.02
Glycerin 2.99
Rheolate™ 5000 (thickener) 3.30
Ethomeen™ (pH adjuster) 0.70
15 Water 2.99
Color 5.00
Total: 100.00
Ingredient Amount(%w/w);
20 Glycerin/4.4 EO ethoxylate (hydrophilic carrier) 88.32
Glycerin 2.99
Rheolate™ 5000 (thickener) 0.00
Ethomeen™ (pH adjuster) 0.70
Water 2.99
25 Color 5.00
Total: 100.00
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Ingredient Amount(%w/w):
Glycerin/6.4 EO ethoxylate (hydrophilic carrier) 85.02
Glycerin 2.99
Rheolate™ 5000 (thickener) 3.30
Ethomeen™ (pH adjuster) 0.70
Water 2.99
Color 5.00
Total: 100.00
10 Ingredient Amount(%w/w):
Glycerin/2.4 EO ethoxylate (hydrophilic carrier) 87.30
Glycerin 3.00
Rheolate™ 5000 (thickener) 0.00
Ethomeen™ (pH adjuster) 0.70
15 Color 5.00
Water 4.00
Total: 100.00
Ingredient Amount^ %w/w):
20 Glycerin/4.4 EO ethoxylate (hydrophilic carrier) 45.02
PEG 300 40.00
Glycerin 2.99
Rheolate™ 5000 (thickener) 3.30
Ethomeen™ (pH adjuster) 0.70
25 Water 2.99
Color 5.00
Total: 100.00
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Ingredient Amount(%w/w):
Glycerin/4.4 EO ethoxylate (hydrophilic carrier) 45.00
PEG 300 40.00
PEG 1450 6.30
Glycerin 0.00
Rheolate™ 5000 (thickener) 0.00
Ethomeen™ (pH adjuster) 0.70
Water 3.00
Color and/or Fragrance 5.00
10 Total: 100.00
Ingredient Amountf % w/w) :
Glycerin/4.4 EO ethoxylate (hydrophilic carrier) 94.30
Glycerin 0.00
15 Rheolate™ 5000 (thickener) 0.00
Ethomeen™ (pH adjuster) 0.70
Water 0.00
Color and/or fragrance 5.00
Total: 100.00
20
Ingredient Amountf%w/w):
Glycerin/4.4 EO ethoxylate (hydrophilic carrier) 98.30
Glycerin 0.00
Rheolate™ 5000 (thickener) 0.00
25 Ethomeen™ (pH adjuster) 0.70
Water 0.00
Color and/or fragrance 1.00
Total: 100.00
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Example 4
The compatibility of the projectile shell with the fill material is critical to the performance of the projectile. Equilibrium will be reached between the hydrophilic components of the shell and the fill materials. These hydrophilic components, such as
5 glycerin and water, serve as shell plasticizers, with the general trend that the more hydrophilic the component, the greater plasticizing effect it has on the shell. Since the projectile shell must be neither too hard, nor too soft, the hydrophilicity of the fill material is obviously very important. If the fill contents are too hydrophilic, such as the case for sample A below, the shell becomes too soft. If the fill material is not hydrophilic enough,
10 such as is the case for example C below, there is a migration of plasticizers, such as glycerin, from the shell to the fill, with the result that the shell becomes too brittle.
Sample Nos. A, B, and C of Example 2 are filled into three gelatin shells and results are summarized below:
15 Sample ID. Ingredient Compatibility with Shell
A Glycerin/2.4 EO Ethoxylate shell too soft
Chromatint Red (Color) B. Glycerin/4.4 EO Ethoxylate compatible
Chromatint Red (Color) 20 C. Glycerin/6.4 EO Ethoxylate shell too brittle
Chromatint Red (Color)
It is therefore concluded that Sample B has the best compatibility with gelatin shells.
In addition to being used as a fill material for paint balls, the use of alkoxylated
25 glycerin in the new composition of the present invention may find applications in other fields. For example, alkoxylated glycerin may be used in a cosmetic formulation as a humectant, as part of a drilling mud or insulating fluid in oil field applications, in pesticide formulations, in cleaning products, personal care products, or as a part of an animal feed humectant. It may also be used in any equipment in war games or as a part of a non-lethal
30 weapon.
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While the present invention may be susceptible to various modifications and alternative forms, the exemplary embodiments discussed above have been shown by way of example. However, it should again be understood that the invention is not intended to be limited to the particular embodiments disclosed herein. Indeed, the present techniques of 5 the invention are to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the following appended claims.