USRE30450E - Surface modified pigments - Google Patents
Surface modified pigments Download PDFInfo
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- USRE30450E USRE30450E US06/026,380 US2638079A USRE30450E US RE30450 E USRE30450 E US RE30450E US 2638079 A US2638079 A US 2638079A US RE30450 E USRE30450 E US RE30450E
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
Definitions
- This invention relates to finely divided particulate inorganic pigments modified with amino organosilanes and the process for their production.
- thermosetting resins such as polyurethanes, epoxy polymers, melamine polymers, phenolic polymers, ureaformaldehyde polymers, unsaturated polyesters, as well as other polymers and elastomers including polyethylenes, polypropylenes, polystyrenes, saturated polyesters, polyamides, polyvinyl compounds, polyisoprenes, polybutadienes, polystyrenebutadienes, and the like.
- thermosetting resins such as polyurethanes, epoxy polymers, melamine polymers, phenolic polymers, ureaformaldehyde polymers, unsaturated polyesters, as well as other polymers and elastomers including polyethylenes, polypropylenes, polystyrenes, saturated polyesters, polyamides, polyvinyl compounds, polyisoprenes, polybutadienes, polystyrenebutadienes, and the like.
- the modified pigments can also be advantageously used as fillers for paper, paints, varnishes, inks, and paper coating compositions.
- Inorganic pigments modified with amino organosilanes have affinity for direct dyes and are useful for imparting various colors to the vehicles.
- An object of this invention is to provide modified pigments especially useful as fillers.
- Another object of this invention is to provide modified pigments which are dyeable with direct dyes and are useful as color-imparting fillers.
- a further object of this invention is to provide modified pigments which can be used as fillers in applications where they had heretofore been unsatisfactory.
- a still further object of the invention is to provide cross-linkable fillers capable of imparting improved abrasion resistance among other improved properties to elastomers.
- the modified pigments of this invention can be prepared by dissolving the desired amount of amino organosilane in a suitable solvent, adding the pigment and heating until the reaction is complete.
- the amount of modifier added depends upon the particular pigment being modified and the use for which it is intended. Generally up to about 15% by weight of the modifier is sufficient for most purposes.
- a particularly useful process of modifying pigments according to this invention involves spray drying pigment slurries having one or more of the amino organosilanes dispersed therein.
- the spray drying process effects a uniform distribution of the modifier on the pigment and virtually instantaneously cures the modifier on the pigment.
- R 1 is hydrogen, alkyl, aryl, cycloalkyl, or alkylaryl
- R 2 is hydrogen, alkyl, aryl, cycloalkyl or alkylaryl
- R 3 is hydrogen, lower alkyl, aryl, lower alkylaryl, or loer arylalkyl
- R 4 is hydrogen, lower alkyl, aryl, lower alkylaryl or lower arylalkyl
- R 5 is hydrogen, lower alkyl, aryl, lower alkylaryl or lower arylalkyl
- X is alkylene, arylene, alkylarylene, arylalkylene, cycloalkylene having secondary and/or tertiary nitrogen present in the chain, and/or primary, secondary, and/or tertiary nitrogen pendant from the chain.
- amino organosilanes are disclosed along with methods for their preparation in U.S. Pat. Nos. 2,832,754; 2,930,809; 3,007,957; and 3,020,302.
- Commercially available amino organosilanes include "A-1100” (gamma aminopropyltriethoxysilane) and "Y-2967” (an amino silane which is a modified gamma aminopropyltriethoxysilane) sold by Union Carbide Corporation, N.Y., N.Y., and "Z-6020” (a diamino functional silane) sold by Dow Corning Corporation, Midland, Michigan.
- .Iadd.Preferred compounds to modify the pigments are amino organosilanes of the formula:
- R is selected from the group consisting of phenylene, lower alkyl substituted phenylene, lower alkoxy substituted phenylene, and lower alkylene
- R' is monovalent hydrocarbon group free of aliphatic unsaturation selected from the group consisting of lower alkyl, aryl, lower alkaryl and lower aralkyl, wherein R' can represent the same or different groups. .Iaddend.
- Pigments advantageously modified in the practice of this invention are finely divided particulate inorganic pigments such as, for example, inorganic compounds of silicon, including hydrated or anhydrous silicas, calcium silicates, magnesium silicates, calcium-magnesium silicates, barium silicates, aluminum silicates, sodium-alumino-silicates, calcium-alumino-silicates, calcium-sodium alumino silicates; clays such as kaolins which include dickite, kaolinite and nacrite, halloysite, montmorillonites including sodium and magnesium bentonites, synthetic or natural zeolites; various metal oxides and carbonates such as zinc oxide, alumina, titania or magnesia, calcium carbonate; and various non-white pigments like carbon blacks, zinc sulfide, ferric oxide and the like.
- inorganic compounds of silicon including hydrated or anhydrous silicas, calcium silicates, magnesium silicates, calcium-magnesium si
- Zeolex® very finely divided precipitated sodium alumino silicate pigments of submicron particle size and disclosed in U.S. Pat. Nos. 2,739,073 and 2,848,346.
- Zerosil® very finely divided precipitated hydrated silicas of submicron particle size and disclosed in copending U.S. Pat. applications Ser. No. 144,168 filed Oct. 10, 1961, and 149,964 filed Nov. 3, 1961.
- Suprex® an air floated kaolin clay with platelike particles of which 87-92% are minus 2 microns.
- Aromex® intermediate super abrasion furnace carbon blacks.
- Silene EF® a precipitated hydrated calcium silicate of very fine particle size.
- Hi-Sil® a precipitated hydrated silica of very fine particle size.
- Celite® a diatomaceous earth which is principally a hydrated silica.
- Alumina C® a hydrated aluminum oxide of small particle size.
- Kadox® a zinc oxide filler
- Titanox® a pigment grade commercial titanium dioxide.
- Ludox® a precipitated silica of very fine particle size.
- “Suprex” was modified with 1.0% by weight with gamma aminopropyltriethoxysilane by adding the appropriate amount of the modifier using water as a solvent and then adding the clay and refluxing for 21/2 hours. The products were recovered and dried. The example was repeated with 2.0% and 3.0% gamma aminopropyltriethoxysilane.
- Zeolex 23 was modified with 1% by weight with gamma aminopropyltriethoxysilane by adding the "Zeolex" to a benzene solution of the modifier and refluxing for 21/2 hours. The product was recovered and dried.
- “Suprex” was modified with 1.0% of "Z-6020” by adding 3.33 pounds “Z-6020” to 667 pounds of water while under agitation. 333 pounds of "Suprex” was slowly added to the solution while continuing the stirring until a homogeneous clay slip resulted. The clay slip was then spray dried in a 7-foot conical spray dryer operated at an inlet temperature of 600° F. and an outlet temperature of 250° F. A finely pulverized, chemically modified clay product was obtained. The example was repeated to produce 2.0% and 3.0% modifications of the "Suprex.”
- Example 4 was repeated using "Y-2967” instead of “Z-6020.”
- Example 4 was repeated using "A-1100" instead of "Z-6020.”
- "Suprex” was modified with 1% of gamma aminopropyltriethoxysilane by adding 10 grams gamma aminopropyltriethoxysilane to 3.5 liters benzene, then adding 1 kilogram "Suprex” clay and refluxing for 3 hours. The modified clay was recovered and dried. This example was repeated using 2% and 3% instead of 1% gamma aminopropyltriethoxysilane.
- Example 7 was repeated using "Z-6020" in place of gamma aminopropyltriethoxysilane.
- Example 7 was repeated using "Y-2967" in place of gamma aminopropyltriethoxysilane.
- the physical properties of the various pigments disclosed herein are significantly altered by modification with the group of silanes disclosed herein.
- kaolin clay when so modified, a dramatic change in its properties is apparent.
- the clay lacked significant affinity for direct dyes, it is modified by the process of this invention to be readily dyeable with direct dyes.
- the modified kaolin clays can be used as a filler for polyurethanes where, before modification, it was unusable since it prevented a cure of the polymer. This is illustrated in Table I in which the following formation was employed:
- the compounds were mixed on a 6-inch by 12-inch laboratory mill and cured for 30 minutes at 307° F., except for the NBS abrasion test where the cure was for 60 minutes at 307° F.
- modified kaolin clay filled polyurethane over both the compound filled with unmodified kaolin and the unfilled compound.
- the increase in abrasion resistance with increased modification of kaolin It is also apparent from the data that unmodified kaolin is unsatisfactory as a filler for polyurethanes since the polymer did not cure.
- the use of modified kaolin clay not only improves the properties of the polyurethane but also decreases the raw material cost since the filler is much less expensive than the polymer.
- Table II demonstrates dramatic improvements in properties of polyurethane filled with amino organosilane modified clays.
- the batches were mixed on a Banbury using speed #1, ram pressure of 30 p.s.i., and a starting temperature of 125° F.; the final batch mix was on a 6-inch by 12-inch mill and the inlet water temperature was 158° F. The compound was cured for 70 minutes at 275° F., then tested. The results are listed in Table III.
- modified Zeolex When modified Zeolex is used as a filler for rubber compounds, it imparts to the rubber improved properties of modulus, tensile strength, tear resistance and abrasion resistance when compared to these same properties in rubber filled with unmodified Zeolex.
- Table IV The results in Table IV are based upon the following recipe:
- the recipe was mixed on a Banbury mixer at speed #1, ram pressure of 30 p.s.i., and at a starting temperature of 125° F.
- the final batch was mixed on a 6-inch by 12-inch mill with a water inlet temperature of 158° F.
- the compound was cured at 292° F., then tested. The results are shown in Table IV.
- the compounds were mixed on a 6-inch by 12-inch laboratory mill and then cured at 260° F. to produce 30-, 45-, and 60-minute cures of each.
- Table V below compares the abrasion index and the 200% modulus level of each of the test materials.
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Abstract
.Iadd.Finely divided particulate inorganic pigment is surface modified with from about 1% to about 15% of an amino organosilane, particularly gamma-aminopropyltriethoxy silane. Thermosetting resins incorporating such modified inorganic pigments exhibit improved physical properties.
Description
This is application is a .Iadd.reissue of U.S. Pat. No. 3,290,165, Ser. No. 269,695 filed April 1, 1963, which is a .Iaddend.continuation-in-part of applicant's copending application Ser. No. 189,321, filed April 23, 1962, entitled "Surface Modified Pigments," and now abandoned.
This invention relates to finely divided particulate inorganic pigments modified with amino organosilanes and the process for their production.
When inorganic pigments are modified with the silanes according to this invention, the properties imparted to them are such that they can advantageously be used as fillers for thermosetting resins such as polyurethanes, epoxy polymers, melamine polymers, phenolic polymers, ureaformaldehyde polymers, unsaturated polyesters, as well as other polymers and elastomers including polyethylenes, polypropylenes, polystyrenes, saturated polyesters, polyamides, polyvinyl compounds, polyisoprenes, polybutadienes, polystyrenebutadienes, and the like.
The modified pigments can also be advantageously used as fillers for paper, paints, varnishes, inks, and paper coating compositions.
By the use of these modified finely divided particulate inorganic pigments, improved physical properties are imparted to the vehicles into which they are incorporated.
Inorganic pigments modified with amino organosilanes have affinity for direct dyes and are useful for imparting various colors to the vehicles.
An object of this invention is to provide modified pigments especially useful as fillers.
Another object of this invention is to provide modified pigments which are dyeable with direct dyes and are useful as color-imparting fillers.
A further object of this invention is to provide modified pigments which can be used as fillers in applications where they had heretofore been unsatisfactory.
A still further object of the invention is to provide cross-linkable fillers capable of imparting improved abrasion resistance among other improved properties to elastomers.
Other objects and advantages will be apparent from the following specification.
I am aware of extensive efforts in the prior art to improve properties of filler pigments by modification with organosilanes. Hydrocarbon silane modifications of pigments do impart improved dispersions in organic vehicles but such modifications do not normally increase reinforcement in vinyl addition polymers unless the hydrocarbon silane carries specific types of unsaturation which serves to promote a more tenacious bridge between the filler and the vehicle. In any case, all these prior art modified pigments are rendered hydrophobic by modification with either saturated or unsaturated hydrocarbon silanes and, furthermore, such silane modified pigments are not valuable reinforcing fillers in saturated thermosetting resins.
I have discovered that modification of filler pigments with saturated amino organosilanes improves reinforcement in a wide variety of vinyl addition as well as thermosetting polymers in that a strong chemical bridge between filler pigment and polymer results. Bridging is accomplished through the amino modified surface of the pigments. Surprisingly, amino organosilane modification improves reinforcement in both vinyl addition and thermosetting polymers, whereas unsaturated organosilane fillers are generally only effective in vinyl addition polymers where unsaturation is present. Another important advantage of amino organosilane modified fillers is that they are usually hydrophilic whereas prior art silane modified fillers are hydrophobic.
The modified pigments of this invention can be prepared by dissolving the desired amount of amino organosilane in a suitable solvent, adding the pigment and heating until the reaction is complete. The amount of modifier added depends upon the particular pigment being modified and the use for which it is intended. Generally up to about 15% by weight of the modifier is sufficient for most purposes.
A particularly useful process of modifying pigments according to this invention involves spray drying pigment slurries having one or more of the amino organosilanes dispersed therein. The spray drying process effects a uniform distribution of the modifier on the pigment and virtually instantaneously cures the modifier on the pigment.
The compounds used to modify the pigments can be depicted by the formula: ##STR1## wherein R1 is hydrogen, alkyl, aryl, cycloalkyl, or alkylaryl; R2 is hydrogen, alkyl, aryl, cycloalkyl or alkylaryl; R3 is hydrogen, lower alkyl, aryl, lower alkylaryl, or loer arylalkyl; R4 is hydrogen, lower alkyl, aryl, lower alkylaryl or lower arylalkyl; R5 is hydrogen, lower alkyl, aryl, lower alkylaryl or lower arylalkyl; and X is alkylene, arylene, alkylarylene, arylalkylene, cycloalkylene having secondary and/or tertiary nitrogen present in the chain, and/or primary, secondary, and/or tertiary nitrogen pendant from the chain. Some of these amino organosilanes are disclosed along with methods for their preparation in U.S. Pat. Nos. 2,832,754; 2,930,809; 3,007,957; and 3,020,302. Commercially available amino organosilanes include "A-1100" (gamma aminopropyltriethoxysilane) and "Y-2967" (an amino silane which is a modified gamma aminopropyltriethoxysilane) sold by Union Carbide Corporation, N.Y., N.Y., and "Z-6020" (a diamino functional silane) sold by Dow Corning Corporation, Midland, Michigan.
.Iadd.Preferred compounds to modify the pigments are amino organosilanes of the formula:
H.sub.2 N--R--Si(OR').sub.3
wherein R is selected from the group consisting of phenylene, lower alkyl substituted phenylene, lower alkoxy substituted phenylene, and lower alkylene, R' is monovalent hydrocarbon group free of aliphatic unsaturation selected from the group consisting of lower alkyl, aryl, lower alkaryl and lower aralkyl, wherein R' can represent the same or different groups. .Iaddend.
Pigments advantageously modified in the practice of this invention are finely divided particulate inorganic pigments such as, for example, inorganic compounds of silicon, including hydrated or anhydrous silicas, calcium silicates, magnesium silicates, calcium-magnesium silicates, barium silicates, aluminum silicates, sodium-alumino-silicates, calcium-alumino-silicates, calcium-sodium alumino silicates; clays such as kaolins which include dickite, kaolinite and nacrite, halloysite, montmorillonites including sodium and magnesium bentonites, synthetic or natural zeolites; various metal oxides and carbonates such as zinc oxide, alumina, titania or magnesia, calcium carbonate; and various non-white pigments like carbon blacks, zinc sulfide, ferric oxide and the like.
All the above fillers are available on a commercial scale and include the following, all of which are finely divided, particulate substances.
Zeolex®, very finely divided precipitated sodium alumino silicate pigments of submicron particle size and disclosed in U.S. Pat. Nos. 2,739,073 and 2,848,346.
Zerosil®, very finely divided precipitated hydrated silicas of submicron particle size and disclosed in copending U.S. Pat. applications Ser. No. 144,168 filed Oct. 10, 1961, and 149,964 filed Nov. 3, 1961.
Suprex®, an air floated kaolin clay with platelike particles of which 87-92% are minus 2 microns.
Aromex®, intermediate super abrasion furnace carbon blacks.
Essex®, semi-reinforcing furnace blacks.
Silene EF®, a precipitated hydrated calcium silicate of very fine particle size.
Hi-Sil®, a precipitated hydrated silica of very fine particle size.
Celite®, a diatomaceous earth which is principally a hydrated silica.
Alumina C®, a hydrated aluminum oxide of small particle size.
Kadox®, a zinc oxide filler.
Titanox®, a pigment grade commercial titanium dioxide.
Cab-O-Sil®, a very finely divided anhydrous silica.
Ludox®, a precipitated silica of very fine particle size.
The following examples illustrate typical methods by which various pigments are surface modified in accordance with this invention.
8 grams of gamma aminopropyltriethoxysilane (A-1100) was dissolved in 3.3 liters of benzene in a 5-liter round bottom flask. 400 grams of carbon black (ISAF) was added and the resulting mixture was refluxed 2 hours. The resulting product contained 2% of the modifier based on the weight of the carbon black.
"Suprex" was modified with 1.0% by weight with gamma aminopropyltriethoxysilane by adding the appropriate amount of the modifier using water as a solvent and then adding the clay and refluxing for 21/2 hours. The products were recovered and dried. The example was repeated with 2.0% and 3.0% gamma aminopropyltriethoxysilane.
"Zeolex 23" was modified with 1% by weight with gamma aminopropyltriethoxysilane by adding the "Zeolex" to a benzene solution of the modifier and refluxing for 21/2 hours. The product was recovered and dried.
"Suprex" was modified with 1.0% of "Z-6020" by adding 3.33 pounds "Z-6020" to 667 pounds of water while under agitation. 333 pounds of "Suprex" was slowly added to the solution while continuing the stirring until a homogeneous clay slip resulted. The clay slip was then spray dried in a 7-foot conical spray dryer operated at an inlet temperature of 600° F. and an outlet temperature of 250° F. A finely pulverized, chemically modified clay product was obtained. The example was repeated to produce 2.0% and 3.0% modifications of the "Suprex."
Example 4 was repeated using "Y-2967" instead of "Z-6020."
Example 4 was repeated using "A-1100" instead of "Z-6020."
"Suprex" was modified with 1% of gamma aminopropyltriethoxysilane by adding 10 grams gamma aminopropyltriethoxysilane to 3.5 liters benzene, then adding 1 kilogram "Suprex" clay and refluxing for 3 hours. The modified clay was recovered and dried. This example was repeated using 2% and 3% instead of 1% gamma aminopropyltriethoxysilane.
Example 7 was repeated using "Z-6020" in place of gamma aminopropyltriethoxysilane.
Example 7 was repeated using "Y-2967" in place of gamma aminopropyltriethoxysilane.
The above examples illustrate the facility with which various inorganic pigments are modified with amino organosilanes.
The examples were repeated using each of the pigments named herein to produce modified pigments having properties similar to those discussed below.
While only three modifiers are exemplified, this is done for convenience since all those disclosed herein have been used for the purpose and come within the scope of this invention.
The physical properties of the various pigments disclosed herein are significantly altered by modification with the group of silanes disclosed herein. For example, when kaolin clay is so modified, a dramatic change in its properties is apparent. Where, before, the clay lacked significant affinity for direct dyes, it is modified by the process of this invention to be readily dyeable with direct dyes. The modified kaolin clays can be used as a filler for polyurethanes where, before modification, it was unusable since it prevented a cure of the polymer. This is illustrated in Table I in which the following formation was employed:
______________________________________
Parts
______________________________________
Vibrathane 5003.sup.1
100
Stearic acid 0.25
Di-Cup 40C.sup.2 5
Clay 60
______________________________________
.sup.1 A polyurethane produced by Naugatuck Chemical Division of U.S.
Rubber Company.
.sup.2 A polymerizing crosslinking agent produced by Hercules Powder
Company.
The compounds were mixed on a 6-inch by 12-inch laboratory mill and cured for 30 minutes at 307° F., except for the NBS abrasion test where the cure was for 60 minutes at 307° F.
TABLE I
__________________________________________________________________________
Example 2
Suprex
Suprex
Suprex
plus 1%
plus 2%
plus 3%
Control
Suprex
Modifier
Modifier
Modifier
__________________________________________________________________________
Parts filler/100 parts polymer
None 60 60 60 60
Tensile, p.s.i 5,240
No cure
3,680
3,770
3,840
Stress, 300%, p.s.i
830 No cure
2,070
3,190
--
Elongation, percent
500 No cure
470 425 265
Shore A Hardness g
56 No cure
71 71 75
NBS Abrasion, percent of standard
129 No cure
122 172 202
__________________________________________________________________________
The results illustrate the improved properties of modified kaolin clay filled polyurethane over both the compound filled with unmodified kaolin and the unfilled compound. Note, for example, the increase in abrasion resistance with increased modification of kaolin. It is also apparent from the data that unmodified kaolin is unsatisfactory as a filler for polyurethanes since the polymer did not cure. The use of modified kaolin clay not only improves the properties of the polyurethane but also decreases the raw material cost since the filler is much less expensive than the polymer.
TABLE II
__________________________________________________________________________
MODIFIED SUPREX CLAYS IN VIBRATHANE 5003
Example 2
Minutes Suprex
1% 2% Example 4
Example
Example 9
Cured at
Unfilled
Filled
Modifier
Modifier
1% Z-6020
1% Z-6020
1% Y-2967
Physical Properties 305° F.
Control
Control
Water
Water
Water Benzene
Benzene
__________________________________________________________________________
200% Modulus 30 430 1,270
1,340
2,900
-- 2,900 1,710
60 500 1,310
1,530
2,990
2,890 1,710 --
75 510 1,330
1,480
2,820
-- 2,860 1,840
300% Modulus 30 830 1,570
2,070
3,190
-- 3,270 2,060
60 1,050
1,640
2,220
3,340
3,330 3,270 2,090
75 1,040
1,630
2,520
3,200
-- 3,240 2,170
Tensile Strength 30 5,240
4,340
3,680
3,770
2,960 3,470 4,040
60 4,890
3,850
3,920
3,490
3,620 3,290 3,610
75 5,320
3,640
3,560
3,510
-- 3,240 3,950
Elongation 30 500 570 470 425 190 365 560
60 440 525 450 335 360 315 500
75 450 505 440 370 -- 300 510
Hardness, Shore A 30 56 72 71 71 75 75 70
60 59 74 73 73 76 76 71
75 59 74 73 73 13 76 71
Crescent Tear 30 65 285 280 238 225 235 303
60 68 270 230 243 205 193 220
75 73 243 231 225 -- 193 225
NBS Abrasion Index, Percent
60 74.8 63.6 77.2 109.5
143.5 131.4 68.2
75 80.3 62.2 87.4 137.0
105.5 152.1 81.5
Hardness, Shore A, NBS Specimens
60 55 71 72 75 76 76 71
75 56 73 73 75 76 76 72
NBS Abrasion (Gum=100%)
60 100 85 103 147 192 176 91
75 107 83 117 183 141 204 109
Compression Set "B" 22 hrs./158° F.
60 5.5 34.0 17.5 11.3 10.1 12.0 25.0
75 5.1 36.7 16.5 12.0 9.5 11.0 23.9
Mooney Viscosity, ML 4'/212° F.
-- 44 60 65 65 83 65 64
Mooney Scorch, MS/265° F.
-- 23 26 20 16 12.5 18 23
__________________________________________________________________________
Table II demonstrates dramatic improvements in properties of polyurethane filled with amino organosilane modified clays.
When modified carbon black is used as the filler in a rubber recipe, good results compared to unmodified black are achieved with a 2% by weight modification using gamma aminopropyltriethoxysilane. The results listed in Table III are based upon tests in the following recipe.
______________________________________
Parts/100 RHC
______________________________________
Smoked sheet 100.0
ISAF carbon black
45.0
Zinc oxide 3.0
Stearic acid 3.0
Pine tar 3.0
Age rite HP.sup.1
1.0
NOBS special.sup.2
0.35
Sulfur 2.75
Total 158.10
______________________________________
.sup.1 An antioxidant containing phenylbeta-naphthylamine and
N,Ndiphenyl-para-phenylenediamine.
.sup.2 Accelerator containing Noxydiethylene benzothlazol2-sulfenamide.
The batches were mixed on a Banbury using speed #1, ram pressure of 30 p.s.i., and a starting temperature of 125° F.; the final batch mix was on a 6-inch by 12-inch mill and the inlet water temperature was 158° F. The compound was cured for 70 minutes at 275° F., then tested. The results are listed in Table III.
TABLE III
______________________________________
Abrasion,
Percent Modulus, Tensile,
Huber-
Pigment Modifier p.s.i. p.s.i. Williams
______________________________________
ISAF Carbon Black
None 1,780 4,590 100.0
Control.
ISAF Carbon Black
.sup.1 1,970 4,720 107.9
______________________________________
.sup.1 2.0% gamma aminopropyltriethoxysilane.
This data indicates that when carbon black is modified with controlled amounts of modifier, the properties which it imparts to rubber are improved in respect to modulus, tensile, and abrasion resistance.
When modified Zeolex is used as a filler for rubber compounds, it imparts to the rubber improved properties of modulus, tensile strength, tear resistance and abrasion resistance when compared to these same properties in rubber filled with unmodified Zeolex. The results in Table IV are based upon the following recipe:
______________________________________
Parts/100 RHC
______________________________________
GRS 1502.sup.1 100.0
Pliolite S6B.sup.2
20.0
Zinc oxide 3.0
Stearic acid 2.0
Cumar MH 21/2.sup.3
7.5
Zeolex 23 66.5
Santocure.sup.4
2.0
DOTG.sup.5 1.0
Sulfur 2.5
Total 204.5
______________________________________
.sup.1 Emulsion copolymer of 23.5% styrene and 76.5% butadiene.
.sup.2 A styrenebutadiene copolymer of high styrene content.
.sup.3 Paracumarene-indene resin.
.sup.4 nCyclohexyl-2-benzothiazole sulfenamide accelerator.
.sup.5 Diortho-tolylguanidine.
The recipe was mixed on a Banbury mixer at speed #1, ram pressure of 30 p.s.i., and at a starting temperature of 125° F. The final batch was mixed on a 6-inch by 12-inch mill with a water inlet temperature of 158° F. The compound was cured at 292° F., then tested. The results are shown in Table IV.
TABLE IV
______________________________________
Cure 200% 300% 400%
Minutes Modulus Modulus Modulus
Tensile
Elongation
______________________________________
PIGMENT-ZEOLEX 23 UNMODIFIED-CONTROL
5 80 -- -- 80 280
10 80 -- -- 80 280
15 470 650 860 1,300 605
20 720 1,000 1,350 1,640 460
30 750 1,060 1,450 1,560 420
______________________________________
PIGMENT-ZEOLEX 23 MODIFIED WITH 10% GAMMA
AMINO-PROPYLTRIETHOXYSILANE
5 690 1,010 1,340 1,970 580
10 910 1,300 1,710 2,480 550
15 1,010 1,400 1,820 2,360 510
20 1,070 1,480 1,920 2,280 470
30 1,090 1,480 1,940 2,360 480
______________________________________
Abrasion Index.sup.1
Shore Hardness
Pigment 10' 15' 20' 10' 15' 20'
______________________________________
Zeolex 23 Control
.sup.2 41.5 47.5 60 72 77
Modified Zeolex 23
61.7 63.0 62.3 76 76 77
______________________________________
Tear Resistance, Avg.
Pigment 5' 10' 15' 20'
______________________________________
Zeolex 23 Control
37.5 38.5 174 160
Modified Zeolex 23
216.5 193.5 195 187.5
______________________________________
.sup.1 Percent of NBS Standard sample.
.sup.2 Not cured.
The results indicate that Zeolex 23 modified with gamma aminopropyltriethoxysilane, when compared with unmodified Zeolex 23 used as a filler for rubber, is faster curing, has increased modulus, increased tensile strength, and improved tear resistance and abrasion resistance.
It should also be noted that physical and "wet" electrical properties of filled resin systems can be significantly improved by treating the fillers in accordance with this invention.
I have found that in addition to the concepts disclosed above, the properties of the modified pigments are affected by the solvent used in their preparation.
The properties of carbon blacks, clays and silicates modified in aqueous systems, such as disclosed in Example 2, vary markedly from the properties of these same pigments modified in nonaqueous systems as disclosed in Examples 1 and 3.
In order to demonstrate these differences, regular Suprex clay, Suprex clay of Example 2, and Suprex clay modified in nonaqueous solvent according to the teachings of Example 7 were used in producing rubber compounds using the following recipe.
______________________________________
Parts by weight
______________________________________
Smoked sheet.sup.1 100
Clay (as specified in Table V)
104
Zinc oxide 5
Sulfur 3
Captax 1
Stearic acid 4
______________________________________
.sup.1 Natural rubber.
The compounds were mixed on a 6-inch by 12-inch laboratory mill and then cured at 260° F. to produce 30-, 45-, and 60-minute cures of each.
Table V below compares the abrasion index and the 200% modulus level of each of the test materials.
TABLE V
______________________________________
Abrasion Index,
200% Modulus
Percent p.s.i.
Clay 30' 45' 60' 30' 45' 60'
______________________________________
Suprex Control 55.0 55.9 53.7 760 960 990
Suprex 3% Modifier
72.8 68.6 65.2 2,000
2,070
2,170
(Benzene)
Suprex 3% Modifier
84.6 85.5 70.7 1,740
1,970
1,990
(Water)
______________________________________
The results as set forth in Table V clearly indicate that clays modified in accordance with the invention impart superior properties to rubber compounds when used as a filler therein. These results also demonstrate that the clays modified in an aqueous system give a higher abrasion resistance and a lower modulus than clays modified in a nonaqueous system.
While natural rubber was used in the recipes tested in Table V, these tests were also conducted with similar results from recipes using SBR, polyurethanes and polybutadiene.
The foregoing is illustrative only and additional modifications may be made without departing from the substance of the invention as defined in the appended claims.
Claims (8)
1. A .Iadd.filler comprising a .Iaddend.finely divided particulate inorganic pigment surface .Iadd.selected from the group consisting of synthetic silicas, silicates, metal oxides, calcium carbonates, zinc sulfides, and carbon blacks, said pigment surface having been .Iaddend.modified .Iadd.by treatment .Iaddend.with from about 1% to 15%, based on the weight of the dry pigment, of an amino organosilane of the formula ##STR2## wherein R1 is selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, and alkylaryl, R2 is selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl and alkylaryl, R3 is selected from the group consisting of hydrogen, lower alkyl, aryl, lower alkylaryl and lower arylalkyl, R4 is selected from the group consisting of hydrogen, lower alkyl, aryl, lower alkylaryl and lower arylalkyl, R5 is selected from the group consisting of hydrogen, lower alkyl, aryl, lower alkylaryl, and lower arylalkyl, X is selected from the group consisting of alkylene, arylene, alkylarylene, arylalkylene, cycloalkylene containing secondary amino nitrogen, and cycloalkylene containing tertiary amino nitrogen.Iadd., the modification of said pigment surface by said organosilane comprising spray drying slurries of said pigment having one or more of the amino organosilanes dispersed therein. .Iaddend. .[.
2. A compound as in claim 1 wherein the finely divided particulate filler is selected from the group consisting of synthetic silicas, silicates, metal oxides, calcium carbonates, zinc sulfides, and carbon blacks..].
3. A compound as in claim 1 wherein the amino organosilane is gamma aminopropyltriethoxysilane.
4. A compound as in claim 1 wherein the amino organosilane is a diamino functional silane.
5. Finely divided particulate hydrated silica, surface modified with from about 1% to 15% by weight based upon the weight of the silica of gamma aminopropyltriethoxysilane.
6. Finely divided particulate sodium alumino silicate pigment, surface modified with from about 1% to 15% by weight, based upon the weight of the pigment, of gamma aminopropyltriethoxysilane.
7. Finely divided particulate carbon black, surface modified with from about 1%to 15% by weight, based upon the weight of the carbon black, of gamma aminopropyltriethoxysilane.
8. Finely divided particulate kaolin clay, surface modified with from about 1% to 15% by weight, based upon the weight of the kaolin clay, of gamma aminopropyltriethoxysilane. .Iadd. 9. A filler comprising a finely divided particulate inorganic pigment surface selected from the group consisting of synthetic silicas, silicates, metal oxides, calcium carbonates, zinc sulfides, and carbon blacks, said pigment surface having been modified by treatment with from about 1% to 15%, based on the weight of the dry pigment, of an amino organosilane of the formula
H.sub.2 N--R--Si(Or').sub.3
wherein R is selected from the group consisting of phenylene lower alkyl substituted phenylene, lower alkoxy substituted phenylene, and lower alkylene, R' is a monovalent hydrocarbon group free of aliphatic unsaturation selected from the group consisting of lower alkyl, aryl, lower alkaryl and lower aralkyl, wherein R' can represent the same or different groups. .Iaddend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/026,380 USRE30450E (en) | 1979-04-02 | 1979-04-02 | Surface modified pigments |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/026,380 USRE30450E (en) | 1979-04-02 | 1979-04-02 | Surface modified pigments |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US04189321 Continuation-In-Part | 1962-04-23 | ||
| US269695A Reissue US3290165A (en) | 1963-04-01 | 1963-04-01 | Surface modified pigments |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE30450E true USRE30450E (en) | 1980-12-16 |
Family
ID=21831498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/026,380 Expired - Lifetime USRE30450E (en) | 1979-04-02 | 1979-04-02 | Surface modified pigments |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE30450E (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232745A1 (en) * | 1986-02-11 | 1987-08-19 | Hewlett-Packard Company | Process for increasing the dispersibility of carbon black |
| EP0468140A2 (en) * | 1990-07-25 | 1992-01-29 | Degussa Aktiengesellschaft | With organosilicium-compound chemically modified carbon blacks, method for their preparation and their use |
| US5356471A (en) * | 1992-08-17 | 1994-10-18 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Pigments of dark surface color |
| EP0816420A1 (en) * | 1996-06-24 | 1998-01-07 | The Goodyear Tire & Rubber Company | Aminosilane compounds in silica-filled rubber compositions |
| US5707437A (en) * | 1994-02-28 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Silanized titanium dioxide pigments resistant to discoloration when incorporated in polymers |
| US5889090A (en) * | 1994-02-28 | 1999-03-30 | E. I. Dupont Denemours & Company | Processibility and lacing resistance when silanized pigments are incorporated in polymers |
| US20030003277A1 (en) * | 2001-05-18 | 2003-01-02 | Cabot Corporation | Ink jet recording medium comprising amine-treated silica |
| US20030224174A1 (en) * | 2002-06-03 | 2003-12-04 | Daniela White | Coating compositions with modified particles and methods of using the same |
| US20030229157A1 (en) * | 2002-06-03 | 2003-12-11 | Schneider John R. | Coating compositions with modified particles and methods of using the same |
| US20040138339A1 (en) * | 2003-01-14 | 2004-07-15 | Freeman Gary M. | Coating composition containing surface treated clay mixture, the surface treated clay mixture used therefor, and methods of their use |
| US6916368B2 (en) | 2002-02-20 | 2005-07-12 | Ppg Industries Ohio, Inc. | Curable film-forming composition exhibiting improved scratch resistance |
| WO2006002085A1 (en) | 2004-06-15 | 2006-01-05 | W. R. Grace & Co.-Conn. | Chemically assisted milling of silicas |
| US20060275597A1 (en) * | 2005-06-07 | 2006-12-07 | Thiele Erik S | Paper and paper laminates containing modified titanium dioxide |
| WO2013181021A1 (en) * | 2012-05-30 | 2013-12-05 | Kamin Llc | Methods and compositions for increasing ink clay loading in heatset ink formulations while maintaining ink gloss, and ink formulations produced therefrom |
| US12018173B1 (en) | 2019-08-21 | 2024-06-25 | Swimc Llc | High physical durability coating compositions |
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| US2742378A (en) * | 1952-08-02 | 1956-04-17 | Gen Tire & Rubber Co | Fillers having vinyl siloxane groups bonded to the surface thereof and copolymers thereof with ethylenically unsaturated polymerizable monomers |
| US2832754A (en) * | 1955-01-21 | 1958-04-29 | Union Carbide Corp | Alkoxysilylpropylamines |
| GB863412A (en) * | 1956-04-17 | 1961-03-22 | Union Carbide Corp | Pigment dispersants |
| US3015569A (en) * | 1958-11-26 | 1962-01-02 | Interchem Corp | Treatment of pigments |
| US3029209A (en) * | 1959-08-12 | 1962-04-10 | Minerals & Chem Philipp Corp | Polyurethane foams filled with organophilic kaolin clay and method for making same |
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| US3168389A (en) * | 1960-12-28 | 1965-02-02 | Pittsburgh Plate Glass Co | Silane forming size and glass fiber strands threated therewith for resin reinforcement |
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| US2832754A (en) * | 1955-01-21 | 1958-04-29 | Union Carbide Corp | Alkoxysilylpropylamines |
| GB863412A (en) * | 1956-04-17 | 1961-03-22 | Union Carbide Corp | Pigment dispersants |
| US3015569A (en) * | 1958-11-26 | 1962-01-02 | Interchem Corp | Treatment of pigments |
| US3029209A (en) * | 1959-08-12 | 1962-04-10 | Minerals & Chem Philipp Corp | Polyurethane foams filled with organophilic kaolin clay and method for making same |
| US3158519A (en) * | 1960-06-30 | 1964-11-24 | Owens Corning Fiberglass Corp | Continuous process for producing molding compounds |
| US3168389A (en) * | 1960-12-28 | 1965-02-02 | Pittsburgh Plate Glass Co | Silane forming size and glass fiber strands threated therewith for resin reinforcement |
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Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0232745A1 (en) * | 1986-02-11 | 1987-08-19 | Hewlett-Packard Company | Process for increasing the dispersibility of carbon black |
| EP0468140A2 (en) * | 1990-07-25 | 1992-01-29 | Degussa Aktiengesellschaft | With organosilicium-compound chemically modified carbon blacks, method for their preparation and their use |
| EP0468140A3 (en) * | 1990-07-25 | 1992-12-02 | Degussa Aktiengesellschaft | With organosilicium-compound chemically modified carbon blacks, method for their preparation and their use |
| US5356471A (en) * | 1992-08-17 | 1994-10-18 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Pigments of dark surface color |
| US5889090A (en) * | 1994-02-28 | 1999-03-30 | E. I. Dupont Denemours & Company | Processibility and lacing resistance when silanized pigments are incorporated in polymers |
| US5707437A (en) * | 1994-02-28 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Silanized titanium dioxide pigments resistant to discoloration when incorporated in polymers |
| US5959004A (en) | 1994-02-28 | 1999-09-28 | E. I. Du Pont De Nemours And Company | Processibility and lacing resistance when silanized pigments are incorporated in polymers |
| EP0816420A1 (en) * | 1996-06-24 | 1998-01-07 | The Goodyear Tire & Rubber Company | Aminosilane compounds in silica-filled rubber compositions |
| US6861115B2 (en) | 2001-05-18 | 2005-03-01 | Cabot Corporation | Ink jet recording medium comprising amine-treated silica |
| US20030003277A1 (en) * | 2001-05-18 | 2003-01-02 | Cabot Corporation | Ink jet recording medium comprising amine-treated silica |
| US6964992B2 (en) | 2001-05-18 | 2005-11-15 | Cabot Corporation | Ink jet recording medium comprising amine-treated silica |
| US20050123697A1 (en) * | 2001-05-18 | 2005-06-09 | Cabot Corporation | Ink jet recording medium comprising amine-treated silica |
| US6916368B2 (en) | 2002-02-20 | 2005-07-12 | Ppg Industries Ohio, Inc. | Curable film-forming composition exhibiting improved scratch resistance |
| US6790904B2 (en) | 2002-06-03 | 2004-09-14 | Ppg Industries Ohio, Inc. | Liquid coating of film-forming resin and particles chemically modified to lower surface tension |
| US20030229157A1 (en) * | 2002-06-03 | 2003-12-11 | Schneider John R. | Coating compositions with modified particles and methods of using the same |
| US20030224174A1 (en) * | 2002-06-03 | 2003-12-04 | Daniela White | Coating compositions with modified particles and methods of using the same |
| US7141618B2 (en) | 2002-06-03 | 2006-11-28 | Ppg Industries Ohio, Inc. | Coating compositions with modified particles and methods of using the same |
| US6808808B2 (en) | 2003-01-14 | 2004-10-26 | Freeman Gary M | Coating composition containing surface treated clay mixture, the surface treated clay mixture used therefor, and methods of their use |
| US20040138339A1 (en) * | 2003-01-14 | 2004-07-15 | Freeman Gary M. | Coating composition containing surface treated clay mixture, the surface treated clay mixture used therefor, and methods of their use |
| WO2006002085A1 (en) | 2004-06-15 | 2006-01-05 | W. R. Grace & Co.-Conn. | Chemically assisted milling of silicas |
| US20110094418A1 (en) * | 2004-06-15 | 2011-04-28 | David Monroe Chapman | Chemically assisted milling of silicas |
| US20060275597A1 (en) * | 2005-06-07 | 2006-12-07 | Thiele Erik S | Paper and paper laminates containing modified titanium dioxide |
| US8043715B2 (en) | 2005-06-07 | 2011-10-25 | E. I. Du Pont De Nemours And Company | Paper and paper laminates containing modified titanium dioxide |
| WO2013181021A1 (en) * | 2012-05-30 | 2013-12-05 | Kamin Llc | Methods and compositions for increasing ink clay loading in heatset ink formulations while maintaining ink gloss, and ink formulations produced therefrom |
| US10752749B2 (en) | 2012-05-30 | 2020-08-25 | Kamin Llc | Methods and compositions for increasing ink clay loading in heatset ink formulations while maintaining ink gloss, and ink formulations produced therefrom |
| US12018173B1 (en) | 2019-08-21 | 2024-06-25 | Swimc Llc | High physical durability coating compositions |
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