USRE30450E - Surface modified pigments - Google Patents

Surface modified pigments Download PDF

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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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modified
weight
pigment
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Joseph Iannicelli
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JM Huber Corp
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

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.
Example 1
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.
Example 2
"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.
Example 3
"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.
Example 4
"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 5
Example 4 was repeated using "Y-2967" instead of "Z-6020."
Example 6
Example 4 was repeated using "A-1100" instead of "Z-6020."
Example 7
"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 8
Example 7 was repeated using "Z-6020" in place of gamma aminopropyltriethoxysilane.
Example 9
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)

I claim:
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.
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Cited By (15)

* Cited by examiner, † Cited by third party
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
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
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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US3150109A (en) * 1961-08-01 1964-09-22 Minerals & Chem Philipp Corp Filled polyurethane foams and method for making same
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US3015569A (en) * 1958-11-26 1962-01-02 Interchem Corp Treatment of pigments
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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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Cited By (25)

* Cited by examiner, † Cited by third party
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
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
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
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
US7141618B2 (en) 2002-06-03 2006-11-28 Ppg Industries Ohio, Inc. Coating compositions with modified particles and methods of using the same
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
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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