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USRE30699E - Polyurethanes containing amino organosilane modified clay - Google Patents

Polyurethanes containing amino organosilane modified clay Download PDF

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USRE30699E
USRE30699E US06/026,381 US2638179A USRE30699E US RE30699 E USRE30699 E US RE30699E US 2638179 A US2638179 A US 2638179A US RE30699 E USRE30699 E US RE30699E
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kaolin
modified
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kaolin clay
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Joseph Iannicelli
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JM Huber Corp
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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

Definitions

  • This invention relates to polyurethane polymer compositions containing finely divided amino organosilane modified kaolin clay fillers.
  • Polyurethane polymer compositions can be formed from a variety of polymers, l.e., thermosetting gums, thermoplastic polymers and liquid or casting polymers.
  • the preparations for various classes and grades of polyurethanes are well known in the art and need not be detailed here; however, the general reaction by which they are formed is by a chain extension process rather than the usual polymerization reaction. In this process a relatively short chain polymer, either a polyester or a polyether, is reacted with an organic diisocyanate to form long chain urethane polymer.
  • the process variations and polymerization variations caused thereby result in a multitude of compositions all broadly falling in one of the three classes mentioned.
  • the polyurethanes have several outstanding properties which make them desirable products, chief among them is abrasion resistance, good low temperature characteristics, good resistance to heat deterioration, ozone cracking, weathering, and oil or solvent swelling.
  • Thermosetting gum vulcanizates have a variety of uses in conveyor belts, roll covers, sandblast-hose tubes and other applications where good abrasion resistance is needed.
  • Thermoplastic resins can be processed on standard extrusion, injection molding, and transfer molding equipment. These resins are useful in small parts such as mallet heads, sprocket gears, adhesive coatings and unsupported sheetings such as fuel tanks, tarpaulins and chute liners.
  • Liquid polyurethane valcanizates exhibit good abrasion resistance, non-marking and a wide range of hardnesses. These products have use in large rolls for the steel industry, fork lift truck wheels, ladies toplifts, ball-joint seals, automotive seals, potting compounds, conveyor belts, V-belts, and tank linings.
  • kaolin clay modified with saturated amino organosilanes are reinforcing fillers for polyurethane polymers and impart improved properties to them. Particularly, modulus and tear resistance are improved with little, if any, degradation of other important properties.
  • the kaoline clays which are suitable as substrates for the modifier are refined clays of the rubber and paper grades.
  • the modified kaolin clays 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 specific modifier used and the intended polymer to be reinforced. Generally from 1% to 3% by weight of the modifier is sufficient for most purposes.
  • a particularly useful process for modifying the kaolin clay involves spray drying kaolin slurries having one or more of the amino organosilanes dispersed therein.
  • the spray drying process effects a uniform distribution of the modifier on the kaolin.
  • Another satisfactory method of modifying the kaolin involves dissolving the desired amount of amino organosilane in a suitable solvent, adding the kaolin and heating until the reaction is complete.
  • 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 lower 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, alkylene containing secondary amino nitrogen, alkylene containing tertiary amino nitrogen, arylene, arylene containing secondary amino nitrogen, arylene containing tertiary amino nitrogen, alkylarylene, alkylarylene containing secondary amino nitrogen, alkylarylene containing tertiary amino nitrogen, alkylarylene, alkylarylene containing secondary amino nitrogen, alkylarylene
  • amino organosilanes are disclosed along with methods for their preparation in U.S. Patents Nos. 2,832,754, 2,930,809, 3,007,957, and 3,020,302.
  • Commercially available amino organo silanes useful in the practice of this invention include "A-1100,” a gamma-aminopropyltriethoxy silane (GAPTS), and "Y-2967,” an amino organosilane which is a modified gamma-aminopropyltriethoxy silane, sold by Union Carbide Corporation, New York, N.Y., "Z-6020,” a diamino functional silane, sold by Dow Corning Corporation, Midland, Michigan.
  • polyurethane polymers suitable for use in this invention are "Vibrathane 5003,” a thermosetting gum which is cross-linked, produced by Naugatuck Chemical Division of U.S. Rubber Company; “Elastothane 455,” a thermosetting gum which is cross-linked, produced by Thiokol; “Genthane S,” a cross-linked thermosetting gum produced by General Chemical; “Estane,” a thermoplastic resin produced by B. F.
  • the gums were mill-mixed or Banbury-mixed and the thermoplastic resins were mill-mixed and injection molded.
  • 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 The data tabulated in Table I indicates the results when 1%, 2% and 3% by weight of GAPTS modified kaolin clay and 1% by weight Silicone Z-6020 modified kaolin clay is the filler.
  • the resin was molded at 390°-410° F. and post cured at 110° C. for 24 hrs. The results are tabulated in Table II.
  • the resin was molded at 390°-410° F. and was not post cured. The results are shown in Table III.
  • the polymer batch was treated as in Example IV. The results are shown in Table V.
  • the examples and data indicate that when the modified kaolin clays useful in this invention are used as fillers in thermosetting gum polyurethanes increases in modulus, hardness and abrasion resistance occur. The remaining properties of the polymer remain within acceptable levels. When these fillers are used to reinforce thermoplastic resins, increases in modulus, tear resistance, and abrasion resistance occur while the remaining polymer properties remain within acceptable levels. When these modified kaolin clay fillers are used to reinforce liquid polymers, increases in modulus, tensile strength, hardness, and tear resistance occur while the remaining properties of the polyurethane remain within acceptable levels. In all the polymers tested the general level of performance of the modified kaolins was superior to the unmodified kaolins.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The instant disclosure is directed to the polyurethane polymer compositions which are filled with a kaolin clay which has been modified with from 1% to 3% of an amino organosilane. The modulus and tear resistance of the polymers is improved without degradation of the remaining properties.

Description

This invention relates to polyurethane polymer compositions containing finely divided amino organosilane modified kaolin clay fillers.
The present application is a continuation-in-part of applicant's copending application Ser. No. 269,695, filed Apr. 1, 1963, now Patent No. 3,290,165, entitled, "Surface Modified Pigments," which in turn is a continuation-in-part of applicant's application Ser. No. 189,321, filed Apr. 23, 1962, entitled, "Surface Modified Pigments," now abandoned.
Polyurethane polymer compositions can be formed from a variety of polymers, l.e., thermosetting gums, thermoplastic polymers and liquid or casting polymers. The preparations for various classes and grades of polyurethanes are well known in the art and need not be detailed here; however, the general reaction by which they are formed is by a chain extension process rather than the usual polymerization reaction. In this process a relatively short chain polymer, either a polyester or a polyether, is reacted with an organic diisocyanate to form long chain urethane polymer. The process variations and polymerization variations caused thereby result in a multitude of compositions all broadly falling in one of the three classes mentioned.
The polyurethanes have several outstanding properties which make them desirable products, chief among them is abrasion resistance, good low temperature characteristics, good resistance to heat deterioration, ozone cracking, weathering, and oil or solvent swelling.
Thermosetting gum vulcanizates have a variety of uses in conveyor belts, roll covers, sandblast-hose tubes and other applications where good abrasion resistance is needed.
Thermoplastic resins can be processed on standard extrusion, injection molding, and transfer molding equipment. These resins are useful in small parts such as mallet heads, sprocket gears, adhesive coatings and unsupported sheetings such as fuel tanks, tarpaulins and chute liners.
Liquid polyurethane valcanizates exhibit good abrasion resistance, non-marking and a wide range of hardnesses. These products have use in large rolls for the steel industry, fork lift truck wheels, ladies toplifts, ball-joint seals, automotive seals, potting compounds, conveyor belts, V-belts, and tank linings.
Despite the fact that the polyurethanes have outstanding properties and are suitable for a large variety of uses, industry is constantly attempting to improve them by various means. Properties which are desirable to improve are modulus, tear resistance, hardness and abrasion resistance. In many cases reinforcing fillers have been tried but on the whole, while some improvements resulted, the degradation of other properties resulted and a completely satisfactory filler has not been found.
It is an object of this invention to provide solid polyprethane vulcanizates and thermoplastic resin compositions containing reinforcing fillers of modified kaolin clays.
Other objects and advantages will be apparent from the following specification.
I have discovered that kaolin clay modified with saturated amino organosilanes are reinforcing fillers for polyurethane polymers and impart improved properties to them. Particularly, modulus and tear resistance are improved with little, if any, degradation of other important properties.
The kaoline clays which are suitable as substrates for the modifier are refined clays of the rubber and paper grades.
The modified kaolin clays 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 specific modifier used and the intended polymer to be reinforced. Generally from 1% to 3% by weight of the modifier is sufficient for most purposes.
A particularly useful process for modifying the kaolin clay involves spray drying kaolin slurries having one or more of the amino organosilanes dispersed therein. The spray drying process effects a uniform distribution of the modifier on the kaolin. Another satisfactory method of modifying the kaolin involves dissolving the desired amount of amino organosilane in a suitable solvent, adding the kaolin and heating until the reaction is complete.
The compounds used to modify the kaolin clays 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 lower 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, alkylene containing secondary amino nitrogen, alkylene containing tertiary amino nitrogen, arylene, arylene containing secondary amino nitrogen, arylene containing tertiary amino nitrogen, alkylarylene, alkylarylene containing secondary amino nitrogen, alkylarylene containing tertiary amino nitrogen, arylalkylene, arylalkylene containing secondary amino nitrogen, arylalkylene containing tertiary amino nitrogen, cycloalkylene, cycloalkylene containing secondary amino nitrogen and cycloalkylene containing tertiary amino nitrogen. Some of these amino organosilanes are disclosed along with methods for their preparation in U.S. Patents Nos. 2,832,754, 2,930,809, 3,007,957, and 3,020,302. Commercially available amino organo silanes useful in the practice of this invention include "A-1100," a gamma-aminopropyltriethoxy silane (GAPTS), and "Y-2967," an amino organosilane which is a modified gamma-aminopropyltriethoxy silane, sold by Union Carbide Corporation, New York, N.Y., "Z-6020," a diamino functional silane, sold by Dow Corning Corporation, Midland, Michigan.
Representative commercially available polyurethane polymers suitable for use in this invention are "Vibrathane 5003," a thermosetting gum which is cross-linked, produced by Naugatuck Chemical Division of U.S. Rubber Company; "Elastothane 455," a thermosetting gum which is cross-linked, produced by Thiokol; "Genthane S," a cross-linked thermosetting gum produced by General Chemical; "Estane," a thermoplastic resin produced by B. F. Goodrich Chemical; "Texin," a thermoplastic resin produced by Mobay; "Multrathane," a liquid polymer produced by Mobay; "Cyanoprene 4590," a liquid polymer produced by American Cyanamid; "Adiprene L," produced by Du Pont; "Vibrathane 6000," produced by Naugatuck; and "Neothane," produced by Goodyear.
In the following formulations the gums were mill-mixed or Banbury-mixed and the thermoplastic resins were mill-mixed and injection molded.
The following formulations illustrate this invention.
Example I 
______________________________________                                    
                    Parts                                                 
______________________________________                                    
Vibrathane 5003       100                                                 
Stearic acid          0.25                                                
Dicup 40C (polymerizing agent)                                            
                      5                                                   
Filler (modified clay)                                                    
                      60                                                  
______________________________________
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.
The data tabulated in Table I indicates the results when 1%, 2% and 3% by weight of GAPTS modified kaolin clay and 1% by weight Silicone Z-6020 modified kaolin clay is the filler.
                                  TABLE I                                 
__________________________________________________________________________
                          1%    2%    3%    1%                            
                          GAPTS GAPTS GAPTS Z-6020                        
                 Control                                                  
                      Kaolin                                              
                          on Kaolin                                       
                                on Kaolin                                 
                                      on Kaolin                           
                                            on Kaolin                     
__________________________________________________________________________
Parts Filler/100 parts Polymer                                            
                 None 60  60    60    60    60                            
Tensile, p.s.i.  3,500                                                    
                      (.sup.1)                                            
                          3,920 3,600 3,840 3,270                         
Stress 300%, p.s.i.                                                       
                 1,040                                                    
                      (.sup.1)                                            
                          2,600 3,390 --    2,520                         
Elongation, percent                                                       
                 440  (.sup.1)                                            
                          470   350   265   365                           
Shore A Hardness 58   --  74    74    74    73                            
NBS Abrasion, percent of Standard                                         
                 100  --  89    134   157   193                           
Minutes Cured at 305° F.                                           
                 30   30  30    30    30    60                            
__________________________________________________________________________
 .sup.1 No cure.
Example II 
______________________________________                                    
              Parts                                                       
______________________________________                                    
       Texin 480A                                                         
                100                                                       
       Modified clay                                                      
                20                                                        
______________________________________
The resin was molded at 390°-410° F. and post cured at 110° C. for 24 hrs. The results are tabulated in Table II.
              TABLE II                                                    
______________________________________                                    
                               1%                                         
                  Con-  Kao-   GAPTS                                      
                  trol  lin    on Kaolin                                  
______________________________________                                    
Parts Filler/100 parts Polymer                                            
                    None    20     20                                     
Stress 300%, p.s.i. 1,720   2,170  2,430                                  
Tensile, p.s.i.     5,700   2,540  2,620                                  
Elongation, percent 640     510    400                                    
Shore A Hardness    75      78     78                                     
NBS Abrasion, percent of Standard                                         
                    100     77     92.5                                   
______________________________________
Example III 
______________________________________                                    
               Parts                                                      
______________________________________                                    
       Texin 480A                                                         
                100                                                       
       Modified clay                                                      
                 20                                                       
______________________________________
The resin was molded at 390°-410° F. and was not post cured. The results are shown in Table III.
              TABLE III                                                   
______________________________________                                    
                      0.25%    0.5%   1%                                  
                      GAPTS    GAPTS  GAPTS                               
         Con-  Kao-   on       on     on                                  
         trol  lin    Kaolin   Kaolin Kaolin                              
______________________________________                                    
Parts Filler/100                                                          
           0       20     20     20     20                                
parts Polymer                                                             
Stress 300%, p.s.i.                                                       
           1,090   1,680  1,725  1,735  1,720                             
Tensile, p.s.i.                                                           
           4,380   4,470  3,340  4,250  4,400                             
Elongation,                                                               
           610     640    560    655    595                               
percent                                                                   
Shore A Hardness                                                          
           85      88     88     88     88                                
______________________________________
Example IV 
______________________________________                                    
              Parts                                                       
______________________________________                                    
Estane 5701     100                                                       
Barium stearate  3                                                        
Modified clay   25 or 50                                                  
______________________________________
The resin was molded 5' at 350° F. held in the mold under pressure until the temperature dropped below 200° F. The results are tabulated in Table IV.
              TABLE IV                                                    
______________________________________                                    
               Con-            Kaolin plus                                
               trol  Kaolin    1% Z 6020                                  
______________________________________                                    
Parts Filler/100 parts Polymer                                            
                 0       25     50   25   50                              
300% Modulus, p.s.i.                                                      
                 1,220   1,580  1,640                                     
                                     2,840                                
                                          3,300                           
ASTM Test "Die" C, lbs./in                                                
                 410     500    300  560  580                             
NBS Abrasion Index, percent                                               
                 492     521    720  1,285                                
                                          16.72                           
NBS Abrasion Shore A                                                      
                 82      90     92   90   92                              
______________________________________
Example V 
______________________________________                                    
             Parts                                                        
______________________________________                                    
Estane 5701    100                                                        
Barium stearate                                                           
                3                                                         
Filler         25, 50 or 100                                              
______________________________________
The polymer batch was treated as in Example IV. The results are shown in Table V.
                                  TABLE V                                 
__________________________________________________________________________
                 Kaolin                                                   
                      Kaolin                                              
                           Kaolin                                         
                                Kaolin  Kaolin                            
                                             Kaolin   Kaolin              
                                                          Kaolin          
           Con-                                                           
              Kao-                                                        
                 plus 2%                                                  
                      plus 2%                                             
                           plus 3%                                        
                                plus 1%                                   
                                     Kao-                                 
                                        plus 2%                           
                                             plus 1%                      
                                                  Kao-                    
                                                     plus                 
                                                          plus 1%         
           trol                                                           
              lin                                                         
                 GAPTS                                                    
                      GAPTS                                               
                           GAPTS                                          
                                Z 6020                                    
                                     lin                                  
                                        GAPTS                             
                                             Z 6020                       
                                                  lin                     
                                                     GAPTS                
                                                          Z               
__________________________________________________________________________
                                                          6020            
Parts Filler/100 parts                                                    
           0  25 25   25   25   25   50 50   50   100                     
                                                     100  100             
Polymer                                                                   
200% Modulus, p.s.i.                                                      
           860                                                            
              -- --   --   --   --   1,700                                
                                        3,500                             
                                             3,740                        
                                                  -- --   --              
300% Modulus, p.s.i.                                                      
           1,440                                                          
              1,780                                                       
                 2,940                                                    
                      3,260                                               
                           3,040                                          
                                3,000                                     
                                     -- --   --   -- --   --              
Shore A Hardness                                                          
           88 93 91   92   91   91   94 94   95   97 97   97              
NBS Abrasion, Index                                                       
           460                                                            
              641                                                         
                 827  703  641  746  624                                  
                                        936  568  334                     
                                                     553  575             
__________________________________________________________________________
Example VI 
______________________________________                                    
              Parts                                                       
______________________________________                                    
Estane 5701     100                                                       
Barium Stearate  3                                                        
Pigment         25 or 50                                                  
______________________________________
The recipe was treated the same as in Example IV. The results are shown in Table VI.
              TABLE VI                                                    
______________________________________                                    
                      Kaolin       Kaolin                                 
                      plus         plus                                   
          Con- Kao-   2%           1%                                     
          trol lin    GAPTS        Z-6020                                 
______________________________________                                    
Parts Filler/100                                                          
            None   25     50   25   50   25   50                          
parts Polymer                                                             
300% Modulus,                                                             
            1,220  1,580  1,640                                           
                               2,880                                      
                                    3,600                                 
                                         2,840                            
                                              3,300                       
p.s.i.                                                                    
ASTM Tear "Die                                                            
            410    500    500  550  480  560  580                         
C," lbs./in                                                               
NBS Abrasion,                                                             
            492    521    720  1,015                                      
                                    1,411                                 
                                         1,285                            
                                              1,672                       
Index percent                                                             
NBS Abrasion,                                                             
            82     90     92   90   91   90   92                          
Shore A Hardness                                                          
______________________________________
Example VII 
______________________________________                                    
             Parts                                                        
______________________________________                                    
Estane 5701    100                                                        
Barium Stearate                                                           
                3                                                         
Filler         10, 20, 60 or 100                                          
______________________________________
The recipe was treated as in Example IV. The results are shown in Table VII.
                                  TABLE VII                               
__________________________________________________________________________
                Con-                                                      
                    Kaolin Plus                                           
                           Kao-                                           
                               Kaolin Plus                                
                                      Kao- -trol 1% Z-6020 lin 1%         
                                      Z-6020 lin                          
__________________________________________________________________________
Parts Filler/100 parts Polymer                                            
                0   10 20  20  60 100 100                                 
300% Modulus, p.s.i.                                                      
                1,280                                                     
                    2,040                                                 
                       2,740                                              
                           1,640                                          
                               3,420                                      
                                  --  2,040                               
ASTM Tear "Die C," lbs./in                                                
                420 500                                                   
                       600 530 540                                        
                                  406 510                                 
NBS Abrasion, Index percent                                               
                570 867                                                   
                       1,095                                              
                           957 1,722                                      
                                  1,465                                   
                                      717                                 
NBS Abrasion, Shore A                                                     
                84  85 89  89  94 95  95                                  
__________________________________________________________________________
Example VIII 
______________________________________                                    
                    Parts                                                 
______________________________________                                    
Adiprene L-100        100                                                 
Methylene-bis-orthochloraniline                                           
                      11                                                  
Pigment               20                                                  
______________________________________
The mixture was cured for 180 minutes at 212° F. The results are shown in Table VIII.
              TABLE VIII                                                  
______________________________________                                    
                                Kaolin                                    
                                Plus 1%                                   
                Control                                                   
                       Kaolin   Z-6020                                    
______________________________________                                    
Parts Filler/100 parts Polymer                                            
                  0        20       20                                    
300% Modulus, p.s.i.                                                      
                  1,530    --       1,940                                 
Tensile, p.s.i.   2,570    1,310    2,710 -Elongation, Percent 495 285 480
                                    5                                     
Shore A Hardness  87       88       90                                    
ASTM Tear "Die C," lbs./in                                                
                  450      408      505                                   
NBS Abrasion, Index Percent                                               
                  224      126      194                                   
______________________________________
The examples and data indicate that when the modified kaolin clays useful in this invention are used as fillers in thermosetting gum polyurethanes increases in modulus, hardness and abrasion resistance occur. The remaining properties of the polymer remain within acceptable levels. When these fillers are used to reinforce thermoplastic resins, increases in modulus, tear resistance, and abrasion resistance occur while the remaining polymer properties remain within acceptable levels. When these modified kaolin clay fillers are used to reinforce liquid polymers, increases in modulus, tensile strength, hardness, and tear resistance occur while the remaining properties of the polyurethane remain within acceptable levels. In all the polymers tested the general level of performance of the modified kaolins was superior to the unmodified kaolins.
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 (3)

I claim:
1. A polyurethane polymer composition containing as a filler, modified kaolin clay, said kaolin clay .Iadd.having been .Iaddend.modified .Iadd.by treatment .Iaddend.with from 1% to 3% by weight with an aminoorganosilane of the formula ##STR2## wherein R1 is selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl, and alkaryl, 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, and X is selected from the group consisting of alkylene, arylene, alkylarylene, arylalkylene, cycloalkylene, cycloalkylene containing secondary amino nitrogen and cycloalkylene containing tertiary amino nitrogen.Iadd., the modification of said kaolin clay being carried out by spray drying kaolin slurries having one or more of said amonoorganosilanes dispersed therein, said spray drying effecting a uniform distribution of said aminoorganosilane on the kaolin. .Iaddend.
2. The composition of claim 1 wherein the filler is kaolin clay modified with from 1% to 3% by weight of a diamino functional silane.
3. The composition of claim 1 wherein the filler is kaolin clay modified with 1% to 3% by weight of gamma-aminopropyltriethoxysilane. .Iadd. 4. A polyurethane polymer composition containing as a filler, modified kaolin clay, said kaolin clay having been modified by treatment with from 1% to 3% by weight of an aminoorganosilane 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, and wherein R' can represent the same or different groups. .Iaddend.
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US269695A Continuation-In-Part US3290165A (en) 1963-04-01 1963-04-01 Surface modified pigments
US480090A Reissue US3390120A (en) 1965-08-16 1965-08-16 Polyurethanes containing amino organosilane modified clay

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5693696A (en) * 1993-12-14 1997-12-02 Mcp Industries, Inc. Modified polyurethane including filler and method of manufacture thereof
US6420456B1 (en) * 1997-05-22 2002-07-16 Bayer Inc. Process for hydrophobicizing particles, and their use as fillers in polymer masterbatches
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
US9260613B2 (en) 2009-07-14 2016-02-16 Imerys Minerals Limited Clear coating compositions comprising particulate inorganic mineral

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Publication number Priority date Publication date Assignee Title
US5693696A (en) * 1993-12-14 1997-12-02 Mcp Industries, Inc. Modified polyurethane including filler and method of manufacture thereof
US6420456B1 (en) * 1997-05-22 2002-07-16 Bayer Inc. Process for hydrophobicizing particles, and their use as fillers in polymer masterbatches
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
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
US9260613B2 (en) 2009-07-14 2016-02-16 Imerys Minerals Limited Clear coating compositions comprising particulate inorganic mineral

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