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Publication numberUSRE30699 E
Publication typeGrant
Application numberUS 06/026,381
Publication dateAug 4, 1981
Filing dateApr 2, 1979
Priority dateApr 2, 1979
Publication number026381, 06026381, US RE30699 E, US RE30699E, US-E-RE30699, USRE30699 E, USRE30699E
InventorsJoseph Iannicelli
Original AssigneeJ. M. Huber Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Coupling; upgrading tear strength and modulus of thermosetting molding materials
US RE30699 E
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.
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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:
H2 N--R--Si--(OR')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.
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       100Stearic acid          0.25Dicup 40C (polymerizing agent)                 5Filler (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    60Tensile, p.s.i.  3,500                 (1)                     3,920 3,600 3,840 3,270Stress 300%, p.s.i.            1,040                 (1)                     2,600 3,390 --    2,520Elongation, percent            440  (1)                     470   350   265   365Shore A Hardness 58   --  74    74    74    73NBS Abrasion, percent of Standard            100  --  89    134   157   193Minutes Cured at 305 F.            30   30  30    30    30    60__________________________________________________________________________ 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     20Stress 300%, p.s.i. 1,720   2,170  2,430Tensile, p.s.i.     5,700   2,540  2,620Elongation, percent 640     510    400Shore A Hardness    75      78     78NBS 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     20parts PolymerStress 300%, p.s.i.      1,090   1,680  1,725  1,735  1,720Tensile, p.s.i.      4,380   4,470  3,340  4,250  4,400Elongation,      610     640    560    655    595percentShore A Hardness      85      88     88     88     88______________________________________
Example IV

______________________________________         Parts______________________________________Estane 5701     100Barium stearate  3Modified 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   50300% Modulus, p.s.i.            1,220   1,580  1,640                                2,840                                     3,300ASTM Test "Die" C, lbs./in            410     500    300  560  580NBS Abrasion Index, percent            492     521    720  1,285                                     16.72NBS Abrasion Shore A            82      90     92   90   92______________________________________
Example V

______________________________________        Parts______________________________________Estane 5701    100Barium stearate           3Filler         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__________________________________________________________________________                                                     6020Parts Filler/100 parts      0  25 25   25   25   25   50 50   50   100                                                100  100Polymer200% 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   97NBS Abrasion, Index      460         641            827  703  641  746  624                                   936  568  334                                                553  575__________________________________________________________________________
Example VI

______________________________________         Parts______________________________________Estane 5701     100Barium Stearate  3Pigment         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   50parts Polymer300% Modulus,       1,220  1,580  1,640                          2,880                               3,600                                    2,840                                         3,300p.s.i.ASTM Tear "Die       410    500    500  550  480  560  580C," lbs./inNBS Abrasion,       492    521    720  1,015                               1,411                                    1,285                                         1,672Index percentNBS Abrasion,       82     90     92   90   91   90   92Shore A Hardness______________________________________
Example VII

______________________________________        Parts______________________________________Estane 5701    100Barium Stearate           3Filler         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 100300% Modulus, p.s.i.           1,280               2,040                  2,740                      1,640                          3,420                             --  2,040ASTM Tear "Die C," lbs./in           420 500                  600 530 540                             406 510NBS Abrasion, Index percent           570 867                  1,095                      957 1,722                             1,465                                 717NBS Abrasion, Shore A           84  85 89  89  94 95  95__________________________________________________________________________
Example VIII

______________________________________               Parts______________________________________Adiprene L-100        100Methylene-bis-orthochloraniline                 11Pigment               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       20300% Modulus, p.s.i.             1,530    --       1,940Tensile, p.s.i.   2,570    1,310    2,710 -Elongation, Percent 495 285 480                               5Shore A Hardness  87       88       90ASTM Tear "Die C," lbs./in             450      408      505NBS 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.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2742378 *Aug 2, 1952Apr 17, 1956Gen Tire & Rubber CoFillers having vinyl siloxane groups bonded to the surface thereof and copolymers thereof with ethylenically unsaturated polymerizable monomers
US2832754 *Jan 21, 1955Apr 29, 1958Union Carbide CorpAlkoxysilylpropylamines
US3015569 *Nov 26, 1958Jan 2, 1962Interchem CorpTreatment of pigments
US3029209 *Aug 12, 1959Apr 10, 1962Minerals & Chem Philipp CorpPolyurethane foams filled with organophilic kaolin clay and method for making same
US3150109 *Aug 1, 1961Sep 22, 1964Minerals & Chem Philipp CorpFilled polyurethane foams and method for making same
US3158519 *Jun 30, 1960Nov 24, 1964Owens Corning Fiberglass CorpContinuous process for producing molding compounds
US3168389 *Dec 28, 1960Feb 2, 1965Pittsburgh Plate Glass CoSilane forming size and glass fiber strands threated therewith for resin reinforcement
US3227675 *May 1, 1963Jan 4, 1966Huber Corp J MSilane-treated clay reinforced resin compositions
US3328339 *Aug 28, 1963Jun 27, 1967Monsanto CoReinforced plastics containing base treated, calcined particulate fillers and organosilane coupling agents
US3350345 *Dec 21, 1962Oct 31, 1967Exxon Research Engineering CoBonded rubber-siliceous materials and process of producing same
US3364050 *Jun 22, 1964Jan 16, 1968Tetra Pak AbMethod of treating a cut edge and its adjacent portion in a porous sheet material
US3388144 *Jul 15, 1965Jun 11, 1968Dow CorningPolymercaptoorgano and polyhydroxyorgano silanes and siloxanes
US3392182 *Feb 12, 1964Jul 9, 1968Goldschmidt Ag ThNovel organosilicon compounds and process for their preparation
US3419517 *Jun 24, 1966Dec 31, 1968Monsanto CoReinforced polyamides and process of preparation thereof
Non-Patent Citations
Reference
1 *Jellinek et al., Silane Finishes for Fibrous Glass, 1957, Presentation before the Society of Plastic Industries, Union Carbide Corp.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5693696 *Jan 16, 1996Dec 2, 1997Mcp Industries, Inc.Modified polyurethane including filler and method of manufacture thereof
US6420456 *May 21, 1998Jul 16, 2002Bayer Inc.Process for hydrophobicizing particles, and their use as fillers in polymer masterbatches
US6808808Jan 14, 2003Oct 26, 2004Freeman Gary MCoating composition containing surface treated clay mixture, the surface treated clay mixture used therefor, and methods of their use
Classifications
U.S. Classification524/262, 524/445
International ClassificationC08K9/06
Cooperative ClassificationC08K9/06
European ClassificationC08K9/06