CA1260913A - Coupling agents for thermoplastics and inorganic reinforcing agents - Google Patents

Abstract

NEW COUPLING AGENTS FOR THERMOPLASTICS
AND INORGANIC REINFORCING AGENTS

Abstract of the Invention Disclosed are novel coupling agents for thermoplastics and inorganic reinforcing agents comprising aminosilanes, azidosilanes, and optionally, tetraalkylsilicates.

Description

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0398p This invention relates to coupling agents containing azidosilanes to improve the adhesion of thermoplastic poly-mers to inorganic reinforcing materials and fillers.
Azidosilanes are known coupling agents for promoting the adhesion of polymers to reinforcing materials and fillers, such as various siliceous materials or calcium carbonate~
For instance, U.S. Patent Nol 3,585,103 discloses azido-silanes (and also polyfunctional sulfonyl azides) as coupling agents for use in adhering polymers to reinforcing materials such as glass. Preparation of such azidosilane compounds is also disclosed in U.S. Pat. No . 3,706,592.
The need for increased coupling ability has led to com-binations of compounds containing azide yroups with other agents. U.S. Patent 3,585,103 discloses, for instance, a combination of aminopropyltrimethoxysilane or other silanes with a polyfunctional sulfonyl azide haviny the formula (N3C0)y-R-~sO2N3)z wherein y + z is at least 2, as a coupling agent for polymers and reinforcing agents. In this combination, there is an excess o~ azide groups over amine groups by a ratio of 2 to 1. It is believed that when the aminosilane and poly-functional sulfonylazide are combined, the reaction of the amine group of the aminosilane with the polyfunctional azide .~ ~ ...

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displaces onLy half of the azide groups present. The remain-ing azide groups can account for the coupling capacity observed in the patent.
U. S. Patent 4,447,495, discloses a combination of azido-silane coupliny agents and tetraalkylsilicates as diluents forthe azidosilanes.
It has never been suggested that the coupling ability of aziodosilanes could be improved by combining them with amino-silanes, because the azidosilane would be expected to react 1~ with the amino group of the aminosilane, resulting in displace-ment of the azide group to produce a substituted sulfonamide that would lack effective coupling capacity.
According to the invention, a method for making a cou-pling agent for treating reinforcing materials and fillers to promote the adhesion of polymers to them, and containing an azidosilane, is characterized in that an aminosilane is added to the azidosilane before or after a reinforcing material or filler is treated with either of the silanes, and if the amino-silane is added to the azidosilane before the reinforcing mate-~O rial or filler is treated, it is treated before the silaneshave been in contact for more then 15 minutes.
Preferably, in the method for making a coupling agent ac-cording to the invention, a tetraalkylsilicate is added to one of the silanes or to the mixture of silanes before the rein-~5 forcing material or filler is treated with the said silane ormixture.
Also according to the invention, a coupling agent con-taining an azidosilane is characterized in that the agent als contains an aminosilane that may react with the azidosilane and contains no more than the amount of a reaction product of the two silanes than would be produced by the said reaction in 15 minutes following the mixing of the silanes.
Preferably, the coupling agent according to the invention also contains a tetraalkylsilicate, which enhances the cou-pliny ability of the mixture of the silanes.
Preferably also, the azidosilane in the coupling agent according to the invention has the formula ( T)b (X)a-Si-[R-(Z)C~d where R is an organic radical; X is a radical selected from the group consisting of halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido, amine and amide radicals T is a radical 5 selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals a is an integer from 1 to 3 b is an integer from O -to 2 c is an integer from 1 to 10: d is an integer from 1 to 3 and a+b+d equals 4 and Z is a radical selected from the group consisting of 1I T fi -O-C-CN2,-OCN3,~nd -S02N3 where R' is a radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and COOR" radicals; where R" is a radical selected from the group consisting of alkyl, cycloalkyl and aryl radicals;
Preferably also, the aminosilane in the coupling agent according to the invention has the formula H2NRSi(R )3 where R is a lower alkyl radical, and R' is a radical select-ed from the group consisting of lower alkoxy and lower alkoxy-methyl radicals.
Also according to the invention, a process for producing a reinforced polymer comprising treating a filler with a cou-pling ayent, mixing the treated filler with a thermoplastic polymer and heating the mixture is characterized in that the coupling agent comprises an azidosilane and an aminosilane J~3~

that have not been in contact with each other more than 15 minutes.
Preferably, the filler or reinforcing agent is a siliceous material or calcium carbonate.
More preferably, the organic radical ~ in the preferred formula for the azidosilane in the coupling agent according to the invention will be selected from the group consisting of hydrocarbon, halo-substituted hydrocarbon, hydrocarbon-oxy-hydrocarbon, hydrocarbon-thio-hydrocarbon and hydrocarbon-sulfonyl-hydrocarbon divalent radicals.
In most preferred embodiments of this invention R will be a divalent organic radical selected from the group consisting of alkylene radicals such as the straight and branched Cl-C20 alkylene radicals which include, for instance, the methylene, ethylene, trimethylene, tetramethylene, penta-methylene, hexamethylene, octamethylene, decamethylene, dode-camethylene, octadecamethylene, etc. radicals; cycloalkylene radicals such as the C3-C20 cycloalkylene radicals which include, for instance, the cyclohexylene, cyclopentylene, cyclooctylene, cyclobutylene, etc. radicals; arylene radicals such as o-, m-,and p-phenylene, naphthylene, biphenylene, etc.
radicals; arylene-dialkylene radicals, such a o-, m-, and p-xylylene diethylene, o-, m-, and p-phenylene diethylene, etc. radicals; alkylene-diarylene radicals such as methylene bis(o-, m- and p-phenylene), ethylene bis(o-, m-, and p-phenylene), etc. radicals; cycloalkylene-dialkylene radicals such as, 1,2-, 1,3- and 1,4-cyclohexane-dimethylene, 1,2- and 1,3-cyclo-pentane dimethylene, etc. radicals; and the alkylene-oxy alkylene radicals, arylene-oxy-arylene radicals, alkarylene -oxyarylene radicals, alkarylene-oxy-alkarylene radicals, aralkylene-oxy-alkylene radicals, aralkylene-oxy-aralkylene radicals, etc. as well as the corresponding thio and sulfonyl radicals, specific examples of which include ethylene-oxy- ethylene, propylene-oxy-butylene, phenylene-oxy-phenylene, methylenephenylene-oxy-phenylenemethylene, phenylene-methylene-oxy-methylenephenylene, ethylene-thio-ethylene~ phenyl-thio-phenylene, phenylenemethylene-thio-methylenephenylene, butylene-sulfonyl-butylene, etc. radicals.
It will, of course, be obvious to those skilled in the art that R can contain other functionl groups, which are substan-tially inert to the reactions in which these compounds areused, such as esters, sulfonate esters, amides, sulfonarnides, urethanes, and the like, as described in the Tho~son U.S.
Patent No. 3,697,551.
Preferably, R' can be hydrogen, alkyl, cycloalkyl, aryl 1~ or -COOR" radicals. The most preferred alkyl, cycloalkyl and aryl radicals are methyl, ethyl, propyl, butyl, isobutyl, cyclohexyl, cycloheptyl, phenyl, tolyl, etc. The radical R"
can be alkyl, cycloalkyl, or aryl with the most preferred radicals being methyl, ethyl, propyl, bu~yl, isobutyl, cyclo-hexyl, cycloheptyl, phenyl, tolyl, etc. In general, X can behydroxy or any hydrolyzable radical. Typical hydrolyzable radicals are the halo radicals which include, for instance, the fluoro, chloro, bromo and iodo radicals; the alkoxy radi-cals including the Cl-C20 straight and branched chain alkoxy radicals such as methoxy, ethoxy, propoxy, butoxy, isobutoxy, octadecyloxy, etc.: the aryloxy radicals such as phenoxy, etc.; the organo oxycarbonyl radicals including the aliphatic oxycarbonyl radicals such as acetoxy, propionyloxy, stearoyloxy, etc.; the cycloaliphatic oxycarbonyl radicals such as cyclohexylcarbonyloxy, etc.; the aromatic oxycarbonyl radicals such as benzoyloxy, xlyloxy, etc.; the azido radical;
the amine radical: the substituted amine radicals such as ethylamine, diethylamine, propylamine, etc.; and the amide radicals such as formamide, acetamide, trifluoroacetamide, benzamide, etc. Generally, T will be a radical selected from the group consisting of alkyl, cyclo-alkyl, aryl, alkaryl, and aralkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, cyclo-heptyl, phenyl, tolyl, benzyl, xylyl, etc.
Typical nitrogen containing azidosilane compounds of this invention as described by the above formula are 3-(trimethoxy-silyl) propyl diazoacetate, 2-(methyldichlorosilyl) ethyl diazoacetate, p-(trimethoxysilyl) benzyl diazoacetate, 10-(3-trimethoxysilylpropy) carbamoyl decyl diazoacetate, 4-(tri-methoxysilyl) butyl-diazo propionate, 3-(ethyldimethoxysilyl) propyl-diazo-~henyl--acetate, 3-(trichloro-silyl) propyl-diazo-carbomethoxy-acetate, 2-(trimethoxysilyl) ethyl-diazo-carbo-phenoxy-acetate, 4-(ethoxydichlorosilyl) cyclohexyl diazoace-tate, 3-(trimethoxysilyl) propyl azido formate, 3-(methyldi-methoxysilyl) propyl azidoformate, 2-chloro-3[3-trimethoXy-silyl) propoxy] propyl azidoformate, 3-(triazidosiyly) propyl azidoformate, 2-(trimethoxysilyl) ethyl azidoformate, 3-(tri-acetoxysilyl) propyl azidoformate, 2-[3-(trimethoxysilyl) pro-poxy] ethyl azidoformate, 3-(methyldiacetosilyl) propyl azido-forma~e, 2-(ethyldipropionyloxysilyl) ethyl azidoformate, p-(trimethoxysilyl) phenyl azidoformate, 4-(diethoxychloro silyl) butyl azidoformate, 4-(ethyldimethoxysilyl) cyclohexyl azidoformate, 3-(phenyldichlorosilyl) propyl azidoformate, 4-(trisdimethylaminosilyl) butyl azidoformate, 5-(trimethoxy-silyl) amylsulfonyl azide, 4-(trimethoxysilyl) cyclohexylsul-fonyl azide, 2-methyl-4-(trichlorosilyl) butylsulfonyl azide, 3-chloro-6-(trimethoxysilyl) hexysulfonyl azide, 6-(trimethoxy-silyl) hexylsulfonyl azide, 2-(trichlorosilyl) ethylsulfonyl azide, 3-(dimethylaminodimethylsilyl) propylsulfonyl azide,

2-(triethoxysilyl) ethylsulfonyl azide, 3-(methyldimethoxy-silyl) propylsulfonyl azide, 3-(trimethoxysilyl) propylsulf-fonyl azide, 4-[diethoxy-(4-sulfonylazidobutyl)silyl) butylsulfonyl azide, p-(trimethoxysilyl) benzenesulfonyl azide, 2-(trimethoxysilyl) ethylbenzenesulfonyl azide, N-3-(triethoxysilyl) propyl-N'-3-azidosulfonylpropylurea, N-3-(triethoxysilyl) propyl-N'-m-azidosulfonylphenylurea, etc.
The azidosilane compounds used in this invention can be prepared by various well-known methods.
Many of the azidosilane compounds used in this invention are liquids, that is liquid at 20-25 C., and a~ atmospheric pressure. However, some are solids. They are characterized in that the diazo or azido portion readily reacts with a wide variety of polymers to effect linkage of the polymer to the ~ O~

azidosilane compound. l'hey are further characterized in that the silane portion of the azidosilane molecule adheres to fillers such as siliceous materials; thus, coupling between the polymer and the filler is achieved.
The above described azidosilane com~ounds readily con-dense to form dimers, trimers and even polymers when heated and/or in the presence of water and acidic or basic con-densation catalysts. secause of the ease with which they condense, it is apparent that many of the azidosilane com-pounds used in this invention (with the exception of those freshly prepared under anhydrous conditions) exist in admix-ture with at least a small amount of their condensation products. Therefore, it is to be understood that the terms "azidosilane" and "azidosilane compound," used in the specifi-cation and claims of this application, include not only thepure monomeric compounds but also mixtures of the monomers with at least a small amount of the condensation products of the monomers.
It may be desirable in some cases to use a condensa-~0 tion ~roduct of an azidosilane compound instead of the monomer. If this is desired, such condensation product can readily be prepared by heating one of the above described azidosilane compounds in the presence of a small amount of water and a conventional condensation catalyst, i.e., acetic ~5 acid, HCl, Hsr, Na~H, NH40H, or the like. A ty~ical dimer would have the general formula 0 - ~i-[R-~Z)c]d where T, R, Z, c and d are as defined above. A typical con~en-sation polymer would have the general formula X~ O ~ 5 j---X

~R-(7)c]d ~R-(Z)c~ n [R-(Z)C~d where X, T, R, ~, c and d are as defined above.
The aminosilane compounds used in this invention, as stated above, have the general formula H2NRSi(R')3 where R and ~' are defined as above.
Typical aminosilane compounds of this invention include, for example, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, l~ aminoethyltriethoxysilane, and aminopropyltrimethoxymethylsilane.
The tetraalkylsilicates that are optionally used in this invention are organosilicons disclosed in said U.S. Patent No.
4,447,4~5.
The fillers that can be coupled to polymers in accordance with this invention are mica, glass, talc, wollastonite, asbestos, sand, novaculite, clay, cement, stone, brick, and calcium carbonate.
The thermoplastic polymers that can be coupled to fillers in accordance with this invention are disclosed ln the said ~o 4,447,495 patent.
Amounts of the coupling agent according to this invention that are necessary to produce the desired coupling between filler and polymer can vary. Generally, the total amount of coupling agent will vary from about 0.1% to about 1.5% based on the weight of the filler used.
As to the relative amounts of the coupling agenk com-ponents, in an aminosilane/azidosilane coupling mixture, the amount of the aminosilane will ~ary from about 0.05% to about ~r ~1 0.95~, and the amount of the azidosilane will vary from about 0.05~ to about 0.95~. These ranges are based on the weight of the filler used. In a coupling mixture having an aminosilane, azidosilane, and tetraalkylsilicate, based on the weight of the filler used, the amount of the azidosilane will vary from about 0.05~ to about 0.95~, the amount of aminosilane will vary from about 0.05% to about 0.95~, and the amount of tetraalkylsilicate will vary from about 0.05~ to about 0.95~.
Preferably, approximately equal amounts of the two silanes are used, on a weight basis, and most preferably on a molar basis.
Once the coupling agent has been applied to the untreated filler, the treated filler is stable and can be stored at ambi-ent temperatures with no loss of coupling activity. However if the aminosilane and azidosilane are combined before being applied to the filler, they must be contacted with the filler within 15 minutes of being combined, or else coupliny ability will begin to deteriorate.
Methods for reacting the fillers, coupling agents, and polymers with one another will be well known to those skilled in the art. Generally, a filler is first treated with the coupling mixture, and the thus treated filler is then coupled with the polymer. Typically, a ~ulverized filler is treated with the coupling agent of this invention, which is dissolved in a solvent at room temperature, and the solvent then allowed to evaporate. Some reaction between the filler and the cou-pling agent is believed to occur after mixing at room tempera-ture because the coupling agent cannot be removed completely from the filler once the filler and coupling agent have been mixed. The reaction between the filler and the coupling agent is completed upon heating after the treated filler and the polymer are mixed. Typically, a pulverized polymer and a filler as treated above are reacted by tumble-blending for several hours at room temperature and heating under pressure to achieve a temperature between about 125C. and about 250C., depending on the specific azidosilane coupling agent employed. The ratio of polymer/treated filler can vary; the more filler used, the less expensive the final product.

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Typically, the ratio of polymer/treated filler will vary from about 1/20 to about 3/5O

Examples The following examples will more fully explain this inven-tion. These exam~les are illustrative only, and the inventionis not limited thereto. All parts are by weight unless indica-ted otherwise. Test results are the average of 5 determina-tions.
Preparation Method 100 parts of the filler are placed in a beaker and solu-tions of the test coupling agents in methylene chloride (about 0.5% solution) are applied with manual stirring. The thus treated fillers are transferred to flat aluminum pans and the solvent is allowed to evapoLate off. Where the polymer is treated, the same method is used. The treated fillers are mixed with the polymer at weight percents as indicated in the tables and tumble-blended in a jar. Test specimens are compression-molded. Molding temperature is at 240C., at contact pressure for 3 minutes, at 5 tons for 4 minutes, and at 10 tons for 3 minutes. The specimen is then cooled while still under pressure.

Examples 1-57 Sample preparations of polymers coupled to fillers usiny the coupling ayents of this invention are prepared as shown above. The preparations are then tested for flex modulus and flex strength according to American Society for Testing &
Materials (ASTM) D790 and for heat deflection temperature according to ASTM ~648 (heat deflection temperature measured for Examples 1-35 only). The test results and formulations for Examples 1-35 are compiled in Tables I - VII.
In Table I, the superior results obtained using the cou-pling agent of this invention is illustrated in Examples 5 and 6 as opposed to prior art controls, illustrated by Examples 2-4, and an untreated control, illustrated by Example 1.
Table II further illustrates this superiority by comparing this invention, as illustrated in Examples 11-14, with prior art controls, as illustrated in Examples 8-10, and an un-treated control, as illustrated by Example 7.
Table III illustrates: (a) how the enhanced coupling achieved by using this invention, as shown in Example 16, and compared with an untreated control, as shown in Example 15, is lost when the coupling agent components are combined 16 hours before treatment of the filler, as shown in Example 17; and (b) how the order of treating the filler with the coupling agent components, as shown in Examples 18-25, has no effect on the coupling achieved compared to the untreated control in Example 15.
To show the storaye capability of this invention, a filler treated as in Example 6 is stored for 5 months and then reacted with a polymer as in Example 6. The flex modulus (x 1,000) measures 1,210 p.s.i., the flex strength measures 8,440 p.s.i., and the 2 heat deflection temperature deter-minations are 134 and 137 C @ 264 p.s.i.
Tables IV and V show that neither N-substituted amino-silanes nor simple amines can be used in the coupling agent ofthis invention. In Table IV it is shown that when an N-sub-stituted aminosilane is used instead of the aminosilanes of this invention, see Example 28, only slight coupling is achieved when compared with an untreated control, as in exam~le 27, and the coupling agent of this invention, as in Example 29. Table V shows that when simple amines are used instead of the aminosllanes of this invention, see Examples 32-35, slightly less coupling is observed than when a prior art coupling agent, as illustrated by Example 31, is used, when compared with an untreated control, as illustrated by Example 30.
Table VI further illustrates the results obtained using the coupling agent of this invention, as shown in Examples 41-45, as compared with prior art coupling agents, as shown in Examples 37-40, and an untreated control, as shown in Example 36.

Table VII shows the results obtained using the coupling agent of this invention in conjunction with various polymers and fillers, as illustrated in Examples 47, 49, 51, 53, 56, and 57, as compared with prior art agents, as illustrated in Example 55, and untreated controls, as illustrated in Examples 4~, 48, 50, 52, and 54.
Legend for Tables I - VII

Dl = *x-azidosulfonylhexyltriethoxysilane (N3S2-C6H12-Si(OEt)3) 10 D2 = *x-azidosulfonylbutyltriethoxysilane (N3SO2-C4~8-Si(OEt)3~
Sl = (p-azidosulfonylphenyl)-ethyltrimethoxysilane CH2CH2SI (OMe)3 /

PP = Stabilized polypropylene, melt-flow rate=4 dg./min., average molecular weight=25,000.
15 APTS = Aminopropyltriethoxysilane TNPS = Tetra-n-propylsilicate DAPTS = Diethylaminopropyltriethoxysilane TES = Tetraethylsilicate E-glass = 1/16 inch milled fiberglass ATH = Alumina trihydrate HDPE = High density polyethylene * "x" signifies random substitution of the azide group on the alkyl chain ~1 ` ~ ~ ~

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Claims (12)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A method for making a coupling agent for treating reinforcing materials and fillers to promote the adhesion of polymers to them, and containing an azidosilane, is charac-terized in that an aminosilane is added to the azidosilane before or after a reinforcing material or filler is treated with either of the silanes, and if the aminosilane is added to the azidosilane before the reinforcing material or filler is treated, it is treated before the silanes have been in contact for more then 15 minutes.

2. A method for making a coupling agent as claimed in claim 1, further characterized in that a tetraalkylsilicate is added to one of the silanes or to the mixture of silanes before the reinforcing material or filler is treated with the said silane or mixture.

3. A coupling agent for treating reinforcing materials and fillers to promote the adhesion of polymers to them, and containing an azidosilane, characterized in that the agent also contains an aminosilane that may react with the azido-silane, and contains no more than the amount of a reaction product of the two silanes than would be produced by the said reaction in 15 minutes following the mixing of the silanes.

4. A coupling agent as claimed in claim 3, further characterized in that the agent also contains a tetra-alkylsilicate.

5. A coupling agent as claimed in claim 4, further characterized in that the tetraalkylsilicate is tetra-n-propyl silicate.

6. A coupling agent as claimed in claims 3, 4 or 5, further characterized in that the azidosilane has the formula where R is an organic radical; X is a radical selected from the group consisting of halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido, amine and amide radicals; T is a radical selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; a is an integer from 1 to 3; b is an integer from 0 to 2; c is an integer from 1 to 10; d is an integer from 1 to 3; and a+b+d equals 4; and 2 is a radical selected from the group consisting of and -SO2N3 where R' is a radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and COOR" radicals; where R"
is a radical selected from the group consisting of alkyl, cycloalkyl and aryl radicals.

7. A coupling agent as claimed in claims 3, 4 or 5, further characterized in that the aminosilane has the formula H2NRSi(R')3 where R is a lower alkyl radical, and R' is a radical selected from the group consisting of lower alkoxy and lower alkoxymethyl radicals.

8. A coupling agent as claimed in claims 3, 4 or 5, further characterized in that the azidosilane is x-azidosulfonylhexyltriethoxysilane, (p-azidosulfonylphenyl)-ethyltrimethoxysilane, or x-azidosulfonylbutyltriethoxysilane.

9. A coupling agent as claimed in claims 3, 4 or 5, further characterized in that the aminosilane is aminopropyltriethoxysilane.

10. A coupling system for coupling fillers to thermoplastic polymers comprising:
(a) at least one azidosilane having the formula where R is an organic radical; X is a radical selected from the group consisting of halo, hydroxy, alkoxy, organo oxycarbonyl, azido, amine and amide radicals; T is a radical selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; a is an integer from 1 to 3; b is an integer from 0 to 2; c is an integer from 1 to 10; d is an integer from 1 to 3; and a+b+d equals 4; and Z is a radical selected from the group consisting of and -SO2N3 where R' is a radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and COOR" radicals; where R"
is a radical selected from the group consisting of alkyl, cycloalkyl and aryl radicals; and (b) at least one aminosilane having the formula H2NRSi(R')3 where R is a lower alkyl radical, and R' is a radical selected from the group consisting of lower alkoxy and lower alkoxymethyl radicals, wherein (a) and (b) are in contact less than 15 minutes before contacting the filler.

11. In a process for treating a filler to improve its adhesion to a thermoplastic polymer, the improvement wherein the filler is treated with a coupling system comprising:
(a) at least one azidosilane having the formula where R is organic radical; X is radical selected from the group consisting of halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido, amine and amide radicals; T is a radical selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; a is an integer from 1 to 3; b is an integer from 0 to 2; c is an integer from 1 to 10; d is an integer from 1 to 3; and a+b+d equals 4; and Z is a radical selected from the group consisting of and -SO2N3 where R' is a radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and COOR" radicals; where R"
is a radical selected from the group consisting of alkyl, cycloalkyl and aryl radicals; and (b) at least one aminosilane having the formula H2NRsi(R')3 where R is an alkyl radical, and R' is a radical selected from the group consisting of lower alkoxy and lower alkoxymethyl radicals, wherein (a) and (b) are in contact less than 15 minutes before treating the filler.

12. In a process for producing a reinforced polymer comprising the steps of:
(1) treating a filler with a coupling system;
(2) mixing the treated filler with a thermoplastic polymer; and (3) heating the mixture;
the improvement wherein the coupling system comprises:
(a) at least one azidosilane having the formula where R is an organic radical; X is a radical selected from the group consisting of halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido, amine and amide radicals; T is a radical selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; a is an integer from 1 to 3; b is an integer from 0 to 2; c is an integer from 1 to 10; d is an integer from 1 to 3; and a+b+d equals 4; and 2 is a radical selected from the group consisting of and -SO2N3 where R' is a radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl and COOR" radicals; where R"

is a radical selected from the group consisting of alkyl, cycloalkyl and aryl radicals; and (b) at least one aminosilane having the formula H2NRSi(R')3 where R is a lower alkyl radical, and R' is a radical selected from the group consisting of lower alkoxy and lower alkoxymethyl radicals, wherein (a) and (b) are in contact less than 15 minutes before treating the filler.