CA1180145A

CA1180145A - Halogenated silane/filler granular or powder preparations

Info

Publication number: CA1180145A
Application number: CA000358301A
Authority: CA
Inventors: Siegfried Wolff; Lothar Rothbuhr; Heinz Grewatta
Original assignee: Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 1979-08-17
Filing date: 1980-08-15
Publication date: 1984-12-27
Also published as: FR2463789A1; IT8049486A0; DE2933346C2; GB2056995A; BR8005064A; JPS5630443A; BE884772A; MX157074A; FR2463789B1; SE8005783L; NL8004246A; CH643277A5; AU6118380A; US4297145A; ZA803596B; ES494251A0; NL190527C; AU531546B2; IT1146236B; LU82715A1

Abstract

ABSTRACT

The invention provides a silane/filler preparation, con-sisting of from 5 to 70% by weight of at least one silane corres-ponding to the following formula in which X is a halogen atom, p is 1 or 2, m is 1 to 5, R1 is a C1-C5-alkyl group, C5-C8-cycloalkyl group or a phenyl group, R is a C1-C5-alkyi group, a C5-C8-cycloalkyl group, a phenyl group or a benzyl group and n is 0, 1 or 2, and respectively balanced to 100% from 95 to 30% by weight of at least one inorganic filler.
The invention also provides a process for the production of a silane/filler preparation which comprises introducing at least one carbon black and/or at least one silicate filler in powder form into a powder m ?xer in a quantity of from 95 to 30% by weight, after which at least one liquid silane as defined above is address in a quantity of from 5 to 70% by weight, respectively balanced to 100% relative to the filler, followed by brief intensive mixing until a powder-form or granular free-flowing preparation is formed. The preparation is used in optionally crosslinkable polymeric moulding compositions or vulcanisable or cross-linkable rubber moulding compositions such as sulphur-vulcanisable mould-ing compositions based on natural rubber and/or synthetic rubber.

Description

;` 1 ~8~

2 --This invention relates to powder-form or granular silane/filler preparations which are used in particular in vulcanisable rubber moulding compositions based on natural or synthetic rubbers or blends thereof which contain at least one synthetic or natural silicate filler and/or carbon black.

Powder-form mi~tures of oligosulphidic silanes and silicate fillers are already known (D~-OS No. 22 55 577), as are powder-form mi~tures of mercaptosilanes and silicate fillers (DE-AS No. 25 28 134). Mi~tures of carbon black and oligosulphidic silanes (DE-OS No. 27 47 277) are also known All these mi~tures are eminently suitable for use in rubber moulding compositions and the alko~y silanes used therefor are of the type which contain sulphur bound to carbon. This sulphur plays a noticeable part in the vulcanisation reaction.
It was all the more surprising then to discover, as ~pplicants have done, that halogen alkylo~ysilanes, of which the typical representative is ~-chloropropyl trietho~y silane (Cl-PTES in short), also produced valuable effects in rubber moulding compositions and valuable property improvements in their vulcanisates. Thus, mi~tures and moulding compositions based on halogen rubbers ~ontaining silicate fillers and halogen silanes of the type in question have already been proposed. It was even more surprising to find, as has now been found, that these silanes produce unexpected effects of an advantageous nature, even in silicate-filled moulding compositions based on the most common halogen-free rubbers, and also surprising improvements in the properties of the vulcanisates -` ~ 18~1~5 In the light of previous experience and irl view of the prior art referred to above, it was even less to be expected that, according to the present invention, some important properties of the rubber mixtures and their vulcanisates can be improved even further by using a silane/filler preparation for the production of the moulding compositions rather than using the silane and the filler separately in the production of the mi~tures.
The present invention provides a silane/filler prepara-tion, consisting of from 5 to 70% by weight of at least one sil-ane corresponding to the following formula I Xp-CmH2m+l_psiRn(OR)3-n in which X is a halogen atom, particularly chlorine or bromine, p is 1 or 2, m is 1 to 5, R is a Cl-C5-alkyl group, C5-C8-cyclo-alkyl group or~ a phenyl group,~ R is a Cl-C5-alkyl group, a C5-C8-cycloalkyl group, a phenyl group, a methoxy ethyl group or a benzyl group and n' is 0, 1 or 2, and respectively balanced to 100% from 95 to 30% by weight of at least one inorganic filler.
The preparations according to the invention are granu-lar or powder-form preparations which are stable in storage, and in general, also stabilise the hydrolysis-sensitive alkoxy sil-anes in the preparations, which in addition - in contrast to the ~ - 3 -

3 lgO~4~
liquid or powder-form starting ma-terials - are present in a non-dust forming, readily processible aggregate state conven-ient to the processor (rubber-processing industry) and which, most importantly, produce valuable effects in rubber mixtures based on natural and/or synthetic rubbers with or without halo-gens in the molecule which are filled with silicate fillers and, optionally, with carbon black. These effects and improvements in the properties of the vulcanisates produced by the silane/
filler preparations according to the invention, which in some in-stances are synergistic effects in relation to the separate addi-tion of silane and filler to the other constituents of the mixture, are explained further below and, in particular, in the Examples.
Carbon blacks which are eminently suitable for the purposes of the invention include the types known per se, parti-cularly the so-called rubber blacks used in the rubber-processing industry, preferably furnace blacks, such as HAF- and ISAF-carbon blacks, and the commercially available powder-form Printex(R) carbon blacks manufactured by DEGUSSA with specific surfaces, as measured by the nitrogen absorption method according to DIN
66 132, of from about 30 to 140 m2/g and mean primary particle sizes (arithmetic mean) of from about 20 to 60 nanometres. Mix-tures of different carbon blacks may also be used for producing the preparations according to the invention, for example mixtures of Printex( )60 and Printex( )300 or mixtures of Printex(R)30 and Printex(R)300. Powder-form products or free-flowing non-tacky granulates are obtained, depending on the production process used and the mixing ratio within the claimed quantitative ratios of silane to carbon black.

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Suitable synthetic silicate fillers are primarily the reinforcing fillers used in the rubber industry, particularly the commercially available powder-form pyroyenic or precipita-ted silicas manufactured by Degussa, such as Aerosil(R), Ul-tra-sil( ) VN3, ~ltrasil( ) VN2, Silteg(R) AS 9, Silteg( ) AS 7, Durosil(R) and Extrusil(R), with specific surfaces (see DIN
66 132) offrom~about 20 to 400 m2/g, preferably from 100 to 250 m /g, and mean primary particle sizes of from about 10 to ~00 nanometres. Mixtures of these various silicas may also be used for producing the preparations according to the invention.
Natural silicate fillers are also suitable for the purposes of the invention, examples being kaolins, clay, chalk, siliceous chalk, diatomaceous earth (kieselguhr), finely pow-dered quartz sands and asbestoses. It is also possible to use fillers in the form of mixed oxides or oxide mixtures of silicon dioxide with the oxides of the metals aluminium, magnesium, cal-cium, barium, zinc and/or titanium.
The silicate fillers may also have been hydrophobised in known manner with silanes of which typical representatives are Degussa's commercial products AEROSIL( ) R 972 (based on pyrogenic silica) and SIPERNAT( ) D 17 (based on precipitated silica).
Synthetic silicates, for example aluminium silicates or alkaline-earth metal silicates, such as magnesium or calcium silicate, with specific surfaces of from about 20 to ~00 m2/g and primary particle sizes of from about 10 to ~00 nm may also be used.

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Filler mixtures, such as silica/kaolin or silica/
kieselguhr/chalk and blends of the silicate-containing reinforcing fillers with the known rubber-grade carbon blacks, ~or example silica/HAF-carbon black or silica/kaolin/lSAF carbon blac~, may also be successfully used for producing the preparations accord-ing to the invention.
The halogen alkoxysilanes corresponding to formula I, which are prepsent in the preparations according to the invention in quantities of from 5 to 70% by weight, preferably in quanti-ties of from lS to 60~ by weight and advantageously in quantitiesof 50% by wei~ht, include in particular the following silanes:
chloromethyl trimethoxysilane, chloromethyl triethoxysilane, bromomethyl triethoxysilane, dichloromethyl triethoxysilane, l-chloro-l-methyl methyl trimethoxysilane, 2-chloroethyl tri-methoxy silane, 2-bromoethyl trimethoxy silane, 2-dibromoethyl trimethoxysilane, 3-bromopropyl trimethoxysilane, 3-chloropropyl trimethoxysilane, 3-dichloropropyl trimethoxysilane, 3-chloro-propyl triethoxysilane, 3-bromopropyl triethoxy silane, 3-dibromo-propyl triethoxysilane, 2-bromo-1-methyl-ethyl tripropoxysilane, 2-dichloroethyl tri-n-butoxy silane, 2-chloroethyl tri-2-methyl propoxysilane, 3-bromopropyl tri-t-butoxy silane, 3-dibromopropyl triisopropoxysilane, 3-bromopropyl tri-n-pentoxysilane, 2-chloro-ethyl tri-2'-ethyl-ethoxysilane, 2-bromo-2-methyl-ethyl dim-ethoxyethoxysilane, 3-dichloropropyl-methoxy-ethoxy-propoxy sil-ane, 3-chloropropyl dimethoxy methyl silane, 3-bromopropyl die-thoxy ethyl silane, 3-chloropropyl. ethoxy diethyl silane, 3-bromopropyl-tris-(l-methoxyethoxy) silane, 3-chloropropyl 3 ~ ~O ~

diethoxy phenyl silane, 3-dichloropropyl dimethoxycyclopentyl silane, 3-bromopropyl di-n-propoxy cyclohexyl silane, 3-chloro-propyl dicyclohexo~y cyclohexyl silane, 3-bromopropyl dietho~y cycloheptyl silane, 3-chloropropyl ethoxyphenylo~yethyl silane, 3-dibromopropyl benzyloxyethoxyethyl silane, 4-chloro-n-butyl trimethoxysilane, 4-bromobutyl -trimethoxysilane, 3-chloro-2-methyl propyl trimethoxysilane, 3-chloro-3-methyl propyl cyclo-octyl dipropo~ysilane, ~-chloro-2-ethyl-propyl dietho~ymethylsilane, 3-bromo-3-ethyl-propyl dimetho~ymethylsilane, 3-chloro-2-methyl propyl dime~thox~rphenylsilane9 5-chloro-n-pentyl trietho~y silane,

4-bromo-1-methyl-butylcyclo-octo~y dimethoxysilane, 4-bromo-2-methyl-butyl triethoxy silane, 2-chloro-2-methyl-ethyl tripentox~r silane, 2-dichloro-2-methyl-ethyl tributyloxy silane, 3-bromopropyl tripheno~ysilane, 3-chloropropyl tribenzylo~ysilane, :l5 3-dibromopropyl tricyclopentoxysilane9 ~-bromopropyl tri-ni-pento~ysilane, dibromomethyl trietho~y silane, dichloromethyl triethoxysilanes, 2-dichloroethyl triethoxy silane, 2-dibromoethyl tri-n-propo~ysilane9 3-dichloropropyl triethoxy silane, 2-dichloro-i-propyl trietho~ysilane, 2-dibromo-i-propyl tri-i-propoxy silane, 3-dichloropropyl tri-n-propo~y silane, 3-dibromo-propyl tri-n-butoxysilane, 4-dichlorobutyl trietho~ysilane, 4-dibromobutyl tri-n~propoxy silane, 5-dichloropentyl trietho~y-silane9 5-dibromopentyl tri-n-propoxy silane and mix-tures of these halogen alkylo~ysilanes. It is preferred -to use those halogen alkylo~ysilanes l~rhich contain one halogen atom (p=l in formula I) and three alko~ysilyl groups and mi~tures thereof.
The silanes corresponding to formula I can be obtained by methods known per se, for ex~ple from halogen silanes still S

containing at least one hydrogen atom, by catalytically con-trolled addition with a halogenated hydrocarbon containing a C-C-double bond (hydrolysis). The halogen atom(s) situated on the silicon atom are then converted into alko~y silanes again in h-nown manner, for e~ample, by alcoholysis. It has been found that the crude silanes emanating from production may be directly used with success for the purposes of the invention providing they are substantially free from hydrolysable halide and hydrogen halide. If present, these impurities are removed by treatment with ammonia or sodium hydride, option-ally followed by rectification.
The preparation is produced in high-speed mixers known ~ se, such as powder mi~ers, propeller mi~ers or bead-forming ~nd granulating machines.
The present invention also relates to -the process for producing the silane/filler preparations described above.
In this process at least one carbon black and/or at least one silicate filler in powder form is introduced into a powder mixer in a quantity of from 95 to ~0~ by weight, at least one liquid silane corresponding to formula I is then added in a quantity of from 5 to 70~ by weight, respectively balanced to 100~ relative to the filler, followed by brief intensive mixing until a powder-form or granular, free-flowing pre-paration is formed.
The silanes may with ad~antage be sprayed onto the particles of the filler(s) in motion in the powder mixer. Alternatively, they are applied in solution or sus-pension to the particles of the filler(s) in motion in the powder mixer.
Production Ex~mples 1) The inorganic filler used is a carbon black having the following test data (Printex (R) 3o, a product of DEGUSSA, Frankfurt-am-Main):

Nitrogen surfaee aceording to DIN 66 132 78 m2/g Mean primary particle size 27 nm pU-value (DIN 53 200) 9 Dibutyl phthalate absorption aecording to DIN 53 601 100 ml/100 g 10 kg of the above-defined carbon black were weighed into a trough-shaped powder mixer 150 litres in capaeity equipped with a propeller-like miæing tool, 10 kg of 3-B chloropropyl triethoxysila~e were then added and the mixture eomponents proeessed with one another and homogenised for 30 seeonds at 360 r.p.m. The apparatus used is described in DE-AS No. 15 92 8610 After withdrawalof the discharge unit1 20 kg of a granulate having a mean partiele diameter of 1.0 mm are removed. The granulate thus produeed was dust~
free~ non-taeky, free-flowing9 storable and meterable and could readily be mixed in in the production of rubber moulding compositions.
2) The filler used for this Example l~as a silica filler (Ultrasil(R) VN 3, a DEGUSSA product) charac-terised by the following test data:

Nitrogen surface 2 according to DIN 66 132 165 to 180 m /g Conductivity of a 4.0~
suspension in water 1000 ~S/cm (S=
Siemens) ~ 3~ 4~

pE-value according to DIN 53 200 6.3 Water content 5.0~ by weight 10 kg of the silica filler are introduced into the same trough-shaped powder mi~er as described in E~ample 1. 10 kg of 3-chloropropyl trietho~rsilane are then sprayed into the mi~er. After spraying in, the two components are intensive-ly mi~ed for another 20 seconds at ~60 r.p.m. Thereafter, the discharge unit of the mi~er is opened and a homogeneous powder-form mixture of the two components is removed.
3) The inorganic filler used in this case was natural aluminium silicate (clay) characterised by the following data:

Sieve residue according to DIN 53 580 43 pm sieve 0.05 Mean particle size 2 ~lm Nitrogen surface according to DIN 66 132 30 m2/g p~-value according to DIN 53 200 5.5 17 kg of the natural aluminium silicate characterised above were întroduced into the powder mi~er described in E~ample 3 kg of 3-chloropropyl trietho~silane were then added, followed by intensive mi~ing for 20 seconds. Thereafter the discharge valve was opened and a homogeneous, powder-form mi~ture of the two components was discharged with the mi~ing tool rotating.
The preparations according to the invention can be used in moulding compositions based on optionally crosslinkable polymers, such as, in particular, thermoplastic polymers, ~ 7 ~

which contain silicate fillers and/or carbon black as filler. Polymers such as these include inter alia poly-olefins 9 SU ch as polyethylene 3 polypropylene, ethylene-propylene copolymers, etc.
The preparations are preferably used with good and une~pected, advantageous results in compositions and moulding compositions based on natural and synthetic rubbers filled with silicate fillers and, optionally, with carbon black. The rubbers include in particular natural rubbers, polybutadiene rubbers, polyisoprene rubbers, butadiene-styrene rubbers~ butadiene-acrylonitrile rubbers, butyl rubbers, terpolymers of ethylene, propylene and unconjugated dienes, carbo~y rubbers, epoxide rubbers and trans-polypente-namers, also halogen rub~ers such as, for e~ample, halogenated butyl rubbers, particularly brominated or chlorinated butyl rubbers, chlorinated rubbers, rubber hydrochlorides a~d, in particular~ the polymers of 2-chloro-1~3-butadiene, also chloro-sulphonated polyethylene, ethylene-propylene co_polymers, ethylene-vinyl acetate copolymers, chemical derivatives of ~o natural rubber and modified natural rubbers. Blends of these rubbers may also be used.
In addition to the fillers9 the rubber moulding com-positions contain the usual constituents, such as cross-linkers, accelerators, antiagers, plasticisers or plasticiser oils, also aliphatic acids such as, for e~ample, stearic acid, metal oxides such as zinc oxide, magnesium o~ide and/or lead oxide, optionally sulphur, stabilisers against ageing9 fatigue, ozone and/or li.gh-t and optionally oligosulphidic silanes , I ~O~l4~

(US-PS No. 3,873,489 or DE-PS No. 25 42 534) which may even replace sulphur as crosslinking agent (DE-PS No, 25 36 674).
The rubber moulding compositions are produced by methods known per se. In the following Application E~amples, the quantities in which the mi~ture components are used are given in parts by weight (PW). The respective comparison mi~tures are identified by the letter "V" before the number.
The corresponding mi~tures containing the preparations accord-ing to the invention are identified by the letter "Et'.

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The figures representing the test results show the following. By adding 7.5 parts by weight of 3-chloropropyl trietho~y silane to the comparison or control mi~ture V4.1, the following improvements are obtained: increase in tensile strength, remarkable increase in moduli and Shore hardness and improvement in abrasion or wear (V4.2). As e~pected, slight improvements in the properties of the vulcanisates are also obtained by the addition of carbon black. The Rheo~eter values are also improved to some extent whereas - again as e~pected -~looney viscosity is impaired (V4.3 compared with V4.1). If,now the si]ane is added (see V4.4 compared with V4.3), the (in some cases very distinct) improvements again occur, e~cept there is no increase in tensile strength.
~owever, if now the preparations according to the invention (cf. E401 and E4.2) are used instead of the separate individual additions, further improvements in the moduli and crosslink density surprisingly occur both in the black mi~ture and also in the white mi~ture. These synergistic effects were confirmed a~ter the preparations had been stored for two months9 which is indicative of high stability in storage of the preparations according to the invention.
5) The following mi~tures based o~ s~ ica-filled poly-2-chloro-1,3-butadiene (Bayprene 210, a~ ~e-~ of Bayer AG) were prepared and ~sted: -25 Constituents Quantities in the mi~tures V5 1 V5.2 E5.1 Polychlorobutadiene 100.0 100.0 100.0 ~lagnesium o~ide, li~ht 4.0 4.0 4.0 Silica filler (cf. E~ample 2) 40.0 40~0 38.0 - ~6 l~0~
Constituents Quanti-ties in the mi~tures V5.1 V5.2 E5.1 Cl-PTES - 2.0 Preparation of equal parts of Cl-PTES and silica filler (cf.
above) Naphthenic plastici~er oil (setting point - 28 C) 15~0 15.0 15.0 Ethylene thiourea 0.75 0.75 0.75 Zinc o~ide (Red Seal Quality)5.0 5.0 5.0 Test Results Tensile strength (in MPa) 11.7 11.4 16.2 Modulus 300 (in MPa) 5.4 10.2 11.1 Breaking elongation (in ~) 540 320 390 Rheometer Test Dmax Dmin ~in Nm) 7.5 9.63 13.10 The test results of E~ample 5 also demonstrate the superior effect of the preparation according to the invention (E5.1) in relation to the separate addition of the constituents of the preparation in equal quantities (V5.2) and in relation to the control mi~ture (V~

6) If, in the mi~tures of E~ample 5, ~ e silica filler is ~ a ~f~
supplemented by a clay ~Supre~ Clay, a ~ ~ of J. M. Huber Corp. Locust, N.J., U.S.A.), the required improvements are also obtained (cfo following Table) Synergistic effects could also be observed in the case of the clay-filled mixture.
Constituents Quantities in the mi~ture V6.1 V6.2 E6.1 Polychlorobutadiene 100.0 100.0 100.0 ~fagnesium o~ide, light 4.0 4~0 4.0 Silica filler 40.0 40.0 40.0 ; - 17 - ~80~

Constituents Quantities in the mixtures V6.1 V6.2 E6,1 Suprex Clay - 11.3 Preparation according to E~ample ~ PTES and Suprex Clay) - - 13.3 Naphthenic plasticOser oil (setting point -28 C) 15~0 15.0 15.0 Ethylene thiourea 0.75 0.75 .75 Zinc o~ide (Red Seal ~uali-ty). 500 5~0 5.0 Tensile strength (in MPa)16,o 14.7 17.7 Modulus (in MPa) 5.0 6.0 12.1 Breaking elongation (in ~) 670 620 430 Industrial applications for the rubber mi~tures or moulding composition~ and their vulcanisates are, for e~ample, industrial rubber articles such as cable sheaths, hoses, heating tubes, also electrical insulations, linings, impregnations and coatings of heat-resistant fabrics, particularly drive belts, V-belts, conveyor belts, roll coverings, seals, tyres, particularly tyre treads, as well as shoe soles, damping and vibration elements and similar articles.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A silane/filler preparation in powder or granular form, consisting of from 5 to 70% by weight of at least one sil-ane corresponding to the following formula I Xp-CmH2m+1-pSiR?(OR)3-n' in which X is a halogen atom, p is 1 or 2, m is 1 to 5, R1 is a C1-C5-alkyl group, C5-C8-cycloalkyl group or a phenyl group, R
is a C1-C5-alkyl group, a C5-C8-cycloalkyl group, a phenyl group a methoxy ethyl group or a benzyl group and n' is 0, 1 or 2, and respectively balanced to 100% from 95 to 30% by weight of at least one inorganic filler.

2. A silane/filler preparation as claimed in claim 1 wherein X is chlorine or bromine.

3. A silane/filler preparation as claimed in claim 1 wherein the inorganic filler is carbon black.

4. A silane/filler preparation as claimed in claim 3 wherein the carbon black is a furnace black having a specific surface (DIN 66 132) of from 30 to 140 m /g and a mean primary particle size of from 20 to 60 nm.

5. A silane/filler preparation as claimed in claim 1 wherein the inorganic filler is a silicate filler produced pyro-genically or by precipitation in aqueous medium.

6. A silane/filler preparation as claimed in claim 5 wherein the silicate filler is a silica filler having a specific surface (DIN 66 132) of from 100 to 250 m /g and a rnean primary particle size of from 10 to 400 nm.

7. A silane/filler preparation as claimed in claim 5 wherein the silicate filler is of the type which has been hydro-phobised with at least one silane.

8. A silane/filler preparation as claimed in claim 1 wherein the inorganic filler is a natural light filler suitable for use in rubber technology.

9. A silane/filler preparation as claimed in claim 8 wherein the natural light filler is kaolin, clay, chalk, sili-ceous chalk or diatomaceous earth, which have been pretreated by the action of heat.

10. A process for the production of a silane/filler preparation which comprises introducing at least one carbon black and/or at least one silicate filler in powder form into a powder mixer in a quantity of from 95 to 30% by weight, after which at least one liquid silane corresponding to the following formula I Xp-CmH2m+1-pSuR?(OR)3-n' in which X is a halogen atom, p is 1 or 2, m is 1 to 5, R1 is a C1-C5-alkyl group, a C5-C8-cycloalkyl group or the phenyl group, R is a C1-C5-alkyl group, a C5-C8-cycloalkyl group, the phenyl group, a methoxy ethyl group or benzyl group, and n' is 0, 1 or 2, is added in a quantity of from 5 to 70% by weight, respec-tively balanced to 100% relative to the filler, followed by brief intensive mixing until a powder-form or granular free-flowing preparation is formed.

11. A process as claimed in claim 10 wherein the sil-ane(s) is/are sprayed onto the particles of the filler(s) in motion in the powder mixer.

12. A process as claimed in claim 10 wherein the sil-ane(s) is/are applied in solution or suspension to the particles of the filler(s) in motion in the powder mixer.

13. An optionally crosslinkable polymeric moulding composition comprising a polymer and prepared using a silane/
filler preparation as claimed in claim 1, 2 or 3.

14. A vulcanisable or crosslinkable rubber moulding composition comprising a rubber and prepared using a silane/
filler preparation as claimed in claim 1.

15. A composition as claimed in claim 14 which is a sulphur-vulcanisable moulding composition based on natural rub-ber and/or synthetic rubber.