KR850000081B1 - Process for silane/filler production - Google Patents

Abstract

Silane/filler composition is prepared from 95-30 wt.% powdered carbon black and/or silicate filler and 5-70 wt.% silane compd. (I) by means of vigorous mixing. In the process, X = halogen atom; p = 1 or 2; m = 1 or 5; R1 = C1-C5 alkyl, C5-C8 cycloalkyl, or phenyl gp.; R = C1-C5 alkyl, C5-C8 cycloalkyl, phenyl, or benzyl gp.; and n = 0, 1, or 2. Applied equipment includes a powder blender, propeller blender, bead pelletizer, or granulator. (I) is halogen alkoxy silane, such as chloro methyl trimethoxy silane, bromo methyl triethoxy silane, etc.

Description

Process for preparing silane / filler composition

The present invention relates to silane / fillers in the form of powders or granules, in particular for use in curable rubber forming compositions based on natural or synthetic rubbers or mixtures thereof containing at least one synthetic or natural silicate filler and / or carbon black. It relates to a process for preparing the composition.

Mixtures in the form of powders of oligosulphidic silanes and silicate fillers are already known (DE-OS No. 2255577), and likewise mixtures in the form of powders of mercaptosilanes and silicate fillers are known (DE-AS No. 25 28 134). Also known are mixtures of carbon black and oligosulphidic silanes (DE-OS No. 2747277). All such mixtures are very suitable for use in rubber forming compositions, wherein the alkoxysilanes used are compounds of the type containing sulfur bound to carbon. The sulfur contained here plays an important role in the curing reaction.

Surprisingly, however, the inventors have found that halogen alkoxy silane compounds, typically 3-chloropropyl triethoxysilane (Cl-PTES), have useful effects on rubber cured compositions and show excellent improvement in the properties of the cured products. It turned out. Mixtures and molding compositions based on silicate fillers and halogen rubbers containing suitable halogensilanes have already been proposed. Even more surprisingly, these silane compounds provide unprecedented very beneficial properties and even significantly improve the properties of cured products, even for silicate-filled molding compositions based on the most common halogen-free rubbers.

According to the prior art as mentioned above, several important properties of the rubber mixture and its cured product are greatly increased by using the silane / filler composition rather than separately using the silane and the filler in the preparation of the molding composition according to the invention. It was hard to expect that it could be improved.

According to the present invention there is provided a silane / filler composition consisting of 5 to 70% by weight of silane of the following general formula (I) and 95 to 30% by weight of at least one inorganic filler (the remaining amount based on 100%) do.

(Ⅰ)

(Ⅰ)

Wherein X represents a halogen atom, in particular chlorine or bromine; p is 1 or 2; m is 1 to 5; R ¹ represents a C ₁ -C ₅ alkyl group, a C ₅ -C ₈ cycloalkyl group or a phenyl group; R represents a C ₁ -C ₅ alkyl group, a C ₅ -C ₈ cycloalkyl group, a phenyl group or a benzyl group; n is 0, 1 or 2.

The composition according to the invention is stable upon storage and generally stabilizes the hydrolysis-sensitive alkoxy silanes in the composition, and in addition to being convenient for use in processing equipment (rubber processing industry) unlike the starting materials in liquid or powder form. For rubber mixtures based on natural and / or synthetic rubbers, which may or may not contain halogens in the molecule, which are present in a cohesive state and are most importantly filled with silicate fillers and optionally carbon black. Excellent effect. The reason for this effect improvement in the properties of the cured product produced using the silane / filler mixture according to the invention is that in some cases a synergistic effect compared to the addition of silane and filler to the other components in the mixture Are described below, and are particularly well described in the Examples.

카본블랙이 있다. 본 발명에 따른 제제의 제조에는 프린텍스

60과 프린텍스

300의 혼합물 또는 프린텍스

30과 프린텍스

300의 혼합물과 같은 서로 다른 카본블랙의 혼합물이 사용될 수도 있다. 사용된 제조공정과 카본블랙에 대한 실란의 정량적비의 범위내에서의 혼합비에 따라 분말형 생성물 또는 자유-유동 비점착성 과립이 수득될 수 있다.The most suitable carbon blacks for the purposes of the present invention are carbon blacks in their own known form, in particular furnace blacks such as rubber blacks, preferably HAF- and ISAF-carbon blacks used in the rubber processing industry. , And commercially available from Degussa, having a specific surface area of 30 to 140 m 2 / g and an average injector size (arithmetic mean) of about 20 to 60 nanometers, measured by the nitrogen absorption method according to DIN 66 132 Printex in powder form

There is carbon black. In the preparation of the preparations according to the invention,

60 and Printex

300 mixtures or printex

Lesson 30 and Printex

Mixtures of different carbon blacks, such as a mixture of 300, may also be used. Depending on the manufacturing process used and the mixing ratio within the quantitative ratio of silane to carbon black, a powdered product or free-flowing non-tacky granules can be obtained.

,

VN 3, 울트라실

VN 2, 실테그

AS 9, 실테그

AS 7, 듀로실

및 엑스트러실

과 같이 비표면적(DIN 66 132 참조)이 20 내지 400㎡/g, 바람직하게는 100 내지 250㎡/g이며, 평균 주입자 크기가 10 내지 400㎚인 분말 형태의 화열성 실리카 또는 침강실리카들이다. 이러한 여러가지 실리카의 혼합물도 본 발명에 따르는 제조방법에 사용할 수 있다.Suitable synthetic silicate fillers are reinforcing fillers mainly used in the rubber industry, in particular aerosils sold by Degussa.

,

VN 3, Ultra Seal

VN 2, Silteg

AS 9, Silteg

AS 7, Durosil

And extruder

And pyrogenic silicas or precipitated silicas in powder form with a specific surface area (see DIN 66 132) of 20 to 400 m 2 / g, preferably 100 to 250 m 2 / g and an average injector size of 10 to 400 nm. Mixtures of these various silicas can also be used in the production process according to the invention.

Natural silicate fillers such as kaolin, clay, chalk, silica chalk, Kielselguhr, fine silica sand and asbestos are also suitable fillers for the production process of the present invention. Fillers in the form of mixed oxides or oxide mixtures of oxides of silicon such as aluminum, magnesium, calcium, barium, zinc and / or titanium and silicon dioxide may also be used.

R 972(화열성 실리카를 기본으로 함) 및 사이퍼나트

D 17(침강 실리카를 기본으로 함)과 같은 실란으로 공지의 방법에 의해 소수성으로 만들 수 있다.Silicate fillers are also commercially available Degussa commercial aerosils

R 972 (based on pyrogenic silica) and cypernath

Silanes such as D 17 (based on precipitated silica) can be made hydrophobic by known methods.

Synthetic silicates having a specific surface area of about 20 to 400 m 2 / g and an injector size of about 10 to 40 nm, for example, aluminum silicates or alkaline earth metal silicates such as magnesium or calcium silicates may also be used.

Mixtures of fillers such as silica-kaolin or silica / diatomaceous earth / choke, and mixtures of silicate-containing reinforcing fillers such as silica / HAF-carbon black or silica / kaolin / ISAF-carbon black with known carbon blacks for rubber It can be used successfully in the method of producing the following composition.

Halogen alkoxysilanes of the general formula (I) which are present in the composition according to the invention in an amount of 5 to 70% by weight, preferably 15 to 60% by weight, advantageously 50% by weight, in particular include the following silanes: Are: chloro methyltrimethoxysilane, chloromethyltriethoxysilane, bromomethyl triethoxysilane, dichloromethyltriethoxysilane, 1-chloro-1-methyl methyl trimethoxy silane, 2-chloroethyl trimeth Methoxy silane, 2-bromoethyl trimethoxy silane, 2-dibromoethyl trimethoxy silane, 3-bromopropyl trimethoxy silane, 3-chloropropyl trimethoxy silane, 3-dichloropropyl trimethoxy Silane, 3-chloropropyl triethoxy silane, 3-bromopropyl triethoxysilane, 3-dibromopropyl triethoxysilane, 2-bromo-1-ethyl tripropoxysilane, 2-dichloroethyl tri -n-butoxysilane, 2-chloroethyltri-2-methyl propoxy Cysilane, 3-bromopropyl tri-butoxy silane, 3-dibromopropyl triisopropoxysilane, 3-bromopropyltri-n-pentoxy silane, 2-chloroethyl tri-2'- Ethyl-ethoxy silane, 2-bromo-2-methyl-ethyl dimethoxyethoxy silane, 3-dichloropropyl-methoxy- methoxy-propoxysilane, 3-chloropropyl dimethoxy methyl silane, 3-bromo Propyl diethoxy ethylsilane, 3-chloropropyl ethoxy diethyl silane, 3-bromopropyl-tris- (1-methoxyethoxy) -silane, 3-chloro propyl diethoxy phenylsilane, 3-dichloropropyl dimethoxy Cyclopentylsilane, 3-bromopropyl di-n-propoxy cyclohexyl silane, 3-chloropropyl dicyclo hexoxy cyclohexylsilane, 3-bromopropyl diethoxy cycloheptyl silane, 3-chloropropyl ethoxyphenyloxy Ethyl silane, 3-dibromopropyl benzyloxyethoxyethyl silane, 4-chloro-n-part Tyltrimethoxysilane, 4-bromobutyl trimethoxysilane, 3-chloro-2-methylpropyl trimethoxysilane, 3-chloro-3-methyl propyl cyclooctyl dipropoxysilane, 3-chloro-2-ethyl -Propyl diethoxymethyl silane, 3-bromo-3-ethyl-propyldimethoxy methylsilane, 3-chloro-2-methylpropyl dimethoxy phenylsilane, 5-chloro-n-pentyl triethoxysilane, 4-bro MO-1-methyl-butylcyclo-octoxy dimethoxysilane, 4-bromo-2-methyl-butyl triethoxysilane, 2-chloro-2-methyl-ethyl tripentoxy silane, 2-dichloro-2- Methyl-ethyl tributyloxy silane, 3-bromopropyl triphenoxy silane, 3-chloropropyl tribenzyloxysilane, 3-dibromopropyl tricyclo pentoxy silane, 3-bromopropyl tri-n-pentoxy Silane, dibromomethyl triethoxy silane, dichloromethyl triethoxy silane, 2-dichloroethyl triethoxy silane, 2-dibromoethyl tetra -n-propoxysilane, 3-dichloropropyl triethoxy silane, 2-dichloro-i-propyl triethoxy silane, 2-dibromo-i-propyl tri-i-propoxy silane, 3-dichloropropyl tri -n-propoxysilane, 3-dibromopropyl tri-n-butoxysilane, 4-dichlorobutyl triethoxy silane, 4-dibromobutyl tri-n-propoxy silane, 5-dichloropentyl trie Oxy silane, 5-dibromo pentyl tri-n-propoxy silane, and mixtures of these halogen alkyloxy silanes.

Preference is given to using halogen alkyloxysilanes containing one halogen atom (when p is 1 in formula (I)) and three alkoxy silyl groups and mixtures thereof.

The silane compound corresponding to the general formula (I) is known per se, for example, by adding (hydrolyzing) a halogenated hydrocarbon containing a CC double bond to the halogen silane containing at least one hydrogen atom under catalytic control. It can be obtained by the method. Halogen atoms present on silicon atoms are converted to alkoxysilanes by known alcoholic decomposition, for example, by known methods. The crude silane compounds produced from such a manufacturing process can be used directly according to the object of the present invention when they contain little hydrolyzable halide and hydrogen halide. However, if such impurities are present, they are treated with ammonia or sodium hydride and then rectified arbitrarily to remove the impurities.

The composition of the present invention is a powder mixer. It is prepared in a high speed mixer such as a propeller mixer or a non-forming machine and a granulator.

According to the present invention there is provided a method of preparing the silane / filler composition described above. In this process, at least one carbon black and / or at least one powdered silicate filler is introduced into the powder mixer in an amount of 95 to 30% by weight, followed by filling the at least one liquid silane of formula (I). Is added in an amount of 5 to 70% by weight to 100% relative to, followed by vigorous mixing for a short time until a powdered, granular or free-flowing composition is formed.

It may be beneficial to spray the silane onto the filler particles flowing in the powder mixer. Alternatively, silane in the form of a solution or suspension may be added to the filler particles flowing in the powder mixer.

Example 1

푸랑크푸르트 암마인 소재의 DEGUSSA 제품) :Carbon black, which has the following experimental data, is used as an inorganic filler.

DEGUSSA products from Frankfurt am Main):

Nitrogen surface area 78 ㎡ / g according to DIN 66132

Average injector size 27㎜

pH value (DIN 53 200) 9

Dibutylphthalate absorbance according to DIN 53 601 100 ml / 100 g

10 kg of carbon black as defined above was added to a trough-type powder mixer having a capacity of 150 liters and having a propeller-type mixing device, and then 10 kg of 3-chloropropyl triethoxysilate was added to mix the mixed ingredients well. 360r. p. Homogenize at m for 30 seconds.

The device used here is described in German Patent Application Publication No. 1592861. After removing the discharge unit, 20 kg of granules having an average particle diameter of 1.0 mm were separated. The granules thus prepared are dust free, non-tacky, free flowing, storageable and measurable and can be easily mixed in the preparation of the rubber molding composition.

Example 2

VN 3, DEGUSSA 제품)를 본 실시예에서의 충진제로 사용한다.Silica Filler with Experimental Data

VN 3, product of DEGUSSA) is used as the filler in this example.

Nitrogen surface area 165 to 180 m2 / g according to DIN 66132

Conductivity of 4.0% suspension in water 100 μS / cm [S = Siemens]

PH according to DIN 53200-value 6.3

Moisture content 5.0 wt%

10 kg of silica filler is introduced into a trough type powder mixer as described in Example 1. Next, 10 kg of 3-chloropropyl triethoxy silane is sprayed into the mixer. After spraying, the two components are mixed vigorously for an additional 20 seconds at 360 rpm. The mixer's discharge unit is then opened to separate a homogeneous powder mixture of the two components.

Example 3

Here, natural aluminum silicate (review) with the following data is used as inorganic filler.

Sieve residue 0.05% in 43 μm sieve according to DIN 53 580

Average particle size 2㎛

Nitrogen surface area 30 ㎡ / g according to DIN 66 132

PH value according to DIN 53 200 5.5

17 kg of the natural aluminum silicate as defined above is introduced into the powder mixer described in Example 1. 3 kg of 3-chloropropyl triethoxy silane are then added and mixed vigorously for 20 seconds. The discharge valve is then opened to discharge the homogeneous powder mixture of the two components while rotating the mixing device.

The composition according to the invention can be used in molding compositions based on any crosslinkable polymer, in particular thermoplastic polymers containing, for example, silicate fillers and / or carbon black as fillers. Such polymers include in particular polyolefins such as polyethylene, polypropylene, ethylene propylene copolymers and the like.

The compositions of the present invention show unexpected excellent results for compositions and molding compositions based on natural and synthetic rubbers filled with silicate fillers and optionally carbon black. Rubbers include, in particular, natural rubbers, polybutadiene rubbers, polyisoprene rubbers, butadiene-styrene rubbers, butadiene-acrylonitrile rubbers, butyl rubbers, ethylene, propylene and terpolymers of non-covalently bonded dienes, carboxy rubbers, epoxides Rubbers and trans-polypentenamers and also halogenated butyl rubbers, in particular halogenated rubbers such as brominated or chlorinated butyl rubbers, chlorinated rubbers, rubber hydrochlorides and especially polymers of 2-chloro-1,3-butadiene, chlorosulfonated polyethylene, ethylene Propylene copolymers, ethylene-vinylacetate copolymers, natural rubbers and chemical derivatives of modified natural rubbers. Mixtures of these rubbers may be used.

In rubber molding compositions, in addition to fillers, conventional components such as crosslinking agents, accelerators, anti-aging agents, plasticizers or plasticizer oils, and also metal oxides such as aliphatic acids such as stearic acid, zinc oxide, magnesium oxide and / or lead oxide, and optionally Oligosulphidic silanes (US Pat. No. 3,875,489 or Germany) which may be used instead of sulfur as stabilizers against sulfur, aging, fatigue, ozone and / or light and optionally as crosslinkers (DE-PS 25 36 674). Patent No. 25 42 534).

The rubber molding composition can be produced by a known method. In the following application examples, the amount of the mixed component is expressed in parts by weight (PW). Each comparative mixture is identified by the letter "V" in front of the number. Mixtures containing the compositions according to the invention are distinguished by the letter "E".

Example 4 Application Example

The following molding compositions or mixtures based on styrene-butadiene rubber (SBR 1500) exhibit a beneficial synergistic effect by using the silane / filler composition according to the invention.

1) 1: 1 mixture of HAF-carbon black and Cl-PTES according to Example 1

2) 1: 1 mixture of silica filler and Cl-PTES according to Example 2

Six mixtures are tested according to known standard methods. The corresponding test results are described in the following table.

(Cure temperature = 160 ° C)

The test results show that: 7.5 parts by weight of 3-chloropropyltriethoxysilane was added to the comparative or control mixture V 4.1 to obtain the following improvements: increase in tensile strength, significant increase in modulus and shore hardness and improvement in wear or wear (V 4.2). As expected, the addition of carbon black showed some improvement in the properties of the cured product. As expected, the pattern viscosity was impaired while the ammeter's value was somewhat improved (compare V 4.1 and V 4.3). If silane is added here (compared to V 4.3 and V 4.3), all aspects except for the increase in tensile strength are improved (in some cases very markedly).

However, using the compositions of the present invention (see E 4.1 and 4.2) instead of adding each of the components separately, surprisingly marked improvement in modulus and crosslink density in both black and white mixtures. This synergistic effect was confirmed even after two months of storage of the composition, and from this fact it can be seen that the composition according to the present invention has a high stability upon storage.

Example 5

The following mixtures are prepared and tested based on silica-filled poly-2-chloro-1,3-butadiene (Bayprene 210, product of Bayer AG):

As a result of the test of Example 5, it was proved that the effect of the composition (E 5.1) according to the present invention is superior to that of separately adding the components of the composition in the same amount separately (V 5.2) and the control mixture (V 5.1). do.

Example 6

The desired improvement can also be obtained when silica filler is supplemented with clay (Suprex Clay, product of J. M. Huber of Locust, NJ) in the mixture of Example 5 (see following table). A synergistic effect can also be obtained with clay-filled mixtures.

Industrial applications for rubber compounds or molding compositions and their cured products include cable sheaths, hoses, heating tubes, electrical insulators, linings of heat-resistant fibers, impregnations and sheaths, in particular drive belts, V-belts, conveyor belts, rolls. Coverings, slabs, tires, especially tire wheelers, as well as soles, braking and vibration mechanisms or other similar products.

Claims (1)

95 to 30% by weight of at least one carbon black and / or at least one silicate filler is introduced into the powder mixer in powder form, and then at least one silane corresponding to formula (I) is added in an amount of 5 to 70% by weight. And vigorously mixing for a short time until a powdered or granular free flowing composition is formed.

(Ⅰ) Wherein X represents a halogen atom; p is 1 or 2; m is 1 to 5; R ¹ represents a C ₁ -C ₅ alkyl group, a C ₅ -C ₈ cycloalkyl group or a phenyl group; R represents a C ₁ -C ₅ alkyl group, a C ₅ -C ₈ cycloalkyl group, a phenyl group or a benzyl group; n is 0, 1 or 2.