CN101061188A - Hydrophobic silicon dioxide and its application in silicon rubber - Google Patents

Hydrophobic silicon dioxide and its application in silicon rubber Download PDF

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Publication number
CN101061188A
CN101061188A CNA200580039607XA CN200580039607A CN101061188A CN 101061188 A CN101061188 A CN 101061188A CN A200580039607X A CNA200580039607X A CN A200580039607XA CN 200580039607 A CN200580039607 A CN 200580039607A CN 101061188 A CN101061188 A CN 101061188A
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alkyl
aryl
methyl
chf
coo
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于尔根·迈尔
马里奥·肖尔茨
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Evonik Operations GmbH
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Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
    • C01B33/183—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process by oxidation or hydrolysis in the vapour phase of silicon compounds such as halides, trichlorosilane, monosilane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3045—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Abstract

To provide a charging system and the like for properly settling a charged fee and the like for a person having settlement authority. A terminal generates request information (S501) and transmits it to a content server (S502). On receipt of settlement instruction information sent from the content server in response to the request information, the terminal transforms the settlement instruction information into a tone signal (S504) and outputs the tone signal as a sound output to a telephone installed in the vicinity of the terminal and connected communicably with a charging server (S505). That is, a sound signal (the tone signal transformed from the settlement instruction signal) is transmitted to the charging server via the telephone. When settlement processing is carried out in the charging server, the terminal receives game data transmitted from the content server and stores them (S507).

Description

Water drain silica and the use in silicon rubber thereof
The present invention relates to water drain silica, its preparation method and the use in silicon rubber thereof.
Be known in to use in the silicon rubber and given hydrophobic pyrolytic silicon dioxide as filler (DE 199 43 666 A1).
US 6,331, and 588 have described and comprise the LSR-silicon rubber of pyrolytic silicon dioxide as filler.For fear of the inadvisable influence of silanol groups to the silicon rubber rheological property, need be according to US 6,331,588 give the surperficial hydrophobic property of pyrolytic silicon dioxide.
According to prior art, in the situation of LSR (fluid silicone rubber), perhaps original position and under being exposed to very high shearing force in give hydrophilic silicon-dioxide hydrophobic property, thereby can reduce viscosity and ductility limit (flow limite), perhaps will give hydrophobic silicon-dioxide for the same reason and be exposed under the high shearing force.
Known to the aerosol adulterated hydrophilic silicon dioxide of potassium (silica) from DE 19650500 A1.
General known silicon-dioxide from EP 1236773 A2 with the adulterated surface modification of potassium.Use therein KCl solution has the concentration of 0.5KCl.The K content of hydrophilic silicon dioxide is 300 μ g/g.In EP 1236773 A2, do not describe particular design surface modification, the potassium doped silica.
The invention provides a kind of according to the mode pyrolysis preparation of flame oxidation or preferred flame hydrolysis and the water drain silica of 0.000001 to the 40 weight % potassium that mixed.
In embodiments of the invention, the BET surface-area of adulterated oxide compound can be 10-1000m 2/ g, and the DBP of pyrolytic oxide absorb be detect less than or be lower than described pyrolytic silicon dioxide normal value 85%.
In a preferred embodiment of the invention, the amount that is used for adulterated potassium can be at 1-20, in the scope of 000ppm.Especially, the potassium content of the preceding silicon-dioxide of surface modification is with K 2The O meter can from 0.15 to 0.32 weight %.
Can set up the hydrophobic property of silicon-dioxide by surface modification.
Can carry out surface modification with one or more compounds in following group:
A) (RO) 3Si (C nH 2n+1) and (RO) 3Si (C nH 2n-1) the type organosilane
R=alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, butyl
n＝1-20
B) R ' x(RO) ySi (C nH 2n+1) and R ' x(RO) ySi (C nH 2n-1) the type organosilane
R=alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, butyl
R '=alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, butyl
R '=cycloalkyl
n＝1-20
x+y＝3
x＝1，2
y＝1，2
C) X 3Si (C nH 2n+1) and X 3Si (C nH 2n-1) type halo organosilane
X＝Cl、Br
n＝1-20
D) X 2(R ') Si (C nH 2n+1) and X 2(R ') Si (C nH 2n-1) type halo organosilane
X＝Cl、Br
R '=alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, butyl
R '=cycloalkyl
n＝1-20
E) X (R ') 2Si (C nH 2n+1) and X (R ') 2Si (C nH 2n-1) type halo organosilane
X＝Cl、Br
R '=alkyl, for example methyl, ethyl
R '=cycloalkyl, n-propyl, sec.-propyl, butyl
n＝1-20
F) (RO) 3Si (CH 2) m-R ' type organosilane
R=alkyl, for example methyl, ethyl, propyl group
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，-NH-CH 2-CH 2-NH 2，
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10 and
R=alkyl, for example methyl, ethyl, propyl group, butyl
-SH
-NR ' R " R  (R '=alkyl, aryl; R "=H, alkyl, aryl; R =
H, alkyl, aryl, benzyl, C 2H 4NR " " R " , wherein R " "=A, alkyl,
And R " =H, alkyl)
G) (R ") x(RO) ySi (CH 2) m-R ' type organosilane
R "=alkyl x+y=2
=cycloalkyl x=1,2
y＝1，2
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，-OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，-NH-CH 2-CH 2-NH 2，
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10 and
R=alkyl, for example methyl, ethyl, propyl group, butyl
-SH
-NR ' R " R  (R '=alkyl, aryl; R "=H, alkyl, aryl; R =H, alkyl, aryl, benzyl, C 2H 4NR " " R " , wherein R " "=A, alkyl, and R " =H, alkyl)
H) X 3Si (CH 2) m-R ' type halo organosilane
X＝Cl、Br
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，-OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，
-NH-CH 2-CH 2-NH 2
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10 and
R=methyl, ethyl, propyl group, butyl
-SH
I) (R) X 2Si (CH 2) m-R ' type halo organosilane
X＝Cl、Br
R=alkyl, for example methyl, ethyl, propyl group
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，-OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，-NH-CH 2-CH 2-NH 2，
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3，
Wherein R=methyl, ethyl, propyl group, butyl
-S x-(CH 2) 3Si (OR) 3, wherein R=methyl, ethyl, propyl group, butyl,
And X=1-10
-SH
J) (R) 2X Si (CH 2) m-R ' type halo organosilane
X＝Cl、Br
R=alkyl, for example methyl, ethyl, propyl group, butyl
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，-OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，-NH-CH 2-CH 2-NH 2，
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10, and R=methyl, ethyl, propyl group, butyl
k)
Figure A20058003960700121
The R=alkyl
R '=alkyl, vinyl
L) D3, D4, D5 type cyclic polysiloxanes, wherein D3, D4 and D5 are interpreted as having 3,4 or 5-O-Si (CH 3) 2The unitary cyclic polysiloxanes of-type
Octamethylcyclotetrasiloxane=D4 for example
Figure A20058003960700131
M) polysiloxane of following type or silicone oil
Figure A20058003960700132
m＝0，1，2，3，...∞n＝0，1，2，3，...∞u＝0，1，2，3，...∞Y＝CH 3，H，C nH 2n+1 n＝1-20Y＝Si(CH 3) 3，Si(CH 3) 2HSi(CH 3) 2OH，Si(CH 3) 2(OCH 3)Si(CH 3) 2(C nH 2n+1)，n＝1-20
R=alkyl, for example C nH 2n+1, wherein n is 1-20; Aryl, the phenyl group of phenyl and replacement for example, (CH 2) n-NH 2, H
R '=alkyl, for example C nH 2n+1, wherein n is 1-20; Aryl, the phenyl group of phenyl and replacement for example, (CH 2) n-NH 2, H
R =alkyl, for example C nH 2n+1, wherein n is 1-20; Aryl, the phenyl group of phenyl and replacement for example, (CH 2) n-NH 2, H
R =alkyl, for example C nH 2n+1, wherein n is 1-20; Aryl, the phenyl group of phenyl and replacement for example, (CH 2) n-NH 2, H
The present invention also provides a kind of preparation according to method surface modification of the present invention, the adulterated pyrolytic silicon dioxide of potassium, described method is characterised in that and will places suitable mixing vessel with the adulterated pyrolytic silicon dioxide of potassium by aerosol, under violent the mixing, randomly at first water and/or diluted acid, mixture with surface-modifying agent or kinds of surface properties-correcting agent sprays described silicon-dioxide then, and randomly continue again to mix 15-30 minute, then tempering 1-6 hour time under 100-400 ℃ temperature.
Can used water be acidified to the pH value of 7-1 with sour example hydrochloric acid.Used surface-modifying agent can be dissolved in appropriate solvent, for example in the ethanol.Can for example mix in the nitrogen and/or tempering in shielding gas atmosphere.
The present invention also provide a kind of preparation according to of the present invention by the method for aerosol with adulterated, surface modification, the pyrolytic silicon dioxide of potassium, described method is characterised in that under the situation of having got rid of oxygen, and silicon-dioxide is mixed as far as possible equably with surface-modifying agent; In the treatment chamber of vertical tube furnace form with continuous uniflux technology, will with small amount of steam, and randomly with the mixture heating up of rare gas element to 200-800 ℃, under preferred 400-600 ℃ the temperature; Make solid and gaseous reaction product separated from one another; And randomly make solid product depickling and drying then.
By aerosol being added flame (for example being used for preparing the flame of pyrolytic silicon dioxide in known manner by flame hydrolysis), with the reaction of the gaseous mixture of flame oxidation or flame hydrolysis before gas mixture colloidal sol equably, make aerosol/gaseous mixture complete reaction in flame, and the adulterated pyrolytic silicon dioxide of separating obtained potassium from gas vapor in known manner, can prepare by the aerosol adulterated pyrolytic silicon dioxide of potassium, the salts solution or the suspension that comprise sylvite are used as aerocolloidal starting material, by atomizing or aerosol generator through binary nozzle, preferably, perhaps prepare aerosol by dissimilar aerosol preparation methods by ultrasonic method.
Potassium chloride solution can have the potassium chloride concentration of 2.4-9.0 weight %.
From Ullmanns Enzyklop  die der technischen Chemie, the Edition version, the 21st volume is known the method for the flame hydrolysis that is used to prepare pyrolytic silicon dioxide in the 464th page.
From DE 19650500, know preparation method by the adulterated pyrolytic silicon dioxide of aerosol.
As segmentation cloth and the subsequently result of high temperature (1000-2400 ℃) in flame hydrolysis of doping component in aerosol, wherein doping component is in by under the specific environment of further pulverizing and/or melting, doped dielectric exists with finely divided form in gas phase during the formation of pyrolytic silicon dioxide, thereby doping component can be incorporated in the pyrolytic silicon dioxide equably.But, also can realize uniform distribution by the mode of suitably selecting raw material salt and the described method of enforcement.
The present invention also provides a kind of silicon rubber, it is characterized in that it comprises according to the present invention by aerosol with the adulterated pyrolytic silicon dioxide of potassium as filler.
If hydrophobic fumed silica according to the present invention is incorporated in the silicon rubber, obtain novel fully silicon rubber characteristic.
Because the potassium that adds, the pattern of pyrolytic silicon dioxide has changed, and makes primary particle also therefore cause low structure than the symbiosis of low degree ground.Can prepare this silicon-dioxide according to DE 19650500.
Also allow in conjunction with the pyrolytic silicon dioxide that has high surface area in a large number for described silicon-dioxide hydrophobic property, the result can realize excellent rheological property astoundingly, and sulfur product (vulcanates) shows unexpected high transparency and mechanical property.
Use for elastomerics, can use molecular weight is 400,000-600,000 polydimethylsiloxane, add conditioning agent for example hexamethyl-or divinyl tetramethyl disiloxane under preparation polydimethylsiloxane and have corresponding end group.In order to improve sulfidation and anti tear growth property (tear growth resistance), the vinyl group that passes through combination a small amount of (＜1%) in the addition chain linked to owner of vinyl dimethyl dichlorosilane (DMCS) (VMQ) usually is as substituting group.
It is that the high viscosity of clarification (water-clear) as 15-30kPas, the water is from deliquescent siloxane polymer that HTV silicon rubber is interpreted as meaning about 10,000 the SiO unit of chain length, viscosity.Use linking agent, filler, catalyzer, tinting pigment, release agent, softening agent, tackifier other composition as silicon rubber.
In the heat-vulcanized situation, the treatment temp routine is in about 140-230 ℃ scope, and carries out cold vulcanization under 20-70 ℃ temperature.In sulfuration, be distinguishing between peroxide crosslinking, the addition-crosslinked and condensation cross-linking.
Peroxide crosslinking is undertaken by radical reaction mechanism, wherein superoxide resolves into free radical under temperature action, the vinyl of free radical and polysiloxane or methyl combines and produce new free radical there, they are again with other polysiloxane chain combination and therefore cause crosslinked on the space then.Two free radicals compound or along with the rise movability of limited gradually chain of degree of crosslinking causes crosslinking reaction to stop.
In the situation of peroxide crosslinking, be suitable for the treatment condition of special process in order to make cross-linked speed, use different superoxide according to treatment process (for example extruding, injection molding, pressing mold expand).For example, need the crosslinked of unusual two-forty, and crosslinked, need low speed crosslinked in the molded articles preparing by injection molding or pressing mold for fear of just beginning when the cavity filling for extruding.
The characteristic of used superoxide is influential to the sulfur product structure, and is therefore also influential to its physical properties.Two fragrant acyl (Diaroyl) superoxide (two (2,4-two chloro-benzoyls) superoxide, dibenzoyl superoxide) cross-linked vinyl and methyl.On the other hand, it is specific crosslinked at dialkyl peroxide (dicumyl peroxide, 2,5 (two-t-butyl peroxy)-2,5-dimethylhexane) vinyl in fact only to take place.
Can control the Shore hardness of sulfur product to a certain extent by the amount of superoxide in the mixture.When the amount of superoxide increases, because more highdensity crosslinked position Shore hardness increases.But excessive superoxide causes elongation at break, tensile strength and the decline of anti tear growth property.According to application, in order to reduce permanent strain and to remove the superoxide split product, peroxide crosslinking needs tempering sulfur product subsequently.Except typical aromatic odour, especially outside the smell that dicumyl peroxide takes place, split product also can damage the physical properties (for example reversion (reversion) in the situation of acidic cleavage product) of sulfur product.
In the situation of filler, have any different between enhancing or non-reinforcing filler.
Non-reinforcing filler is characterised in that and the very weak interaction of siloxane polymer.They comprise carbon chalk, silica powder, diatomite, mica, kaolin, Al (OH) 3And Fe 2O 3Particle diameter is at the order of magnitude of 0.1 μ m.Their purpose is to improve the viscosity of compound and the Shore hardness and the Young's modulus of increase vulcanized rubber with unvulcanized state.In the situation of surface-treated filler, can also realize the raising of tear strength.
Reinforcing filler is surface-area＞125m especially 2The silicon-dioxide of the high dispersing of/g.Enhancement is owing to the combination between filler and the siloxane polymer.This silanol group (3-4.5SiOH group/nm that is combined in the silicic acid surface 2) and α-, form by hydrogen bridge band between the silanol group of alpha, omega-dihydroxy-polydimethylsiloxane with the oxygen of siloxane chain.These filler/interpolymer interactions cause the change of viscosity increase and second-order transition temperature and crystallization behavior.Polymkeric substance/filler key causes the mechanical properties improvement, but also may cause the crape sclerosis (crepe hardening) of rubber.
Talcum is in the mid-way of enhancing and non-reinforcing filler.
Filler also is used for special effect.These fillers comprise ferric oxide, zirconium white or the barium zirconate that is used to increase thermostability.
As for other composition, silicon rubber can comprise catalyzer, linking agent, tinting pigment, release agent, softening agent, tackifier.
Particularly need softening agent for setting up low Young's modulus.Interior viscosity accelerator-based in can interact on the one hand with substrate and on the other hand with the interactional functional silane of across-linked siloxane polymer (mainly in RTV-1 rubber, using).
Lower molecular weight or be rich in compound (diphenyl silanodiol for example, the H of monomer silanol 2O) offset the crape sclerosis.They are by having prevented that with the filler faster response silanol group of siloxane polymer and filler from interacting too strong.Corresponding effect also can realize by partly apply filler (handling filler with trimethyl silane) with trimethyl silyl.
Can also or it be mixed with organic polymer (butadiene-styrene copolymer) at modified siloxane polymkeric substance (phenyl polymer, boron-containing polymer) chemically.
In a preferred embodiment of the invention, silicon rubber can be LSR-silicon rubber.
Fluid silicone rubber (LSR) in fact aspect molecular structure corresponding to HTV, but the mean molecule chain length is low 6 times, therefore and viscosity is low 1000 times (20-40Pas).The processor can obtain two kinds of components (A and B) equally, and described component has comprised filler, vulcanizing agent and other additive randomly.
Use with the HTV mixture in identical silicon-dioxide and additive as filler.Distribute if realization is uniform, the viscosity that original polymer is low need be mixed with thorough in the mixing device of special exploitation in strong especially combination.For the ease of taking in filler and avoiding crape sclerosis, give to silicon-dioxide during married operation and by hexamethyl-disilazane (HMDS is also referred to as HMDZ) that complete hydrophobicity-original position is given in most applications.
By hydrosilication, promptly by of the addition of the complex-catalyzed following methyl hydrogen siloxane (in molecule, having at least 3 SiH groups) of the Pt (0) that measures at ppm to the polymkeric substance vinyl, carry out the sulfuration of LSR mixture, linking agent and catalyzer exist with independent component when carrying.Special inhibitor, for example 1-ethynyl-1-hexalin prevention begins to vulcanize and set up at room temperature about 3 days working life too early behind blending ingredients.By platinum and inhibitor concentration can be in sizable scope the adjusting ratio.
Because compare, addition-crosslinkedly can not disturbed, so the LSR mixture is used for the preparation of conductive silicon rubber product gradually by furnace black (in the HTV mixture, preferably using acetylene black) with (conventional in the HTV situation) peroxide cure.Compare graphite or metal-powder, preferably silver-colored, conductive furnace black is easier sneaks into and easier dispersion.Silicon rubber according to the present invention has following advantage:
The test of LSR (fluid silicone rubber) shown with the aerosil with same or similar surface-area (pyrolytic silicon dioxide) compare, hydrophobic adulterated oxide compound according to the embodiment of the invention 5 and 6 shows very good binding and dispersion behavior, and described compound has much lower viscosity and ductility limit.Particularly the remarkable high transparency of sulfur product is favourable.
Use is according to the adulterated silicon oxide of hydrophobic potassium of the present invention, caused the very material of low viscosity and ductility limit because its rudimentary structure can be used.Because their hydrophobic characteristics, they are very easy to and combination and dispersion apace.Therefore, will they not place under the high shearing force during the preparation of silastic mixture.The saving of energy and material cost is an additional advantage for the user.In addition, silicon rubber according to the present invention shows the optical property of improvement with the form of very high transparency.
Embodiment
The preparation of low structure powder
Use the burner apparatus described in the DE 196 50 500.
Embodiment 1
Mix with aerosol from the Klorvess Liquid preparation
At about 130 ℃ of SiCl that evaporate 4.44kg/h down 4And be transferred in the core pipe according to the burner of DE 196 50500.In this pipe, add 3.25Nm again 3The hydrogen of/h and 5.25Nm 3The x of/h 1: air and 0.55Nm 3The oxygen of/h.This gaseous mixture burner nozzle internally flows in the combustion chamber of water-cooled flame tube and burning.For fear of caking, also in the chuck nozzle of central nozzle, adding 0.5Nm 3(chuck) hydrogen and the 0.2Nm of/h 3The nitrogen of/h.
Also from environment, add 40Nm in the flame tube under being in slight decompression 3The air of/h.
Second kind of gaseous fraction introducing in the tube axial is made up of the aerosol from 2.5% KCl salt brine solution preparation.Used aerosol generator is the binary nozzle that realizes 247g/h aerosol atomizing output.Pass through 3.5Nm 3The carrier gas of/h make described water salt aerosol by indirect heating pipeline and leave inwardly projecting orifice, temperature out is 153 ℃.Introduce the aerosol of so introducing that contains sylvite in the flame and therefore change the character of gained pyrolytic silicon dioxide.
Behind flame hydrolysis, by applying decompression reactant gases and the adulterated pyrolytic silicon dioxide of institute's handy potassium (oxide compound) are passed through cooling system, and therefore the particle air-flow is cooled to about 100-160 ℃.In strainer or cyclonic separator, from exhaust flow, isolate solid.Obtain the mixed pyrolytic silicon dioxide of potassium oxide of gained with finely divided white powder form.In next procedure, under 400-700 ℃ temperature, remove the hydrochloric acid that adheres to the residual quantity on the doping silicon dioxide by handling with aeriferous air-flow.
The BET surface-area of gained pyrolytic silicon dioxide is 107m 2/ g.Analyzing the potassium oxide content of determining is 0.18 weight %.
In table 1, summed up preparation condition.In table 2, represent flame parameters, and in table 3, provided other analytical data of gained silicon-dioxide.
Embodiment 2
Mix with aerosol from the Klorvess Liquid preparation
Step is as shown in Example 1:
At about 130 ℃ of SiCl that evaporate 4.44kg/h down 4And be transferred in the core pipe according to the burner of DE 196 50500.In this pipe, add 4.7Nm again 3The hydrogen of/h and 5.7Nm 3The air of/h and 1.15Nm 3The oxygen of/h.This gaseous mixture burner nozzle internally flows in the combustion chamber of water-cooled flame tube and burning.For fear of caking, also in the chuck nozzle of central nozzle, adding 0.5Nm 3(chuck) hydrogen and the 0.2Nm of/h 3The nitrogen of/h.
Also from environment, add 25Nm in the flame tube under being in slight decompression 3The air of/h.
Second kind of gaseous fraction introducing in the tube axial is made up of the aerosol from 9% KCl salt brine solution preparation.Used aerosol generator is the binary nozzle that realizes 197g/h aerosol atomizing output.Pass through 4Nm 3The carrier gas of/h make described water salts solution by indirect heating pipeline and leave inwardly projecting orifice, temperature out is 123 ℃.Therefore, the aerosol of so introducing that contains sylvite has changed the character of gained pyrolytic silicon dioxide.
Behind flame hydrolysis, by apply decompression with the adulterated pyrolytic silicon dioxide of reactant gases and gained by cooling system, and therefore the particle air-flow is cooled to about 100-160 ℃.In strainer or cyclonic separator, from exhaust flow, isolate solid.Obtain the mixed pyrolytic silicon dioxide of potassium oxide of gained with finely divided white powder form.In next procedure, under 400-700 ℃ temperature, remove the hydrochloric acid that adheres to the residual quantity on the doping silicon dioxide by handling with aeriferous air-flow.
The BET surface-area of gained pyrolytic silicon dioxide is 127m 2/ g.
In table 1, summed up preparation condition.In table 2, represent flame parameters, and in table 3, provided other analytical data of gained silicon-dioxide.
Embodiment 3
Mix with aerosol from the Klorvess Liquid preparation
At about 130 ℃ of SiCl that evaporate 4.44kg/h down 4And be transferred in the core pipe according to the burner of DE 196 50500.In this pipe, add 2.5Nm again 3The hydrogen of/h and 7Nm 3The oxygen of/h.This gaseous mixture burner nozzle internally flows in the combustion chamber of water-cooled flame tube and burning.For fear of caking, also in the chuck nozzle of central nozzle, adding 0.3Nm 3(chuck) hydrogen and the 0.2Nm of/h 3The nitrogen of/h.
Also from environment, add 45Nm in the flame tube under being in slight decompression 3The air of/h.
Second kind of gaseous fraction introducing in the tube axial is made up of the aerosol from 2.48% KCl salt brine solution preparation.Used aerosol generator is the binary nozzle that realizes 204g/h aerosol atomizing output.Pass through 3.5Nm 3The carrier gas of/h make described water salts solution by indirect heating pipeline and leave inwardly projecting orifice, temperature out is 160 ℃.Therefore, the aerosol of so introducing that contains sylvite has changed the character of gained pyrolytic silicon dioxide.
Behind flame hydrolysis, by applying decompression reactant gases and the adulterated pyrolytic silicon dioxide of institute's handy potassium (oxide compound) are passed through cooling system, and therefore the particle air-flow is cooled to about 100-160 ℃.In strainer or cyclonic separator, from exhaust flow, isolate solid.
Obtain the mixed pyrolytic silicon dioxide of potassium oxide of gained with finely divided white powder form.In next procedure, under 400-700 ℃ temperature, remove the hydrochloric acid that adheres to the residual quantity on the doping silicon dioxide by handling with aeriferous air-flow.
The BET surface-area of gained pyrolytic silicon dioxide is 208m 2/ g.Analyzing the potassium oxide content of determining is 0.18 weight %.
In table 1, summed up preparation condition.In table 2, represent flame parameters, and in table 3, provided other analytical data of gained silicon-dioxide.
Embodiment 4
Mix with aerosol from the Klorvess Liquid preparation
At about 130 ℃ of SiCl that evaporate 4.44kg/h down 4And be transferred in the core pipe according to the burner of DE 196 50500.In this pipe, add 2.0Nm again 3The hydrogen of/h and 6.7Nm 3The air of/h.This gaseous mixture burner nozzle internally flows in the combustion chamber of water-cooled flame tube and burning.For fear of caking, also in the chuck nozzle of central nozzle, adding 0.3Nm 3(chuck) hydrogen and the 0.2Nm of/h 3The nitrogen of/h.
Also from environment, add 35Nm in the flame tube under being in slight decompression 3The air of/h.Second kind of gaseous fraction introducing in the tube axial is made up of the aerosol from 2.48% KCl salt brine solution preparation.Used aerosol generator is the binary nozzle that realizes 246g/h aerosol atomizing output.Pass through 3.5Nm 3The carrier gas of/h make described water salts solution by indirect heating pipeline and leave inwardly projecting orifice, temperature out is 160 ℃.Introduce the aerosol of so introducing that contains sylvite in the flame and therefore change the character of gained pyrolytic silicon dioxide.
Behind flame hydrolysis, by applying decompression reactant gases and the adulterated pyrolytic silicon dioxide of institute's handy potassium (oxide compound) are passed through cooling system, and therefore the particle air-flow is cooled to about 100-160 ℃.In strainer or cyclonic separator, from exhaust flow, isolate solid.
Obtain the mixed pyrolytic silicon dioxide of potassium oxide of gained with finely divided white powder form.In next procedure, under 400-700 ℃ temperature, remove the hydrochloric acid that adheres to the residual quantity on the doping silicon dioxide by handling with aeriferous air-flow.
The BET surface-area of gained pyrolytic silicon dioxide is 324m 2/ g.Analyzing the potassium oxide content of determining is 0.18 weight %.
In table 1, summed up preparation condition.In table 2, represent flame parameters, and in table 3, provided other analytical data of gained silicon-dioxide.
Table 1
Experiment condition in the adulterated pyrolytic silicon dioxide preparation
Embodiment number SiCl 4 kg/h Primary air Nm 3/h O 2Add Nm 3/h H 2Core Nm 3/h H 2Chuck Nm 3/h N 2Cover Nm 3/h Gas temperature ℃ Potassium salt soln KCl-weight % Aerosol amount g/h Aerosol air Nm 3/h BET m 2/g
1 4.44 5.25 0.55 3.25 0.5 0.2 153 2.5 247 3.5 107
2 4.44 5.7 1.15 4.7 0.5 0.2 123 9 195 4 127
3 4.44 7 0 2.5 0.3 0.2 160 2.48 204 3.5 208
4 4.44 6.7 0 2.0 0.3 0.2 139 2.48 246 3.5 324
Explain:
Air capacity in primary air=core pipe; H 2Hydrogen in core=core pipe;
The gas temperature at gas temperature=core pipe nozzle place; Aerosol amount=the change into mass velocity of the salts solution of aerosol form;
The amount of carrier gas in aerosol air=aerosol (air)
Table 2
Flame parameters in the adulterated pyrolytic silicon dioxide preparation
Embodiment number γ core [-] λ core [-] vk norm [m/sec]
1 2.77 1.01 20.8
2 4.00 1.00 25.9
3 2.13 1.17 21.6
4 1.71 1.40 20.0
Explain:
The ratio of hydrogen in γ core=core pipe; The ratio of oxygen in λ core=core pipe; For the accurate calculation of γ and λ and definition referring to EP 0 855 368; Vk Norm=in standard conditions (273K, discharge velocity 1atm).
Table 3
The analytical data of the sample that obtains according to embodiment 1-4
Embodiment number BET [m 2/g] The pH [-] of 4% aqueous dispersions With K 2The potassium content [weight %] of O meter DBP under the 16g weight [g/100g] Tap density [g/l] Compacted density [g/l]
1 107 7.07 0.18 n.e. 24 32
2 127 7.71 0.316 n.e. 31 42
3 208 6.66 0.15 234 19 25
4 324 6.35 0.18 305 17 22
Explain: the pH value of pH 4%sus.=4% aqueous dispersions; The DBP=dibutyl phthalate absorption, the n.e.=device does not detect end points.
Embodiment
The operation of hydrophobic property
The preparation of embodiment 5
The hydrophilic K-doped silica of describing among the 2.5kg embodiment 3 is placed mixing tank and under violent the mixing, at first sprays 0.125kg water, then by binary nozzle spray 0.3kg hexamethyldisilazane.When spray is finished, continue again to mix 15 minutes, then 25 ℃ of following tempering 5 hours, then 120 ℃ of following tempering 2 hours.
The preparation of embodiment 6
The hydrophilic K-doped silica of describing among the 2.5kg embodiment 4 is placed mixing tank and under violent the mixing, at first sprays 0.125kg water, then by binary nozzle spray 0.45kg hexamethyldisilazane.When spray is finished, continue again to mix 15 minutes, then 25 ℃ of following tempering 5 hours, then 120 ℃ of following tempering 2 hours.
Use the test of the adulterated hydrophobic fumed silica of potassium in the silicon rubber according to the present invention
Table 4
Analytical data
BET surface-area [m 2/g] The pH value K 2O content [weight %] Compacted density [g/l] Drying loss [%]
Embodiment 5 163 9.1 0.15 38 0.8
Embodiment 6 232 9.0 0.18 40 1.2
The product of test card 4 in LSE siloxanes prescription.Use has the hydrophilic original prod material as a comparison of the aerosil (pyrolytic silicon dioxide) of comparable surface-area.
LSR silicon rubber
In rail mounted dissolver (planetary dissolver), (50/500min-1 rail mounted mixing tank/dissolver plate) is in conjunction with 20% silicon-dioxide, then at high speed (100/2000min at a slow speed -1) disperseed 30 minutes down.
After combination, mixture forms low viscous flowable materials.After disperseing in 30 minutes, viscosity descends slightly.
When can not be in conjunction with hydrophilic original prod according to identical method, perhaps can only be during in conjunction with hydrophilic original prod with low concentration, embodiment 5 and 6 can be easily combined and be shown and determine good wetting properties and low-down rheological property, and particularly the ductility limit of measuring as flowable is near 0Pa.
In identical concentration, hydrophobic comparison silicon-dioxide is because too high thickening effect and no longer can be in conjunction with (table 5).
Table 5
Rheological property with 20% silicon-dioxide
Silicon-dioxide Ductility limit [Pa] Viscosity D=10s -1 [Pa·s]
Embodiment 3 * - -
Embodiment 4 * - -
Embodiment 5 0 350
Embodiment 6 0 326
*: because too high thickening effect, this concentration (20%) product can't in conjunction with.
Then, mixture is crosslinked, changes standard recipe (be not more than for drying loss 0.3% dewatering filling optimum), and making increases the consumption (catalyzer and inhibitor remain unchanged) of linking agent according to the higher drying loss of used hydrophilic filler.
Table 6
Mechanics and optical property with sulfur product of 20% silicon-dioxide
Silicon-dioxide Tensile strength [N/mm 2] Final elongation [%] Anti tear growth [N/mm] Hardness [Shore A] Rebound resilience [%] Transparency [DE/D65]
Embodiment 5 3.9 244 3 48 62 35
Embodiment 6 4.3 304 21 44 62 53
Summed up the result of mechanics and optical test in the table 6.Should be mentioned that especially the mixture according to embodiment 6 has very high transparency, this is that any other products institute is irrealizable.The anti tear growth property that comprises according to the mixing object height of silicon-dioxide of the present invention also is wonderful.

Claims (8)

1. with the mode pyrolysis preparation of flame oxidation or preferred flame hydrolysis and the water drain silica of 0.000001 to the 40 weight % potassium that mixed.
According to claim 1 hydrophobic or surface modification, by aerosol with potassium adulterated pyrolytic silicon dioxide, it is characterized in that it below being selected from one or more compounds in the group carry out surface modification:
A) (RO) 3Si (C nH 2n+1) and (RO) 3Si (C nH 2n-1) the type organosilane
The R=alkyl
n＝1-20
B) R ' x(RO) ySi (C nH 2n+1) and R ' x(RO) ySi (C nH 2n-1) the type organosilane
The R=alkyl
R '=alkyl
R '=cycloalkyl
n＝1-20
x+y＝3
x＝1，2
y＝1，2
C) X 3Si (C nH 2n+1) and X 3Si (C nH 2n-1) type halo organosilane
X＝Cl、Br
n＝1-20
D) X 2(R ') Si (C nH 2n+1) and X 2(R ') Si (C nH 2n-1) type halo organosilane
X＝Cl、Br
R '=alkyl
R '=cycloalkyl
n＝1-20
E) X (R ') 2Si (C nH 2n+1) and X (R ') 2Si (C nH 2n-1) type halo organosilane
X＝Cl、Br
R '=alkyl
R '=cycloalkyl
n＝1-20
F) (RO) 3Si (CH 2) m-R ' type organosilane
The R=alkyl
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，-NH-CH 2-CH 2-NH 2，
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10 and
R=alkyl, for example methyl, ethyl, propyl group, butyl
-SH
-NR ' R " R  (R '=alkyl, aryl; R "=H, alkyl, aryl; R =H, alkyl, aryl, benzyl, C 2H 4NR " " R " , wherein R " "=A, alkyl, and R " =H, alkyl)
G) (R ") x(RO) ySi (CH 2) m-R ' type organosilane
R "=alkyl x+y=2
=cycloalkyl x=1,2
y＝1，2
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，-OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，-NH-CH 2-CH 2-NH 2，
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10 and
R=alkyl, for example methyl, ethyl, propyl group, butyl
-SH
-NR ' R " R  (R '=alkyl, aryl; R "=H, alkyl, aryl; R =H, alkyl, aryl, benzyl, C 2H 4NR " " R " , wherein R " "=A, alkyl, and R " =H, alkyl)
H) X 3Si (CH 2) m-R ' type halo organosilane
X＝Cl、Br
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，-OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，
-NH-CH 2-CH 2-NH 2
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10, and R=alkyl, for example methyl, ethyl, propyl group, butyl
-SH
I) (R) X 2Si (CH 2) m-R ' type halo organosilane
X＝Cl、Br
R=alkyl, for example methyl, ethyl, propyl group
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，-OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，-NH-CH 2-CH 2-NH 2，
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3，
Wherein R=methyl, ethyl, propyl group, butyl
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10, and R=alkyl, for example methyl, ethyl, propyl group, butyl
-SH
J) (R) 2XSi (CH 2) m-R ' type halo organosilane
X＝Cl、Br
The R=alkyl
m＝0，1-20
R '=methyl, aryl (for example-C 6H 5, the phenyl group that replaces)
-C 4F 9，-OCF 2-CHF-CF 3，-C 6F 13，-O-CF 2-CHF 2
-NH 2，-N 3，-SCN，-CH＝CH 2，-NH-CH 2-CH 2-NH 2，
-N-(CH 2-CH 2-NH 2) 2
-OOC(CH 3)C＝CH 2
-OCH 2-CH(O)CH 2
-NH-CO-N-CO-(CH 2) 5
-NH-COO-CH 3，-NH-COO-CH 2-CH 3，-NH-(CH 2) 3Si(OR) 3
-S x-(CH 2) 3Si (OR) 3, wherein X=1-10, and R=alkyl, for example methyl, ethyl, propyl group, butyl
-SH
Figure A2005800396070006C1
The R=alkyl
R '=alkyl, vinyl
L) D3, D4, D5 type cyclic polysiloxanes
Octamethylcyclotetrasiloxane=D4 for example
Figure A2005800396070006C2
M) polysiloxane of following type or silicone oil
Figure A2005800396070006C3
m＝0，1，2，3，...∞n＝0，1，2，3，...∞u＝0，1，2，3，...∞Y＝CH 3，H，C nH 2n+1 n＝1-20Y＝Si(CH 3) 3，Si(CH 3) 2HSi(CH 3) 2OH，Si(CH 3) 2(OCH 3)Si(CH 3) 2(C nH 2n+1)，n＝1-20
R=alkyl, aryl, (CH 2) n-NH 2, H
R '=alkyl, aryl, (CH 2) n-NH 2, H
R "=alkyl, aryl, (CH 2) n-NH 2, H
R =alkyl, aryl, (CH 2) n-NH 2, H
3. according to the method for the silicon-dioxide of the preparation surface modification of claim 1 or 2, it is characterized in that and to place suitable mixing vessel by aerosol with the adulterated pyrolytic silicon dioxide of potassium, under violent the mixing, randomly at first water and/or diluted acid, mixture with surface-modifying agent or kinds of surface properties-correcting agent sprays described silicon-dioxide then, and randomly continue again to mix 15-30 minute, then tempering 1-6 hour time under 100-400 ℃ temperature.
According to the preparation surface modification of claim 1 or 2, by the method for aerosol with the adulterated pyrolytic silicon dioxide of potassium, it is characterized in that under the situation of having got rid of oxygen, described silicon-dioxide is mixed as far as possible equably with surface-modifying agent; In the treatment chamber of vertical tube furnace form,, mixture and rare gas element are heated to 200-800 ℃, preferred 400-600 ℃ temperature with continuous uniflux technology; Make solid and gaseous reaction product separated from one another; Randomly make solid product depickling and drying then.
5. according to the purposes of silicon-dioxide in silicon rubber of the surface modification of claim 1 or 2.
6. silicon rubber, it is characterized in that it comprise according to claim 1 or 2 by aerosol with the adulterated pyrolytic silicon dioxide of potassium as filler.
7. according to the silicon rubber of claim 6, it is characterized in that described filler is that the BET surface-area of described adulterated oxide compound is 10-1000m with the mode pyrolysis preparation of flame oxidation or flame hydrolysis and the oxide compound of 0.000001 to the 40 weight % dopant that mixed 2The DBP of/g and pyrolytic oxide absorb be detect less than or be lower than this pyrolytic silicon dioxide normal value 85%.
8. according to the silicon rubber of claim 6 or 7, it is characterized in that described silicon rubber is LSR silicon rubber.
CNA200580039607XA 2004-11-18 2005-10-29 Hydrophobic silicon dioxide and its application in silicon rubber Pending CN101061188A (en)

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Application publication date: 20071024