Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS20020037936 A1
Publication typeApplication
Application numberUS 09/740,039
Publication dateMar 28, 2002
Filing dateDec 20, 2000
Priority dateDec 22, 1999
Also published asUS7282236, US20040024070, US20070202030
Publication number09740039, 740039, US 2002/0037936 A1, US 2002/037936 A1, US 20020037936 A1, US 20020037936A1, US 2002037936 A1, US 2002037936A1, US-A1-20020037936, US-A1-2002037936, US2002/0037936A1, US2002/037936A1, US20020037936 A1, US20020037936A1, US2002037936 A1, US2002037936A1
InventorsGunther Michael, Volker Kasack, Rudiger Nowak
Original AssigneeGunther Michael, Volker Kasack, Rudiger Nowak
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydrophobic silica
US 20020037936 A1
Abstract
Hydrophobic, pyrogenically produced silica having a tamped density of 55 to 200 g/l is produced by hydrophobizing pyrogenically produced silica and then compacting it. The silica may be used for the production of dispersions.
Images(5)
Previous page
Next page
Claims(10)
1. A hydrophobic, pyrogenically produced silica, having a tamped density of 55 to 200 g/l.
2. The hydrophobic, pyrogenically produced silica according to claim 1 having a tamped density of 60 to 200 g/l.
3. The hydrophobic, pyrogenically produced silica according to claim 1 which is hydrophobicized by reaction with a halogen-free silane.
4. The hydrophobic, pyrogenically produced silica according to claim 4 wherein said silica has a chloride content of less than or equal to 100 ppm.
5. A process for the production of the hydrophobic, pyrogenically produced silica as claimed in claim 1, comprising hydrophobizing pyrogenically produced silica and then compacting said silica.
6. The process according to claim 5 wherein said compacting is by roller compactor.
7. The process according to claim 5 wherein said compacting is by belt filter press.
8. A hydrophobic, pyrogenically produced silica having been produced by the process of claim 5.
9. Use of the hydrophobic, pyrogenically produced silica as claimed in claim 1 for the production of dispersions.
10. A dispersion of a hydrophobic, pyrogenically produced silica produced by the process of claim 5.
Description
    REFERENCE TO A RELATED APPLICATION
  • [0001]
    This application claims the benefit of provisional application 60/171,667 filed Dec. 27, 1999 which is relied on and incorporated by reference.
  • INTRODUCTION AND BACKGROUND
  • [0002]
    This invention relates to a hydrophobic, pyrogenically produced silica, to a process for the production thereof and to the use thereof.
  • [0003]
    It is known to compact hydrophilic, pyrogenically produced silica (EP 0 280 854 B1). Disadvantageously, as tamped or bulk density increases, thickening action declines in a linear manner. Dispersibility also falls as density increases. This results in unwanted speckling. Thus, once compacted, a hydrophilic, pyrogenically produced silica may only be used for a limited number of applications.
  • [0004]
    It is therefore an object of the present invention to avoid the problems of compacted, hydrophobic, pyrogenically produced silica of the past.
  • SUMMARY OF THE INVENTION
  • [0005]
    The above and other objects of the present invention can be achieved by developing a hydrophobic, pyrogenically produced silica having a tamped density of 55 to 200 g/l. The tamped density is preferably from 60 to 200 g/l.
  • [0006]
    A feature of the present invention is a process for the production of the hydrophobic, pyrogenically produced silica having a bulk density of 55 to 200 g/l, which process is characterised in that pyrogenically produced silica is hydrophobized using known methods and then compacted.
  • [0007]
    Hydrophobing can preferably be performed by means of halogen-free silanes. The chloride content of the silica can be less than or equal to 100 ppm, preferably from 10 to 100 ppm. Compaction can be performed by means of a roller compactor. Compaction can preferably be performed by means of a belt filter press according to EP 0 280 851 B1, which reference is relied on and incorporated by reference.
  • [0008]
    The hydrophobic, pyrogenically produced silica used for purposes of the present invention can be, for example, the silicas known as:
  • [0009]
    Aerosil R 812 or Aerosil R 812S, having the group —O—Si (CH3)3
  • [0010]
    Aerosil R 202, Aerosil MS 202, Aerosil MS 202, Aerosil R 106 or
  • [0011]
    Aerosil R 104 having the group
  • [0012]
    Aerosil R 805 having the group
  • [0013]
    These are commercially available products from Degussa Hüls AG.
  • [0014]
    The hydrophobic, pyrogenic silica according to the invention having a tamped density of 55 to 200 g/l exhibits the following advantages:
  • [0015]
    Transport costs are distinctly lower as a result of the higher tamped density.
  • [0016]
    Once dispersed, the silica according to the invention is in the form of relatively small aggregates. In other words, the dispersions are more finely divided because the silica according to the invention is more readily dispersible.
  • [0017]
    The dispersions produced using the silica according to the invention exhibit a lower Grindometer value.
  • [0018]
    Both UV transmission transparency and visual transparency of the dispersions are distinctly improved by using the silica according to the invention.
  • [0019]
    Dispersions containing the silicas according to the invention exhibit distinctly increased stability because the tendency towards settling is distinctly lower.
  • [0020]
    Another advantage of the silica according to the invention is reduced dusting during incorporation and the distinctly reduced incorporation or wetting time in for example, liquid systems.
  • [0021]
    In comparison with hydrophobic, pyrogenic silica of a lower bulk density, the hydrophobicity of the silica according to the invention is unchanged. Thickening action is also unchanged.
  • DETAILED DESCRIPTION OF THE INVENTION
  • [0022]
    The present invention will be further understood with reference to the following detailed embodiments thereof.
  • EXAMPLE 1
  • [0023]
    Various hydrophobic, pyrogenically produced silicas are investigated, wherein different compaction states are compared.
  • [0024]
    The following definitions apply:
  • [0025]
    bulk=pulverulent, unmodified silica
  • [0026]
    CF=silica compacted with a Carter filter
  • [0027]
    VV 60=silica compacted to a tamped density of approx. 60 g/l
  • [0028]
    VV 90=silica compacted to a tamped density of approx. 90 g/l
  • [0029]
    Aerosil grades R 202, US 202, US 204, R 812, R 812S and R 805 are investigated. The results are shown in Table 1.
  • [0030]
    As evaluated by the Corning Glass methanol wettability method, the degree of compaction has virtually no appreciable influence on hydrophobicity. Viscosity also exhibits no clear systematic dependency upon tamped density. Especially for R 812, dispersibility improves with increasing density. R 812 S, which contains more SiOH groups than R 812, exhibits the above phenomenon less markedly.
  • [0031]
    US 202 and US 204 have very comparable rheological properties and are inferior to AEROSIL R 202.
  • [0032]
    Surprisingly, the compacted variants, in particular of R 812, R 202 and US 202/4, exhibit an incorporation time reduced by up to half. The compacted silicas moreover exhibit reduced dusting.
    444701 444702 444703 444704 444705
    AER AER AER AER AER 144706 414707 414708 144709 441710 444711
    202 202 202 202 805 AER805 AER805 AFR805 AER812 AER812 AER8I2
    PA Test Method CE CF VV60 VV90 bulk CF VV60 VV90 bulk CF VV60
    0330 Viscosity, 459 456 382 430 190 184 185 178
    epoxy before cure
    0335 Viscosity, 544 54.7 49.4 52.8 42 41.7 39 43
    epoxy after cure
    0340 Thickening action 11.7 133 11.5
    0410 Cindometer value 127 102 92
    0420 Methanol wettability
    0701 Tamped density 45 50 51 75 44 62 55 68 45 44 50
    0920 Agglomerate strength 11 20 18 15 15 20
    0930 Handr. [sic] sieve 0 24 4 27 0 36 7 19 0 0
    oversize
    0955 Effectiveness 258 271 203 266 235 260 236 258 166 185 169
    0965 Effectiveness (UT) 280 290 226 295 271 284 270 288 197 213 209
    0975 Settling (effectiveness) 15 15 15 8 10 15 10 5 13 15 8
    444713 444714 444715 444716
    444712 AER AER AER AER 444717 444718 444719 444720 444721 444722 444723
    AER812 812S 812S 812S 812S US202 US202 US202 US204 US204 US204 US204
    PA Test Method VV90 bulk CF VV60 VV90 bulk CF VV60 bulk CF VV60 VV90
    0330 Viscosity, 3504 377.6 380.8 3792 350.4 358.4 368
    epoxy before cure
    0335 Viscosity, 507 45.9 453 49.9 47 52.6 50.7
    epoxy after cure
    0340 Thickening action 11.1 17.3 17.3 18.2 17
    0410 Cindometer value 77 93 110 110 100
    0420 Methanol wettability
    0701 Tamped density 73 49 50 58 75 39 50 67 44 45 57 71
    0920 Agglomerate strength 22 28 10 15 16 23
    0930 Handr. [sic] sieve 12 0 0 0 4 0 27 36 0 0 3 20
    oversize
    0955 Effectiveness 159 168 169 187 209 320 304 320 186 193 192 201
    0965 Effectiveness (UT) 225 201 200 216 235 336 327 346 223 225 225 230
    0975 Settling (effectiveness) 5 8 8 3 0 15 10 3 10 10 10 10
  • EXAMPLE 2
  • [0033]
    Investigation of the influence of higher compaction on applicational properties
    AE R 812, AE R 812,
    AE R 812, compacted compacted
    uncom- RHE RHE
    pacted UB 3847-2 UB 3847-3
    UB 3847-1 (4) (5) AE R 812
    10 kg 15 kg 20 kg RHE
    sack sack sack specific.
    Tamped density (DIN ISO g/l  50  87 106 approx.
    787/11) 50
    Effectiveness, ethanol 184 214 209 216 1)
    (0955)
    Effectiveness (UT), 218 260 290 236 1)
    ethanol (0965)
    Settling vol. %  10  1  1   1)
    (effectiveness, high-
    speed mixer)
  • [0034]
    1. Determined on standard sample (UB 3391) RHE in the above table indicates the Rheinfelden plant located in Germany.
  • [0035]
    Rheological testing:
  • [0036]
    Polymer: Araldit M (biphenol-1-expoxy resin by Ciba-Geogy, in the form of clear yellow liquid).
  • [0037]
    Thixotroping agent: R 202 and R 812 Additive:
  • [0038]
    Sample A R 812 10 kg 2-10123
    Storage time 5 rpm 50 rpm
    in days [mPa*s] [mPa*s] T.I.
    Sample production date: 24.02.1994  Spindle: 5
    0 16600 4460 3.72
    80-85μ
    Sample AR 812 15 kg 1.0/8 min
    Sample production date: 24.02.1994 Spindle: 5
    0 15100 4060 3.72
    50-60μ
    Sample A R 812 20 kg 0.6/14 min
    Sample production date: 24.02.1994 Spindle: 5
    0 15100 4020 3.73
    50-60μ
  • [0039]
    Compaction may amount to a type of predispersion. Accordingly, effectiveness values rise with tamped density, i.e. the particles effectively present in the ethanol dispersion become smaller and the compacted samples exhibit distinctly less settling. Any suitable organic solvent can be used to form the dispersion.
  • [0040]
    The compacted samples accordingly have a more favourable Grindometer value in Araldit. However, since the larger particles have a decisive influence on thickening action, the property declines slightly on compaction.
  • [0041]
    It may be seen from the graph of effectiveness values that, while the highly compacted AEROSIL R 812 sample may indeed still be broken up with the Ultra-Turrax mixer (0965), it can no longer be broken up with the high speed mixer (0955). Due to the smaller surface area of AEROSIL R 202 (and to the consequently theoretically improved dispersibility), this phenomenon hardly occurs with AEROSIL R 202.
  • [0042]
    As compaction rises, the particles effectively present in an ethanol dispersion thus become smaller and 90° angle scattering rises due to Rayleigh scattering. Total scattering (over all angles), however, falls and the samples become distinctly more transparent on visual inspection, as is also substantiated by the UV transmission spectra.
  • [0043]
    Compaction has no influence on hydrophobicity, which in each case substantially corresponds to that of the standard sample.
  • EXAMPLE 3
  • [0044]
    Investigation of the influence of higher compaction on applicational properties.
    AE R 202, AE R 202,
    AE R 812, compacted compacted
    uncompacted RHE RHE
    UB 3848-1 UB 3848-2 UB 3848-3
    2-02024 2-01024- 2-01024- AE R 202
    10 kg (2) (3) RHE
    sack 15 kg sack 20 kg sack specific.
    Tamped density (DIN ISO 787/11) g/l  51  93 119 approx. 60 3)
    Effectiveness, ethanol (0955) 319 334 336 334 1)
    Effectiveness (UT), ethanol (0965) 346 365 373 339 1)
    Settling vol.%  10  5  1
    (effectiveness, high-speed mixer)
  • [0045]
    1) Determined on standard sample (UB 3391)
  • [0046]
    3) Guide value
  • [0047]
    The compacted AEROSIL R 202 samples behave in a similar manner to the compacted AEROSIL R 812 samples.
  • [0048]
    Reference is thus made to Example 2 with regard to the discussion.
  • [0049]
    The parameter of “effectiveness” reported in the tables herein relates to the high degree of fineness of the particle. This is therefore an indicator of high transparency and good stability of the resulting dispersions.
  • [0050]
    Further variations and modifications of the foregoing will be apparent to those skilled in the art and are intended to be encompassed by the claims appended hereto.
  • [0051]
    German priority application filed Dec. 22, 2000 199 61 933.6 is relied on and incorporated herein by reference.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US7095929May 15, 2003Aug 22, 2006Degussa AgCable gels for optical fibre cables
US7452600 *Jul 29, 2003Nov 18, 2008Degussa AgSilica
US8022130 *Nov 17, 2004Sep 20, 2011Evonik Degussa GmbhAdhesive and sealant systems
US8202502Jul 6, 2007Jun 19, 2012Cabot CorporationMethod of preparing hydrophobic silica
US8435474 *Jul 6, 2007May 7, 2013Cabot CorporationSurface-treated metal oxide particles
US8455165Jul 6, 2007Jun 4, 2013Cabot CorporationCyclic-treated metal oxide
US20050232556 *May 15, 2003Oct 20, 2005Rudiger NowakCable gels for optical fibre cables
US20050244642 *Jul 29, 2003Nov 3, 2005Jurgen MeyerSilica
US20070129480 *Nov 17, 2004Jun 7, 2007Rudiger NowakAdhesive and sealant systems
US20080069753 *Jul 6, 2007Mar 20, 2008Cabot CorporationMethod of preparing hydrophobic silica
US20080070140 *Jul 6, 2007Mar 20, 2008Cabot CorporationSurface-treated metal oxide particles
US20080070143 *Jul 6, 2007Mar 20, 2008Cabot CorporationCyclic-treated metal oxide
US20080070146 *Jul 6, 2007Mar 20, 2008Cabot CorporationHydrophobic-treated metal oxide
US20100254876 *Nov 18, 2008Oct 7, 2010Evonik Degussa GmbhFlakes hydrophobic through-and-through and comprising pyrogenically prepared silicon dioxide
US20130129597 *Jan 17, 2013May 23, 2013Cabot CorporationSurface-treated metal oxide particles
WO2009074433A1 *Nov 18, 2008Jun 18, 2009Evonik Degussa GmbhFlakes hydrophobic through-and-through and comprising pyrogenically prepared silicon dioxide
Classifications
U.S. Classification516/111
International ClassificationC01B33/18, C09C1/30
Cooperative ClassificationC01P2006/80, C09C1/309, C01P2006/20, C01P2004/61, Y10T428/2995, C09C1/3684, C01P2004/50, C09C1/3036, C01P2006/22, C01B33/18, C01P2006/11, C01P2006/90, C01P2006/10, C09C1/3081
European ClassificationC09C1/30D4F, C09C1/30P, C09C1/36D12, C09C1/30D12, C01B33/18
Legal Events
DateCodeEventDescription
Apr 16, 2001ASAssignment
Owner name: DEGUSSA-HULS AKTIENGESELLSCHAFT, GERMANY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MICHAEL, GUNTHER;KASACK, VOLKER;NOWAK, RUDIGER;REEL/FRAME:011696/0475;SIGNING DATES FROM 20010124 TO 20010130
Oct 6, 2001ASAssignment
Owner name: DEGUSSA AG, GERMANY
Free format text: MERGER;ASSIGNOR:DEGUSSA-HULS AKTIENGESELLSCHAFT;REEL/FRAME:012322/0909
Effective date: 20010209
Feb 22, 2010ASAssignment
Owner name: EVONIK DEGUSSA GMBH,GERMANY
Free format text: CHANGE ADDRESS;ASSIGNOR:EVONIK DEGUSSA GMBH;REEL/FRAME:023985/0296
Effective date: 20071031
Owner name: DEGUSSA GMBH,GERMANY
Free format text: CHANGE OF ENTITY;ASSIGNOR:DEGUSSA AG;REEL/FRAME:023998/0937
Effective date: 20070102
Owner name: EVONIK DEGUSSA GMBH, GERMANY
Free format text: CHANGE ADDRESS;ASSIGNOR:EVONIK DEGUSSA GMBH;REEL/FRAME:023985/0296
Effective date: 20071031
Owner name: DEGUSSA GMBH, GERMANY
Free format text: CHANGE OF ENTITY;ASSIGNOR:DEGUSSA AG;REEL/FRAME:023998/0937
Effective date: 20070102
Feb 23, 2010ASAssignment
Owner name: EVONIK DEGUSSA GMBH,GERMANY
Free format text: CHANGE OF NAME;ASSIGNOR:DEGUSSA GMBH;REEL/FRAME:024006/0127
Effective date: 20070912
Owner name: EVONIK DEGUSSA GMBH, GERMANY
Free format text: CHANGE OF NAME;ASSIGNOR:DEGUSSA GMBH;REEL/FRAME:024006/0127
Effective date: 20070912