CA2041102C - Flame-resistant polyorganosiloxane compound - Google Patents

Flame-resistant polyorganosiloxane compound Download PDF

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Publication number
CA2041102C
CA2041102C CA002041102A CA2041102A CA2041102C CA 2041102 C CA2041102 C CA 2041102C CA 002041102 A CA002041102 A CA 002041102A CA 2041102 A CA2041102 A CA 2041102A CA 2041102 C CA2041102 C CA 2041102C
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CA
Canada
Prior art keywords
weight
compound
composition according
flame
intumescent
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA002041102A
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French (fr)
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CA2041102A1 (en
Inventor
Roland Leroux
Jurgen Thurk
Reinhard Jonas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schott AG
Dow Silicones Deutschland GmbH
Original Assignee
Dow Corning GmbH
Schott Glaswerke AG
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Application filed by Dow Corning GmbH, Schott Glaswerke AG filed Critical Dow Corning GmbH
Publication of CA2041102A1 publication Critical patent/CA2041102A1/en
Application granted granted Critical
Publication of CA2041102C publication Critical patent/CA2041102C/en
Anticipated expiration legal-status Critical
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/28Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04Ingredients characterised by their shape and organic or inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Silicon Polymers (AREA)
  • Sealing Material Composition (AREA)
  • Building Environments (AREA)

Abstract

A flame-resistant, hardenable polyorganosiloxane composition is described with a content of 2 to 40 weight % hollow glass balls with an outside diameter of up to 200 µm and 3 to 50 weight % of an inorganic intumescent compound which expands at a temperature form 80 to 250°C. The preferred intumescent compound is expandable graphite. The composition can replace the previous compounds provided with polyhalogenated diphenyl compositions in fireproof windows.

Description

FLAME-RESISTANT POLYORGANOSILOXANE COMPOSITION
[0001] Hardenable polyorganosiloxane compositions are most used as high-quality sealing and adhesive materials which can be subjected to high stress. They harden permanently elastically and are used for sealing gaps, e.g. in the field of plumbing and in building, as well as in the manufacture of windows, e.g. as a rebate seal when bedding window panes in frames with putty or for joining glass panes together.
[0002] It is often necessary to make these compositions flame-resistant which up to now was achieved most effectively by adding halogenated diphenyl compounds, e.g.
octabromodiphenyl ether or nonabromodiphenyl (e.g. Geman patent 29 09 462 or German patent application 30 41 031). These halogenated diphenyl compounds in case of fire may form the polyhalogenated dibenzofurans or dibenzodioxins known to be toxic.
Although the flame-resistant polyorganosiloxane compositions prepared in this way generally have adequate flameproofing properties their use should be restricted for the reasons stated above.
[0003] It is the object of the invention to find a fl~une-resistant, hardenable polyorganosiloxane composition of comparable effect which is free from halogenated diphenyl compounds.
[OOOa] Surprisingly, we have found that a well-balanced combination of hollow glass balls and intumescent compound has a flameproofing effect similar to the halogenated diphenyl compounds previously used for this purpose.
2S [0005] The invention provides in one of its aspects a flame-resistant, hardenable polyorganosiloxane composition characterised by a content of 2 to 40 weight %
hollow glass balls with an outside diameter of up to 200 pm and 3 to SO weight % of an inorganic intumescent compound which expands at a temperature from 80 to 240°C.
[0006] The hollow glass balls should have an outside diameter of up to about 200 pm and be present in a quantity from 2 to 40 weight % in the polyorganosiloxane composition.
Hollow glass balls with an outside diameter of less than S pxn can be manufactured only with great difficulty, and therefore expensively, so that for practical reason smaller balls should no longer be used. If the diameter of 200 pm is exceeded an ever increasing proportion of the balls are destroyed by breaking when mixed into the poly-organosiloxane composition. Balls with a diameter of over 60 pm cause increasing roughness of the surface of the finished compound. As this is generally undesirable balls with a diameter of less than 60 ~.m, particularly less than SU pm, are preferred. The quantity of hollow glass balls should not exceed 40 weight % in the composition as the composition then becomes so stiff that it can only be handled with difficulty. In case of a proportion below 2 weight % the effect becomes too small. Particularly preferred is a content from about 6 to 25, in.
particular 10 to 20 weight %. Apart from the flameproofing effect, addition of the hollow glass balls also causes an often desirable reduction in the density and thermal conductivity of the composition.
(0007] In order to keep the flameproofing effect as great as possible it is further advantageous if the balls are filled with a gas which does not in any way contribute to any possible burning, i.e. a non-combustible gas, wherein by combustible gas is also meant oxygen or air. In particular nitrogen and carbon dioxide are available as a charge for the balls but other gases, such as in particular sulphur hexafluoride, are conceivable too wherein balls with the latter gas charge are not commercially available at present. The use of a particular type of glass for the balls is not critical. Both borosilicate glass and ordinary soda-lime glass can be used. The balls which are usually available commercially are made of soda-lime glass.
[0008] The second essential for flameproofing properties is the intumescent compound. The intumescent compound should be of the inorganic kind in order to avoid the formation of readily inflammable cleavage products. It is also important that foaming of the intumescent compound begins before the spontaneous combustion temperature of polyorganosiloxanes or of the softeners etc optionally contained in the polyorganosiloxane composition or of the pyrolysis products formed from them is reached. On the other hand, the intumescent compound should of course still be stable at the highest temperatures of use and working that occur. It has therefore proved to be very generally advantageous if the intumescent compounds begin to foam at temperatures between about 80 and 250°C. It is easy here for anyone skilled in the art to select within this temperature range the intumescent compound or a mixture of different intumescent materials which have the most favourable reaction temperature or the most favourable reaction temperature range for the intended purpose_ Of course, other intumescent materials with a higher initiating temperature may be added as well, which then cause additional intumescence at a later point in time, or those which release non-combustible or flame-retardant gases under temperature stress.
[0009] The intumescent compound should be used in a quantity from 3 to SO
weight %. Below 3 weight % an adequate effect is no longer obtainable and above SO
weight % the polyorganosiloxane composition in case of fire is expanded so much that the resulting composition no longer has sufficient cohesion. Good results are obtained with a content from 5 to 26 weight % of intumescent compound. The optimum content can easily be ascertained by preliminary tests, wherein it is to be taken into account that the use of intumescent compounds with high intumescence allows a lower percentage content, and that intumescent compounds with lower intumescence must be added in a larger quantity.
[0010] Intumescent compounds are abundantly available commercially and well known to anyone skilled in the art. As intumescent compounds there are used compounds which in case of fire either expand greatly themselves or which split off e.g.
water of crystallisation or binding in vapour form or carbon dioxide and hence cause a very great increase in volume of the whole polyorganosiloxane compound. Suitable for use within the above temperature range are e.g. vermiculites, perlites, mica, expandable graphite, wermlandite, thanmasite, hydrotalcite etc. Most particularly good results are obtained with expandable graphite, preferably in quantities from S to 25 weight %, in particular from 7 to 15 weight %.
[0011] The formulations of polyorganosiloxane matrices which can be made flame-resistant by the content o f hollow glass balls and inorganic intumescent compound according to the invention, are well known to anyone skilled in the art and are described in countless publications. The matrices consist of a base polymer, optionally a softener, fillers and reinforcing materials as well as a crosslinking agent or crosslinlcing catalyst. As base polymers there are used mainly polydimethyl and polydimethylphenyl siloxanes which contain crosslinking groups containing hydroxyl or vinyl or hexenyl, preferably those which are terminally blocked with these groups. Silicone oils, i.e. generally dimethyl polysiloxanes or dimethylphenyl siloxanes terminally blocked with methyl, are used as softeners, the content of which is preferably kept as low as possible due to their higher inflammability. To improve the mechanical properties of the end product soot or silicic acid, particularly pyrogenic silicic acid, is added to the compound. Inert fillers are e.g.
diatomaceous earth.

Crosslinking catalysts are e.g. peroxides for compounds which should be hardenable only at an elevated temperature. For cold setting two-component compounds the matrix is crosslinked with e.g. tetraethyl silicate as the crosslinking agent and e.g.
dibutyltin dilaurate as the catalyst. In case of cold-setting single-component compositions, e.g.
the so-called acetoxy system, crosslinking takes place by means of a crosslinking agent which can be activated by atmospheric moisture. With these compositions care must be taken that the intumescent compound does not accidentally initiate hardening. Details of matrices and catalyst systems can be found in the current handbooks, e.g. Noll, "Chemistry and Technology of Silicones", Verlag Chemise, Weinheim/Bergstr 1960 or "Silicones, Chemistry and Technology", Vulkan Verlag, Essen 1989. Independently of the selected crosslinking system the properties of hardened, crosslinked silicone rubbers are similar to each other so that the addition of hollow glass balls and intumescent compounds according to the invention works in all cases. The polymer matrices as well as crosslinking agents, catalysts etc are available both separately and in largely pre-prepared mixtures from numerous well-known chemical companies.
[0012] In any case that basic structure of the flame-resistant, hardenable polyorganosiloxane composition according to the invention or the compound to be worked into suitable silicone rubber products may be as follows:
a. 10 to 85 weight % uncatalysed ordinary commercial siloxane (base polymer);
b. 0 to 30 weight % polyorganosiloxane as softener (silicone oil, e.g.
polydimethyl siloxane terminally blocked with methyl);
c. 0 to 50 weight % higher disperse, active filler as reinforcing component (pyrogenic silicic acid);
d. 0 to 10 weight % pigments, pure or in paste form;
e. 0.5 to 15 weight % crosslinking agent/catalyst, matched to the respective crosslinking system;
~ 0 to 50 weight % inactive filler;
g. 2 to 40 weight % hollow glass balls; and h. 3 to SO weight % intumescent compound.

[0013) The polyorganosiloxane compositions according to the invention have excellent flameproofing properties without need to fear the formation of toxic pyrolysis products in case of fire.
Example [0014] A flame-resistant, hardenable polyorganosiloxane composition of the following composition was prepared:
66 weight % polydimethylphenyl siloxane terminally blocked with OH;
4.5 weight % atmospheric moisture-reacting crosslinking agent of the acetate type (including 0.02 weight % Sn catalyst);
4.5 weight % pyrogenic silicic acid as reinforcing agent;
weight % air-filled hollow glass balls of diameter about 40 um; and 15 10 weight % expandable graphite (manufacturer: SI<iRI, type FR 90-60/80).
[0015] A fireproof double glazing unit consisting of a pre-stressed borosilicate glass pane with a thickness of 6mm and a float glass pane with a thickness of 4mm, was produced by holding the panes at a distance of l2mm from each other by means of a steel spacer and cementing them in the edge gap with the above-mentioned compound. After hardening of the composition the unit was installed in a steel frame and the rebates above the sealing strips sealed, also with the compound described above. After hardening of the composition, the window was subjected to a fire test in accordance with DIN 4102., part 13, the borosilicate glass pane being located on the flame side. It turned out that the composition maintained its sealing function up to the end of the test after 60 minutes and that above all on the side remote from the fire no flames arose from the seal or pyrolysis products thereof. Such a good fireproofing effect could previously be obtained only with the flameproofing combination of chalk and a highly brominated diphenyl compound described in German patent 29 09 462.

Claims (10)

1. A flame-resistant, hardenable polyorganosiloxane composition characterised by a content of 2 to 40 weight % hollow glass balls with an outside diameter of up to 200 µm and 3 to 50 weight % of an inorganic intumescent compound which expands at a temperature from 80 to 240°C.
2. A composition according to Claim 1 characterised by a content of 10 to 20 weight % hollow glass balls.
3. A composition according to Claim 1 characterised in that the hollow glass balls are filled with a non-combustible gas.
4. A composition according to Claim 1 characterised by a content of 5 to 25 weight % intumescent compound.
5. A composition according to Claim 1 characterised in that the intumescent compound is selected from the group consisting of vermiculite, perlite, mica, expandable graphite, wermlandite, thanmasite and hydrocalcite.
6. A composition according to Claim 5 characterised by the use of expandable graphite as the intumescent compound.
7. A composition according to Claim 6 characterised by a content of 8 to 15 weight % expandable graphite.
8. Use of a polyorganosiloxane composition according to Claim 1 as a flame-resistant adhesive and sealing compound.
9. Use of a polyorganosiloxane composition according to Claim 1 as an adhesive and sealing compound for fire-retardant windows.
10. A method for improving the fire resistance of a polyorganosiloxane composition which comprises providing in a hardenable polyorganosiloxane composition from 2 to 40 weight % of hollow glass balls with an outside diameter of up to 200 µm and 3 to 54 weight % of an organic intumescent compound which expands at a temperature from 80°C to 240°C.
CA002041102A 1990-04-25 1991-04-24 Flame-resistant polyorganosiloxane compound Expired - Fee Related CA2041102C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4013161A DE4013161A1 (en) 1990-04-25 1990-04-25 FLAME RESISTANT POLYORGANOSILOXANE
DE4013161.0 1990-04-25

Publications (2)

Publication Number Publication Date
CA2041102A1 CA2041102A1 (en) 1991-10-26
CA2041102C true CA2041102C (en) 2003-02-25

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CA002041102A Expired - Fee Related CA2041102C (en) 1990-04-25 1991-04-24 Flame-resistant polyorganosiloxane compound

Country Status (5)

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EP (1) EP0453912B1 (en)
JP (1) JP2666004B2 (en)
AT (1) ATE118233T1 (en)
CA (1) CA2041102C (en)
DE (2) DE4013161A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4120561A1 (en) * 1991-06-21 1992-12-24 Hilti Ag ADHESIVE, SEALING AND ADHESIVE MADE ON SILICONE BASE
DE4135678A1 (en) * 1991-10-30 1993-05-06 Chemie Linz (Deutschland) Gmbh, 6200 Wiesbaden, De Thermally expandable fire protection materials - contain expanded graphite, polymeric binders, substances which form carbon skeleton when exposed to fire, and hollow microspheres, etc.
DE4200458C2 (en) * 1992-01-10 1995-09-21 Flam X Brandschutz Use of a fire retardant mass for the production of flexible fire protection tarpaulins
DE19620816A1 (en) * 1996-05-23 1997-11-27 Wacker Chemie Gmbh Crosslinkable organopolysiloxane compositions to be flame-resistant elastomers
JP2000204332A (en) * 1999-01-08 2000-07-25 Minnesota Mining & Mfg Co <3M> Heat-peeling adhesive composition and bonded structural form
EP1314753B1 (en) * 2001-11-24 2006-12-27 Prometheus Developments Ltd. Fire retardant composition
CN107586456A (en) * 2017-09-30 2018-01-16 太仓市金锚新材料科技有限公司 Novel high-strength silicone rubber fireproof preserving and sealing material
CN107586457A (en) * 2017-09-30 2018-01-16 太仓市金锚新材料科技有限公司 The preparation method of high-strength silicone rubber fire retardant anticorrosion encapsulant
AU2020245498B2 (en) * 2019-03-26 2023-06-01 Ppg Industries Ohio, Inc. Intumescent coating composition

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5316883A (en) * 1976-07-30 1978-02-16 Nitto Electric Ind Co Electric insulator
US4299872A (en) * 1977-09-16 1981-11-10 The United States Of America As Represented By The Secretary Of The Navy Intumescent material-honeycomb thermal barrier
US4286013A (en) * 1980-08-29 1981-08-25 Minnesota Mining & Manufacturing Company Flame barrier
JPS6022017B2 (en) * 1981-10-14 1985-05-30 信越化学工業株式会社 Flame-resistant silicone rubber composition
US4404305A (en) * 1982-02-16 1983-09-13 Dow Corning Corporation Flame retardant polyorganosiloxane resin compositions
US4433069A (en) * 1983-01-03 1984-02-21 Dow Corning Corporation Method for preparing flame resistant polysiloxane foams and foams prepared thereby
US4689358A (en) * 1985-08-06 1987-08-25 The Brooklyn Union Gas Company Insulating polymer concrete
US4719251A (en) * 1985-08-19 1988-01-12 Dow Corning Corporation Silicone water base fire barriers
DE3602888A1 (en) * 1986-01-31 1987-08-06 Bayer Ag INTUMESCENT POLYSILOXANE MOLDS

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Publication number Publication date
EP0453912A2 (en) 1991-10-30
EP0453912A3 (en) 1992-04-15
ATE118233T1 (en) 1995-02-15
JP2666004B2 (en) 1997-10-22
DE4013161A1 (en) 1991-11-07
CA2041102A1 (en) 1991-10-26
DE4013161C2 (en) 1993-08-05
EP0453912B1 (en) 1995-02-08
DE59104525D1 (en) 1995-03-23
JPH0657140A (en) 1994-03-01

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