CA2041102C - Flame-resistant polyorganosiloxane compound - Google Patents
Flame-resistant polyorganosiloxane compound Download PDFInfo
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- 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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- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000011521 glass Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 235000019362 perlite Nutrition 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 239000010451 perlite Substances 0.000 claims 1
- 239000010455 vermiculite Substances 0.000 claims 1
- 229910052902 vermiculite Inorganic materials 0.000 claims 1
- 125000006267 biphenyl group Polymers 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- -1 siloxanes Chemical class 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000004826 dibenzofurans Polymers 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
Landscapes
- 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)
- Sealing Material Composition (AREA)
- Silicon Polymers (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.
[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.
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;
[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.
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.
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 |
Family
ID=6405050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002041102A Expired - Fee Related CA2041102C (en) | 1990-04-25 | 1991-04-24 | Flame-resistant polyorganosiloxane compound |
Country Status (5)
| Country | Link |
|---|---|
| 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)
| 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 |
| ATE349486T1 (en) * | 2001-11-24 | 2007-01-15 | Prometheus Developments Ltd | FLAME-RESISTANT 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 |
| SG11202109998QA (en) * | 2019-03-26 | 2021-10-28 | Ppg Ind Ohio Inc | Intumescent coating composition |
Family Cites Families (9)
| 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 |
-
1990
- 1990-04-25 DE DE4013161A patent/DE4013161A1/en active Granted
-
1991
- 1991-04-13 EP EP91105903A patent/EP0453912B1/en not_active Expired - Lifetime
- 1991-04-13 DE DE59104525T patent/DE59104525D1/en not_active Expired - Fee Related
- 1991-04-13 AT AT91105903T patent/ATE118233T1/en not_active IP Right Cessation
- 1991-04-24 CA CA002041102A patent/CA2041102C/en not_active Expired - Fee Related
- 1991-04-25 JP JP3121822A patent/JP2666004B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0453912A3 (en) | 1992-04-15 |
| EP0453912B1 (en) | 1995-02-08 |
| JPH0657140A (en) | 1994-03-01 |
| JP2666004B2 (en) | 1997-10-22 |
| ATE118233T1 (en) | 1995-02-15 |
| CA2041102A1 (en) | 1991-10-26 |
| EP0453912A2 (en) | 1991-10-30 |
| DE4013161A1 (en) | 1991-11-07 |
| DE4013161C2 (en) | 1993-08-05 |
| DE59104525D1 (en) | 1995-03-23 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |