Flame Retardant Polymer Compositions

(19) United States US 20100056687A1 (12) Patent Application Publication (10) Pub. No.: US 2010/0056687 A1 Diakoumakos et al. (43) Pub. Date: Mar. 4, 2010 (54) FLAME RETARDANT POLYMER (30) Foreign Application Priority Data COMPOSITIONS Dec. 20; 2002 (GB) ................................. .. 0229810.7 (75) Inventors: Constantinos D. Diakoumakos; Publication Classification Trumpington (GB); Dimiter (51) Int CL Lubomirov Kotzev; Corby (GB) C08K 5/09 (2006.01) B05D 3/02 (2006.01) Correspondence Address: C 08K 3/38 (2006.01) Patent Counsel C08K 3/10 (2006.01) Huntsman Advanced Materials Americas LLC C 08K 3/16 (2006.01) Legal Dept., 10003 VVoodloch Forest Drive C03K 3/22 (2006.01) The Woodlands, TX 77380 (US) C08K 3/34 (2006.01) (52) U.S. Cl. .................... .. 524/396; 427/385.5; 524/399; (73) Assignee: Huntsman Advanced Materials Americas LLC; The Woodlands; TX (US) (21) Appl. No.: 12/613,691 (22) Filed: Nov. 6, 2009 Related U.S. Application Data (63) Continuation of application No. 10/ 539,844; filed on Jan. 20; 2006; now Pat. No. 7,635,728; filed as appli- cation No. PCT/GB2003/005503 on Dec. 18; 2003. 524/400; 524/404; 524/405; 524/406; 524/413; 524/431; 524/434; 524/436; 524/437; 524/442; 524/443; 524/445; 524/456; 977/773 (57) ABSTRACT Flame retardant compositions are disclosed which comprise (a) at least one particulate material which expands on the application of heat and (b) at least one particulate nano-filler; together with at least one polymer and/or at least one curable monomer or oligomer. The compositions may also contain certain silicon-based materials. Flarne-retardant composi- tions comprising polyorganosiloxanes containing one or more functional groups selected from amino; hydroxyl; meth- acrylic; acrylic and epoxy groups; are also disclosed. US 2010/0056687 A1 FLAME RETARDANT POLYMER COMPOSITIONS [0001] The present invention relates to flame retardant polymer compositions and to curable compositions for pre- paring them. [0002] In the modern polymer industry, flame-retardants that are used in polymers are generally based on halogens (mainly Cl and Br) and organic or inorganic phosphorus compounds (e.g. ammonium polyphosphate, red phospho- rus). Classically, intumescent fire retarded materials contain a char-forming agent which can be a polyol (e.g. pentaerythri- tol), a catalyst for char formation (usually a phosphoric acid derivative) and a foaming agent, typically melamine. Although these reduce hazards during polymer pyrolysis and combustion by retarding a fire, they nevertheless can generate large amounts of smoke, and they also present serious eco- logical threats. There is a need for non-toxic (halogen-, phos- phorus- and melamine-free), ecologically safe fire retardant or flame retardant or fire resistant (these terms being synony- mous for present purposes) compositions characterized by low flammability and limited smoke levels. [0003] lntumescent materials have been used as flame retardants. Expandable graphite has attracted interest over the last few years for the development of novel chemical intu- mescent systems. For example U.S. Pat. No. 3,574,644 describes a process for increasing the flame resistance of flammable materials by the incorporation of expandable graphite flakes, while U.S. Pat. No. 6,472,070 describes fire- resistant paints containing amongst other ingredients, an epoxy resin, a hardener, and expandable graphite. [0004] Particulate materials known as nanofillers may also be used in composite materials. For example, Wo 99/09070 describes polymer foams which may contain nanofillers. W0 00/ 66657 describes a polymer composition comprising a polymer and a nano -clay together with a second polymer, and GB 2367064 describes a polymer composition containing a polyolefin together with a nano-clay filler and an additional filler. WO 99/35186 describes nanocomposites based on a polymeric matrix and a layered double hydroxide, and pro- vides information on the preparation of such materials. [0005] We have now found that enhanced flame retardancy in polymer systems can be obtained by using a specific com- bination of particulate flame retardants. Accordingly, the invention provides a particulate composition for use as a flame retardant additive, which comprises (a) at least one particulate material which expands on the application of heat and (b) at least one particulate nano-filler. [0006] The particulate compositions of the present inven- tion may be used in the manufacture of flame-proof polymers, and may be composited directly with the polymer, or with one or more curable monomers, oligomers and/or polymers for subsequent curing to produce the finished polymer. Accord- ingly, the invention further provides a composition containing a particulate composition according to the invention together with at least one polymer and/ or at least one curable monomer or oligomer. [0007] Any desired monomer, oligomer or polymer, or any mixture thereof, may be present. The fire retardant compo si- tions are suitable for inclusion in a wide variety of composi- tions which contain or can be cured to give polymers or polymer-based materials, for example, polyamides, nylons, polyesters, epoxy resins, ABS combinations, halogenated Mar. 4, 2010 polymers such as poly(vinyl chloride) (PVC), polyethylenes, polypropylenes, polyurethanes, polyacrylates/poly- methacrylates (home- and copolymers), polystyrenes, poly- chlopropene, phenolics, silicones, and silicone rubbers and copolymers and combinations of polymers. Preferably a cur- able monomer, oligomer or polymer contains one or more groups selected from epoxy, acrylic, methacrylic, amine, hydroxyl, carboxyl, anhydride, olefinic, styrene, acetoxy, methoxy, ester, cyano, amide, imide, lactone, isocyanate or urethane. The compositions may if appropriate contain a cur- ing agent. For example, the composition may comprise a mixture of a polyisocyanate bearing at least two isocyanate groups with a polyol bearing at least two hydroxyl groups or with an amine or a carboxylic acid; or a mixture of acrylates or methacrylates with an appropriate initiator. [0008] The invention also provides a cured article which comprises a polymer matrix in association with a flame retar- dant composition according to the invention. [0009] The invention also provides a process for the manu- facture of a cured article, which comprises admixing at least one particulate material which expands on the application of heat, at least one particulate nano filler, and at least one curable monomer, oligomer or polymer, and subsequently curing the resulting mixture. The three components of the curable mixture may be mixed together in any desired order, although preferably the nano-filler is dispersed within the curable material as a first step. Curing may be carried out by any appropriate method, for example the application of heat or light, or the addition of a suitable curing agent, for example an amine, carboxylic acid, carboxylic acid ar1hydride, or phe- nol. [0010] Compositions according to the invention are espe- cially suitable for use as adhesives, sealants thermal insula- tors and coatings. Accordingly, the invention further provides a method of making an adhesive bond, a seal or a coating, which comprises applying a monomer, oligomer and/or poly- mer-containing composition according to the invention to a substrate and if required curing said composition. [0011] The material comprising component (a) is such that it expands on the application of heat such as experienced during a fire. The material should be such that it expands when exposed to a temperature of above 500° C., preferably above 300° C., especially above 100° C. Preferably compo- nent (a) comprises expandable graphite. [0012] Expandable graphite may be manufactured from natural crystalline graphite flake. Deposits of crystalline graphite are numerous and found around the world, usually as inclusions in metamorphic rock, or in the silts and clays that result from their erosion. Graphite is recovered from the ore by crushing and flotation and is usually beneficiated to give graphite flake that is 90-98% carbon. Crystalline graphite consists of stacks of parallel planes of carbon atoms. Because no covalent bonding exists between the layers other mol- ecules can be inserted between them (intercalation). In one commercial process for the production of expandable graph- ite, sulphuric acid is inserted into the graphite after which the flake is washed and dried. The intercalant is trapped inside the graphite lattice, so the final product is a dry, pourable, non- toxic material with minimal acidity (pH~3-4). When the intercalated graphite is exposed to heat or flame, the inserted molecules decompose to generate gas. The gas forces apart the carbon layers and the graphite expands. [0013] The flakes of expandable graphite are generally plate-like. For a 50-mesh flake, the typical length and width US 2010/0056687 A1 are about 0.5 mm, with the largest particles generally being about 0.9 mm, while the typical thickness is about 0.08 mm. For a 80-mesh flake, the typical length and width are about 0.4 mm whilst the typical thickness is about 0.07 mm. A wide variety of expandable graphites of different particle sizes, acidity, decomposition temperatures, and expansion efli- ciency, are nowadays commercially available (e.g. GRAF- GUARD® product series by Graftech). Any of these are suitable foruse in the present invention. The various grades of expandable graphite available typically expand when exposed to temperatures in the range of 160 to 260° C. or higher. [0014] The proportion of component (a), especially expandable graphite, used in a monomer, oligomer and/or polymer-containing composition of the invention preferably ranges between 0.1 and 95% w/w, preferably between 1 and 40% w/w. [0015] Nano-fillers are particles of a sub-micron size. Typi- cal nano-fillers may comprise silica, barium sulphate or, espe- cially, clays. A nano-clay is an ionic phyllosilicate; it may be any hydrophilic or organophilic layer silicate obtainable from a natural or synthetic layer silicate. Such materials have a sheet-type or platey multiscale structure. At the Angstrom scale is the platelet, which is 0.7-1 nm thick and several hundred nanometers long and wide (ca. 100-1000 nm). As a result individual sheets have aspect ratios (Length/Thickness, L/T) varying from 200-1000 or even higher, with a majority of platelets in the 200-400 range after purification. In other words, these sheets usually measure approximately 200>20 6.0 7.0 5.0 4.0 20.0 6.0 9.0 10.0 Dripping 0 0 0 0 0 0 0 0 0 extinction time (sec) Afterglow (sec) 0 0 0 0 0 0 0 0 0 Smoke level 5 2 2 2 4 2 2 4 3 *indicates a comparative example [0104] Upon comparing compositions C3 and Cl (compari- son), C2 (comparison) and C4, the synergy of expandable graphite with the nano-clay is seen not only as regards enhanced flame retardancy but also and most importantly the smoke suppression effect. When no expandable graphite is present (comparison composition C6), the inorganic addi- tives alone are not able to achieve the same flame resistance. The flammability test data of the compositions C5 (compari- son) and C10 provide strong evidence of effective smoke Resin or dispersion Silicone fluid 65000 D4608 D5006 MY—05 10 Silicone Wacker CLM 42205 D3710 Tolylene diisocyanate DBTDL Ammonium Octamolybdate C11 C12 C13 C14 C15 5 7 4 6 0 10.0 11.0 10.0 7.0 7.0 0 0 0 0 0 length, no dripping, no afterglow and limited smoke) was far better than any of the epoxy-based comparison compositions. Examples 28-49 Preparation of Novel Flame Retardant Compositions Based on Silicon Polymeric Platforms [0107] The following formulations were prepared accord- ing to the procedure described below TABLE 6 Compositions s2 s3 s4 s5 S6 s7 S8 s9 S10 s11 Wt-(g) 15.00 15.00 15.00 15.00 15.00 15.00 14.76 14.76 14.76 14.76 14.76 1.85 1.85 1.85 1.85 1.85 1.85 1.65 1.65 1.65 1.65 1.65 US 2010/0056687 A1 9 TABLE 6-continued Expandablegraphite 0.18 0.90 1.86 2.97 4.23 0.15 0.87 1.83 220-80B Zincborate Aluminum trihydroxide Compositions S12 S13 S14 S15 S16 S17 S18 S19 Resin or dispersion Wt. (g) Silicone fluid 65000 14.40 D4608 15.84 15.84 15.84 15.84 D5006 15.84 15.84 15.84 MY-0510 1.76 1.76 1.76 1.76 1.76 1.76 1.76 1.76 Silicone Wacker CLM 42205 D3710 Tolylene diisocyanate DBTDL AmmoniumOctamolybdate 0.68 0.68 0.68 0.68 0.76 0.72 0.72 Expandablegraphite 1.60 1.72 1.56 1.56 1.76 0.72 0.24 220-80B Zincborate 2.28 2.32 2.44 2.24 2.52 2.4 2.32 Aluminumtrihydroxide 2.28 2.32 2.44 2.24 2.52 2.4 2.32 [0108] Procedure: [0113] [0109] The ingredients of the formulations S1-S19 were added and mixed as follows: [0110] 1” addition: All the components but the epoxy resin MY-0510 or the D4608 or the D5006 (where applicable). Thorough mixing. [0111] 2"d addition: The epoxy resin MY-0510 or the D4608 or the D5006 (where applicable), was added to the previously prepared mixtures. [0112] Subsequently, they were mixed thoroughly and then coated on aluminium strips (for flammability testing) accord- ing to the procedure described above. [0117] Mar. 4, 2010 2.89 4.11 S20 S21 20.00 22.00 1.34 1.34 0.10 0.12 1.00 2.34 3.34 3.34 The ingredients of the formulations S20-S21 were added and mixed as follows: [0114] 15’ addition: All the components except the tolylene diisocyanate. Thorough mixing. [01 15] 2”’ addition: Tolylene diisocyanate was added to the previously prepared mixtures. [01 1 6] Subsequently, they were mixed thoroughly and then coated on aluminium strips (for flammability testing) accord- ing to the procedure described above. The following Table summarizes the BSS7230 flammability test results for the reference compositions. TABLE 7 Compositions BSS7230 Test S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 Extinction time 0 0 0 0 0 0 42 8 0 0 0 0 (sec) Burn length (cm) 6.00 4.00 3.00 3.00 3.00 2.00 20.00 8.00 4.00 4.00 1.00 2.00 Dripping 0 0 0 0 0 0 0 0 0 0 0 0 extinction time (sec) Afterglow (sec) 0 0 0 0 0 0 0 0 0 0 0 0 Smoke level 2 4 4 4 4 4 3 3 1 1 0 0 Compositions BSS7230 Test S13 S14 S15 S16 S17 S18 S19 S20 S21 Extinction time 10 0 0 0 0 0 0 15 0 (sec) Burn length (cm) 7.00 2.00 2.50 2.00 1.00 3.00 4.00 13.00 3.00 Dripping 0 0 0 0 0 0 0 0 0 extinction time (sec) Afterglow (sec) 0 0 0 0 0 0 0 0 0 Smoke level 5 0 1 0 0 2 3 2 1 US 2010/0056687 A1 [0118] An additive-free composition (S1) presented a very good flame proofness that was further enhanced by the intro- duction of expandable graphite (loads>5% w/w) and nano- clay. Compositions, S1 -511 illustrate the effect of varying amounts of expandable graphite. Flammability test data of the S1 composition compared to those of the S2-S6 compositions shows a synergy between silicon and expandable graphite. [0119] The effect of nano-clay in a silicon-based composi- tion is further enhanced when it is combined with other inor- ganic additives for loads of expandable graphite higher than 3% w/w (compositions S12 and S17). The effect of including expandable graphite in silicon-based compositions is illus- trated by comparing the flarmnability test data of the compo- sitions S13 and S17. The role of ammonium octamolybdate in silicon-based compositions seems to be rather positive for decreased flammability (S14 and S17) rather than acting as a smoke suppressant. Aluminium trihydroxide (S16) appears to behave like ammonium octamolybdate in silicon-based poly- meric platforms. [0120] The flammability test data of the S17-S19 compo- sitions confirm the synergy between silicon and expandable graphite. The improvement of the fire resistance of a much softer material, a silicon-based polyurethane, is illustrated by compositions S20 and S21. Composition S17 presented the best flame retardancy performance achieved. Examples 50-65 Preparation of Novel Flame Retardant Compositions Based on Silicon and Carbon Polymeric Blends [0121] The following formulations were prepared accord- ing to the procedure described below TABLE 9 CS1 CS2 CS3 CS4 CS5 CS6 Resin or dispersion Silicone fluid 65000 D3508 MY—05 10 Tetraethylpentamine Silicone Wacker CLM 42205 Voranol EP1900 D3710 D371 1 Tolylene diisocyanate DBTDL D3 61 1 D3 81 1 Poly(urethane- methacrylate) Dimthelyl p-toluidine Benzoyl peroxide Ammonium Octamolybdate Expandable grpahite 220- 80B Zinc borate 13.34 13.34 6.12 8.98 8.98 9.80 8.92 1.04 2.10 4.44 4.44 13.02 5.58 1.04 11.84 2.10 3.16 3.16 0.88 2.06 0.90 2.08 0.88 2.06 2.94 2.94 2.98 2.98 2.94 Aluminum trihydroxide 2.94 CS7 2.14 14.16 3.70 Mar. 4, 2010 10 [0122] Procedure: [0123] The ingredients of the formulations CS1-CS13 were added and mixed as follows: [0124] 15’ addition: All the components except the epoxy resin MY-0510 or the D3508 (where applicable). Thorough mixing. [0125] 2”’ addition: The epoxy resin MY-0510 or the D3508 (where applicable), was added to the previously pre- pared mixture. [0126] Subsequently, they were mixed thoroughly and then coated on aluminium strips (for flammability testing) accord- ing to the procedure described above. [0127] The ingredients of the formulations CS 1 4-C14 were added and mixed as follows: [0128] diisocyanate and the benzoyl peroxide, respectively. Thor- ough mixing. [0129] oxide were added to their corresponding previously prepared 1” addition: All the components except the tolylene 2”’ addition: Tolylene diisocyanate and benzoyl per- mixtures . [013 0] Subsequently, they were mixed thoroughly and then coated on aluminium strips (for flammability testing) accord- ing to the procedure described above. [0131] The following Table summarizes the BSS7230 flammability test results for the reference compositions. Compositions CS8 CS9 CS10 CS11 CS12 CS13 CS14 CS15 Weight(g) 2.14 1.06 1.06 0.54 0.54 15.56 16.50 8.45 15.00 15.38 3.70 3.94 3.94 4.08 4.08 10.00 10.00 11.00 11.00 1.26 1.26 0.12 0.12 5.30 3.63 3.00 0.60 0.33 0.92 0.92 0.92 0.92 0.86 2.14 2.16 2.16 2.16 2.00 3.06 3.08 3.08 3.10 2.86 3.06 3.08 3.08 3.10 2.86 US 2010/0056687 A1 TABLE 10 Mar. 4, 2010 Compositions BSS7230Test CS1 CS2 CS3 Extinction time 0 0 0 0 19 0 22 3 (sec) Burn length (cm) 15.0 3.0 16.0 3.0 >20 2.0 >20 6.0 Dripping 0 0 0 0 0 0 8 0 extinction time (sec) Afterglow (sec) 0 0 0 0 0 0 0 0 Smoke level 4 1 4 2 5 2 5 3 [0132] In the case of blending carbon- and silicon-based platforms followed by subsequent crosslinking of both or at least one i.e. in the case one of the two polymers is not functional, it becomes evident that even when extremely low amounts of silicone are used (down to 3% w/w) and even without the introduction of any organic/inorganic additives (compositions CS9 and CS11) a dramatic decrease in the extinction time compared with the reference R1 composition was achieved. Example 66 [0133] In order to assess the physical/mechanical proper- ties of the compositions of the present application, a commer- cially available and non-flame retarded, two component epoxy-based adhesive the EPIBOND 1590® ((Trade Mark, Vantico Ltd.) was reformulated (Adhesive 1) according to the claimed compositions and its flame retardancy along with an array of physical/mechanical properties was recorded. [0134] Procedure: [0135] Preparation of Part A of the Adhesive 1 [0136] The resin part of the EPIBOND 1590® (70 g) and Cloisite 10A® (7.25 g) were mixed in a high shear mixer for 4-6 h. Subsequently, 7.00 g of Grafguard 220B, 3.00 g of ammonium octamolybdate, 10.00 g of Firebrake-ZB and 10.00 g of Apyral-22 were added to the mixture and mixing was continued in a low shear mixer for about an hour. [0137] Preparation of Part B of the Adhesive 1 [0138] The hardener part of the EPIBOND 1590® (70 g) and 7.00 g of Grafguard 220B, 3.00 g of ammonium octamo- lybdate, 10.00 g of Firebrake-ZB and 10.00 g of Apyral-22 were mixed in a low shear mixer for about an hour. [0139] The two components of the Adhesive 1 were mixed in a mixing ratio of 1.95:1 w/w (Part A: Part B). The curing process of the samples prepared was: a) 7 days @ 23° C. (Adhesive 1-23C) and 4 h @ 60° C. (Adhesive 1-60C) [0140] The following Table depicts the physical/mechani- cal properties of the Adhesive 1-23C and the Adhesive 1-60C. The flame retardancy of the both samples was tested accord- ing to the flame retardancy method described in the Experi- mental and in a “blue” flame. TABLE 11 Adhesive Adhesive EPIBOND Physical/Mechanical Properties 1-23C 1-60C 1590 ® Glass transition temperature (° C.) 58 72 n.d. by DSC Glass transition temperature (° C.) 60 82 n.d. by TMA CS4 CS5 CS6 CS7 CS8 CS9 CS10 CS11 CS12 CS13 CS14 CS15 24 3 27 3 4 0 0.00 >20 2.5 >20 6.0 10.0 3.5 3.5 12 0 16 0 0 0 0 0 0 0 0 0 0 0 5 3 5 3 2 0 0 TABLE 1 1 -continued Adhesive Adhesive EPIBOND ’hysical/ Mechanical Properties 1-23C 1-60C 1590 ® Glass transition temperature (° C.) 146 143 n.d. 3y DMA* Thermal expansion coefficient (10’° - 78 82 n.d. (4) below glass transition Thermal expansion coefficient (10’° - 110 124 n.d. (4) above glass transition Young’s storage modulus (MPa) @ 775 567 n.d. 23 ° C. Charpy impact strength (KI/m2) n.d. 3 n.d. :racture energy (J/m2) 438 1263 n.d. :racture toughness (MPa - mm) 1 2 n.d. Compression strength (MPa) 38 57 n.d. Compression modulus (MPa) 123 8 1440 n.d. nap shear strength (MPa) 14 18 n.d. Average peel load (N) 24 n.d. n.d. Extinction time (sec) 0 0 15 Dripping (sec) 0 0 0 3urn length (cm) 2 2 18 Smoke 1 1 5 *The samples were tested after been remained at 23° C. for 6 months. Example 67 [0141] In order to assess the thermal insulation potential of the compositions of the present application, the Adhesive 1-23C prepared as mentioned in Example 66, was tested according to the thermal insulation assessment method. Example 68 [0142] The thermal insulation of a specimen of EPIBOND 1590® cured at 23° C. for 7 days was also assessed according to the thermal insulation assessment method. In its case the flame applied for only 165 sec because the specimen was completely burned out after this time. Example 69 [0143] FIG. 1 depicts the results recorded by the thermal insulation assessment method for the Adhesive 1-23C and the EPIBOND 1590® prepared and tested in Examples 67 and 68, respectively. After 165 see the specimen of EPIBOND 1590® was completely burned out with maximum recorded temperature of approx. 565° C., exceeding by much the mate- rials initial decomposition temperature. In contrast Adhesive 1-23C remained dimensionally intact after approx. 260 sec. Above 180-200 sec, the temperature of the Adhesive 1-23Cremained almost levelled (maximum temperature recorded: 226° C.). US 2010/0056687 A1 1-29. (canceled) 30. A composition comprising (a) at least one expandable particulate material which expands on the application of heat and (b) at least one particulate intercalated nano-clay, together with at least one polymer and/ or at least one curable monomer or oligomer. 31. The composition according to claim 30, which also comprises at least one other particulate material having fire retardant properties. 32. The composition according to claim 31 wherein the particulate material having fire retardant properties is a metal oxide/ acid, a hydrate, a hydroxide, a carbonate, a sulphate, a silicate, a nitride, a molybdate or a stearate. 33. The composition according to claim 31 wherein the particulate material having fire retardant properties is a zinc or calcium borate, starmate or molybdate, a zinc or magne- sium stearate, an ammonium molybdate, a calcium hydrox- ide, an aluminum trihydroxide, a silicon oxide, a silicon nitride, a boron nitride, a sodium metalsilicate pentahydrate, a potassium tetraborate tetrahydrate, a magnesium hydrox- ide, a magnesium silicate, a titanium oxide, a ferric oxide, a molybdenum oxide, a lead phthalate, a stannous chloride, or a complex thereof. 34. The composition according to claim 30 which com- prises two or more particulate materials having fire retardant properties. 35. The composition according to claim 31 wherein the particulate material having fire retardant properties is present in an amount of from 1 to 95% w/w based on the total weight of the composition. 36. The composition according to claim 30 wherein the polymer and/or curable monomer or oligomer contains one or more epoxy, acrylic, methacrylic, amine, hydroxyl, carboxyl, anhydride, olefinic, styrenes acetoxy, methoxy, ester, cyano, amide, imide lactone or urethane groups. 37. The composition according to claim 30 wherein the intercalated nano-clay is present in an amount of from 0.1 to 95% w/w based on the total weight of the composition. 38. The composition according to claim 30 wherein the expandable particulate material is present in an amount of from 0.1 to 95% w/w based on the total weight of the com- position. 39. The composition according to claim 30 which is an adhesive, sealant or coating composition. 40. A cured article which comprises a polymer matrix in association with at least one expandable particulate material which expands on the application of heat and at least one intercalated nano-clay. Mar. 4, 2010 41. A process for the manufacture of a cured article which comprises admixing at least one expandable particulate mate- rial which expands on the application of heat with at least one intercalated nano-clay and at least one curable monomer, oligomer and/ or polymer to form a mixture and subsequently curing the mixture. 42. A method of making an adhesive bond, seal or coating comprising applying a composition according to claim 30 to a substrate and curing the composition. 43. A composition comprising (i) one or more reactive monomers, oligomers and/or polymers containing reactive species selected from the group consisting of: a. epoxy-functional compounds and resins in combination with amino-functional compounds, resins, oligomers, or polymers; b. hydroxy-functional compounds, oligomers, polymers in combination with isocyanate-functional monomers, dimers, oligomers, or polymers; c. methacrylic or acrylic functional monomers in combi- nation with methacrylic or acrylic functional oligomers or polymers; d. amino-functional polyorganosiloxane in combination with epoxy-functional compounds, resins or oligomers; e. hydroxy-functional polyorganosiloxane in combination with isocyanate-functional monomers, dimers or oligo- mers; f. methacrylated or acrylated polyorganosiloxane; g. epoxy-functional compounds and resins and amino- functional compounds, resins, oligomers, orpolymers in combination with amino -functional polyorganosiloxane and epoxy-functional compounds, resins or oligomers; h. hydroxy-functional compounds, oligomers, or polymers and isocyanate-functional monomers, dimers, oligo- mers, or polymers in combination with hydroxy-func- tional polyorganosiloxane and isocyanate-functional monomers, dimers or oligomers; and i. methacrylic or acrylic functional monomers, oligomers or polymers in combination with methacrylated or acry- lated polyorganosiloxane; (ii) expandable graphite; (iii) intercalated nano-clay; and optionally (iv) one or more flame retardant additives and smoke suppressants selected from the group consisting of zinc borate, aluminum trihydroxide, and ammonium octamo- lybdate. 44. The composition according to claim 43, wherein the polyorganosiloxane is polydimethylsiloxane. 45. The composition according to claim 43 wherein the clay is montmorillonite. * >X< * >X< *