ORGANOPOLYSILOXANE FOAM WITH EXPANDED PERLITE

Abstract

An insulating, compressible, and flame-resistant foamed material is provided. It comprises a polyorganosiloxane foam, a fire retardant, and expanded perlite. The foamed material is useful for providing heat insulation, flame resistance, and compressibility for applications such as lithium-ion batteries.

Claims

1. An insulating, compressible, and flame-resistant foamed material comprising, based on the weight of the foamed material, from 35 to 95 weight percent of a polyorganosiloxane foam; from 1 to 30 weight percent of a fire retardant; and from 1 to 15 weight percent of expanded perlite; wherein the foamed material has a density in the range of from 0.10 to 0.90 g/cm.sup.3.

2. The foamed material of claim 1 wherein the foamed material comprises from 50 to 80 weight percent of the polyorganosiloxane foam, from 2 to 20 weight percent of the fire retardant, and from 2 to 10 weight percent expanded perlite.

3. The foamed material of claim 2 wherein the fire retardant is Al(OH).sub.3, Mg(OH).sub.2, MgCO.sub.3.Math.3H.sub.2O, or Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.Math.4H.sub.2O, MgCa(CO.sub.3).sub.2, AlO(OH), NaHCO.sub.3, or hydrated MgSO.sub.4, or a combination thereof.

4. The foamed material of claim 1 which has a density in the range of from 0.15 to 0.50 g/cm.sup.3.

5. The foamed material of claim 2 which has a density in the range of from 0.15 to 0.50 g/cm.sup.3.

6. The foamed material of claim 3 which has a density in the range of from 0.15 to 0.50 g/cm.sup.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0005] The present invention is an insulating, compressible, and flame-resistant foamed material comprising, based on the weight of the foamed material, from 35 to 95 weight percent of a polyorganosiloxane foam; from 1 to 30 weight percent of a fire retardant; and from 1 to 15 weight percent of expanded perlite; wherein the foamed material has a density in the range of from 0.10 to 0.90 g/cm.sup.3.

[0006] The polyorganosiloxane foamed material of the present invention can be prepared by modification of a method such as described in U.S. Pat. No. 5,358,975. For example, a polydimethylsiloxane functionalized with at least two, and preferably at least three SiH groups (a) is advantageously contacted with one or more hydroxyl containing compounds which is water, an alcohol, diol, polyol, or a compound containing at least one silanol group (b), a divinyl-functionalized polydimethylsiloxane (c), a hydrosilylation catalyst such as a platinum-based catalyst (d), a fire retardant (e), and expanded perlite particles (f) to form a crosslinked network of an insulating, compressible, and flame-resistant foamed material with SiCH.sub.2CH.sub.2Si groups and SiOR groups, where R is H or a the structural unit (i.e., the reaction product) of the alcohol, the diol, the polyol, or the silanol. The total of components (a), (b), and (c) range from 35 or from 40 weight percent, to 80 or to 70 weight percent of the polyorganosiloxane foam.

[0007] It may be advantageous to prepare the foamed material using a 2-part approach wherein in a first vessel a first portion of the divinyl-functionalized polydimethylsiloxane; a first portion of the fire retardant; the hydrosilylation catalyst; the hydroxyl containing compound or compounds; and a first portion of expanded perlite are blended to form a Part A composition. In a second vessel, the remaining portion of the divinyl-functionalized polydimethylsiloxane; a polymer resin blend, which is a mixture of a divinyl-functionalized polydimethylsiloxane and a crosslinked organopolysiloxane resin; the remaining portion of the fire retardant; the polydimethylsiloxane functionalized with at least three SiH groups; and the remaining portion of the expanded perlite are blended to form a Part B composition. Parts A and B are then combined and mixed, then poured between two release film sheets to form the foamed material of the present invention.

[0008] The fire retardant is a metal hydroxide, carbonate, hydroxide-carbonate, or hydrate that, upon heating, releases CO.sub.2 or water or both. Examples of fire retardants include Al(OH).sub.3, Mg(OH).sub.2, Ca(OH).sub.2MgCO.sub.3.Math.3H.sub.2O (nesquehonite), Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.Math.4H.sub.2O (hydromagnesite), MgCa(CO.sub.3).sub.2 (huntite), AlO(OH) (boemite), NaHCO.sub.3, and hydrated MgSO.sub.4 (epsomite). The polyorganosiloxane foamed material comprises from 1 or from 2 or from 3 weight percent, to 30 or to 20 or to 15 weight percent of the fire retardant, based on the weight of the foamed material.

[0009] The foamed material further comprises from 1 or from 2 to 15 or to 10 weight percent of expanded perlite. Expanded perlite may be formed by heating perlite ore rapidly to a temperature in the range of from 750 C. to 1000 C. The resulting expanded particles generally have a dry bulk density in the range of from 0.03 to 0.20 g/cm.sup.3. The mean volume particle size is typically in the range of from 0.1 m to 1000 m using a dynamic light scattering analyzer such as a Beckman Coulter LS 130 Particle Size Analyzer.

[0010] The resultant barrier material has a density in the range of from 0.10 g/cm.sup.3 or from 0.15 g/cm.sup.3, to 0.90 g/cm.sup.3 or to 0.50 g/cm.sup.3.

[0011] In another aspect, the present invention is a composition comprising, based on the weight of the composition, a) from 2 to 50 weight percent of a polysiloxane functionalized with at least two SiH groups and having a degree of polymerization in the range of from 5 to 1000; b) from 1 to weight 50 percent of water, an alcohol, a diol, a polyol, or a compound containing one or more silanol groups; c) from 10 to 90 weight percent of a polysiloxane functionalized with at least one ethylenically unsaturated group and having a degree of polymerization in the range of from 20 to 2000; wherein the total concentration of components a, b, and c is in the range of from 35 to 95 weight percent, based on the weight of the composition; d) a catalytic amount of a hydrosilylation catalyst; e) from 1 to 30 weight percent of a fire retardant; and f) from 1 to 35 weight percent expanded perlite particles.

[0012] In yet another aspect, the present invention is a battery module comprising a shell containing an array of spatially separated battery cells and polyorganosiloxane foam material contacting adjacent battery cells. The polyorganosiloxane foam may contact battery cells by filling the spaces between adjacent battery cells with the foam and/or by covering the batter cells with the foam. The battery module may further comprise end plates at the internal edges of the shell that are in direct or indirect contact with battery cells nearest the edges. The foam material can be inserted into cavities between adjacent battery cells and between the cells and end plates; alternatively, the foam precursor can be applied onto the cells and into the cavities, then cured to form the foamed material.

[0013] The foamed material of the present invention has been found to provide the desired properties of heat insulation, flame resistance, and compressibility in battery thermal barrier applications.

[0014] In the following examples, M.sub.w and M.sub.n of the ViMe.sub.2SiO.sub.1/2/(CH.sub.3).sub.3SiO.sub.1/2/SiO.sub.4/2 resin was determined by gel permeation chromatography using a gpc column packed with 5-mm diameter sized divinyl benzene crosslinked polystyrene beads pore type Mixed-C (Polymer Laboratory). Tetrahydrofuran was used as the mobile phase and detection was carried out by a refractive index detector.

Example 1Preparation of Foamed Organopolysiloxane Article With Expanded Perlite Particles

[0015] A first component (Part A) was prepared by mixing together, using a Flacktek Speed Mixer, a dimethylvinylsiloxy end-capped polydimethylsiloxane having a viscosity of 40,000 mPas (Polymer 1, 11.0 pbw), a 64:36 w/w blend of 1) a dimethylvinylsiloxy-terminated polydimethylsiloxane, having a viscosity of 1,900 mPa.Math.s, and 0.22 wt. % of Vi; and 2) a ViMe.sub.2SiO.sub.1/2/(CH.sub.3).sub.3SiO.sub.1/2/SiO.sub.4/2 resin, having a ViMe.sub.2SiO.sub.1/2:(CH.sub.3).sub.3SiO.sub.1/2:SiO.sub.4/2 structural unit ratio of 5:40:55, a M.sub.n of 5000 and a M.sub.w of 21,400 (Polymer-Resin Blend, 62.9 pbw); and Micral 855 aluminum hydroxide (14.7 pbw). The contents were stirred at 2000 rpm for 30 s, after which time, a complex of Pt(0) and divinyltetramethyldisiloxane (0.9 pbw, 0.62 wt % Pt), 1,4-butanediol (2.5 pbw), and benzyl alcohol (3.2 pbw) were added to the mixture and the contents were stirred at 2000 rpm for 30 s. Finally, Omyasphere TP-312 FQ expanded perlite particles (mean volume average particle size of 63 m; 4.8 pbw) were added to the mixture and the contents were stirred at 2000 rpm for 30 s.

[0016] A second composition (Part B) was similarly prepared by mixing together Polymer 1 (8.6 pbw), Polymer Resin Blend (49.5 pbw), and Hymod M855 aluminum hydroxide (25.6 pbw). The contents were stirred at 2000 rpm for 30 s, after which time a linear organohydrogenpolysiloxane having a viscosity of 30 mPa.Math.s and 1.6 wt % SiH content (6.5 pbw), and a polydimethylorganohydrogensiloxane with viscosity of 5 mPa.Math.s and 0.7 wt % SiH content (4.9 pbw) were added to the mixture and the contents were stirred at 2000 rpm for 30 s. Then, Omyasphere TP-312 FQ expanded perlite particles (mean volume average particle size of 63 m, 4.8 pbw) were added to the mixture and the contents were stirred at 2000 rpm for 30 s.

[0017] Equal amounts of Parts A and B were then mixed, and the mixture was poured between two release film sheets (matte mylar film). The initial (before foaming) thickness was controlled at 0.045 inch using a nip roller. The sample was cured at 70 C. for 5 min, then 100 C. for 15 min, producing a foam sheet that was used for further testing. (Density=0.29 g/cm.sup.3)

Example 2Preparation of Foamed Organopolysiloxane Article With Expanded Perlite Particles

[0018] The process for preparing the foamed article of Example 1 was carried out in substantially the same way except that Omyasphere 235 T-FQ expanded perlite particles (mean volume average particle size of 124 m, 4.8 pbw) were used in Parts A and B. (Density=0.31 g/cm.sup.3).

Example 3Preparation of Foamed Organopolysiloxane Article With Expanded Perlite Particles

[0019] The process for preparing the foamed article of Example 1 was carried out in substantially the same way except that Omyasphere 235 T-FQ expanded perlite particles (9.1 pbw) were used in Parts A and B. (Density=0.35 g/cm.sup.3)

Comparative Example 2Preparation of Foamed Organopolysiloxane Article With Hollow Glass Beads

[0020] The process for preparing the foamed article of Example 1 was carried out in substantially the same way except that 3M iM16K hollow glass beads (mean volume average particle size of 20 m, 20 pbw) were used in Parts A and B. (Density=0.28 g/cm.sup.3). The amount of beads were selected to give a similar filler volume as the expanded perlite in Example 1.

Thermal Insulation and Flammability

[0021] The foams prepared as described in the examples were tested for thermal insulation and flammability using a hot plate set onto a hydraulic press. The hot plate was set at 600 C. with an insulator on the top of surface. Four thermocouples (K-type) were fixed onto an aluminum heat sink (440.47) using Kapton tape. A sample (44) was then placed and fixed onto the heat sink using Kapton tape. An additional thermocouple (K-type) was attached to the sample surface using Kapton tape. The insulator was removed from the hot surface and the sample attached to the heat sink was rapidly placed onto the hot surface with the sample surface facing the hot plate surface, and the Al heat sink facing the opposite side. The pressure was quickly increased to 355 kPa. The interfacial temperature between the hot plate surface and the sample surface, and the interfacial temperature between the sample surface and the heat sink were recorded using a data logger. Once the time reached 300 s, the pressure was released, and the test was ended. A temperature at the sample surface of <300 C. was considered acceptable. No observable flame throughout the test is considered acceptable flame resistance.

Hardness

[0022] Hardness was measured using a Shore 00 durometer. A test specimen was placed on a hard flat surface. The indenter of Shore 00 durometer was then pressed onto the specimen making sure that it was parallel to the surface. The hardness was read during firm contact with the specimen. A hardness of <80 was considered acceptable.

Compression Force

[0023] Compression force was measured using a TA.HDplus texture analyzer equipped with a 100 kg load cell, an aluminum probe with a diameter of 40 mm, and a flat heavy-duty aluminum substrate. A silicone foam sample was cut in a circle using a die cut with a diameter of 1 and placed between the substrate and the probe. The probe was initially set at the same height as the sample thickness, and lowered at the rate of 1 mm/s until the pressure maxed out. The sample thickness and pressure were recorded as a compression force curve. The pressures at 30% of original sample thickness were recorded. A compression force of <500 kPa was considered acceptable.

Foam Density

[0024] Foam density was calculated based on the average thickness and weight of two foam samples with a diameter of 1 inch.

[0025] The properties of the expanded perlite filled organopolysiloxane article were compared to two other foams: Comparative Example 1, which is a commercial organopolysiloxane article (COHRlastic Silicone Foam, available from Stockwell Elastomerics), which was similar in construction to the example foams except it did not contain expanded perlite; and Comparative Example 2, which is a foam containing 3M Glass Bubbles iM16K Hollow Glass Microspheres.

[0026] Table 1 is a summary of performance properties for the foams of the Examples 1-3 the commercial comparative foam, and the foam containing hollow glass microspheres. Density was measured in g/cm.sup.3; Hardness was measured in Shore 00 units; Compressive Force (Force) was measured in kPa@30% compression; Temperature at 600 C. (T after 300 s) refers to the sample surface temperature after 300 s; and Flammability refers to observability of a flame during the thermal insulation test.

[0027] TP-312-FQ refers to Omyasphere TP-312-FQ Expanded Perlite; 235T-FQ refers Omyasphere 235-T-FQ Expanded Perlite; and iM16K refers to 3M Glass Bubbles iM16K Hollow Glass Microspheres.

TABLE-US-00001 TABLE 1 Properties of Organopolysiloxane Article Property Criteria Comp. 1 Example 1 Example 2 Example 3 Comp. 2 Filler none TP-312-FQ 235 T-FQ 235 T-FQ iM16K Density <0.9 0.23 0.289 0.307 0.354 0.282 Hardness <80 35 61 65 75 82 Force <500 17 158 202 424 791 T after 300 s <300 C. 334 266 255 251 266 Flammability No Flame No Flame No Flame No Flame No Flame No Flame

[0028] Table 1 illustrates that the expanded perlite containing foams of the present invention pass all tests, while the sample without expanded perlite (Comparative Example 1) fails the test for thermal insulation test, and the sample with hollow glass microsphere filler (Comparative Example 2) fails the test for compression force.