CA2247194C - Dispersions of delaminated particles in polymer foams - Google Patents
Dispersions of delaminated particles in polymer foams Download PDFInfo
- Publication number
- CA2247194C CA2247194C CA002247194A CA2247194A CA2247194C CA 2247194 C CA2247194 C CA 2247194C CA 002247194 A CA002247194 A CA 002247194A CA 2247194 A CA2247194 A CA 2247194A CA 2247194 C CA2247194 C CA 2247194C
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- ethylene
- polymer foam
- melt
- ammonium salt
- Prior art date
- 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
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 90
- 239000006260 foam Substances 0.000 title claims abstract description 55
- 239000002245 particle Substances 0.000 title claims abstract description 28
- 239000006185 dispersion Substances 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 10
- -1 polypropylene Polymers 0.000 claims description 28
- 229920000098 polyolefin Polymers 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000003760 tallow Substances 0.000 claims description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- SWSFKKWJEHRFFP-UHFFFAOYSA-N dihexadecyl(dimethyl)azanium Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC SWSFKKWJEHRFFP-UHFFFAOYSA-N 0.000 claims description 2
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 claims description 2
- CJBMLKNLJXFFGD-UHFFFAOYSA-N dimethyl-di(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCC CJBMLKNLJXFFGD-UHFFFAOYSA-N 0.000 claims description 2
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- 229920004889 linear high-density polyethylene Polymers 0.000 claims description 2
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- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 claims description 2
- GLFDLEXFOHUASB-UHFFFAOYSA-N trimethyl(tetradecyl)azanium Chemical class CCCCCCCCCCCCCC[N+](C)(C)C GLFDLEXFOHUASB-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
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- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
This invention relates to a polymer foam prepared by dispersing on organophilic multi-layered material into a melt comprising an olefinic or styrenic polymer having polar functionality so that at least a portion of the polymer intercalates between layers of the particles;
and expanding the polymer with a blowing agent under such condition to form the polymer foam. The organophilic multi-layered material can also be dispersed into an olefinic or styrenic monomer, which can then be polymerized to form a polymer melt prior to, or along with the foaming step.
and expanding the polymer with a blowing agent under such condition to form the polymer foam. The organophilic multi-layered material can also be dispersed into an olefinic or styrenic monomer, which can then be polymerized to form a polymer melt prior to, or along with the foaming step.
Description
DISPERSIONS OF DELAMINATED PARTICLES IN POLYMER FOAMS
This invention relates to polymer foams prepared from resins having dispersed therein delaminated or exfoliated organophilic mufti-layered particles.
Nanocomposites, which are compositions comprising single layers such as silicate layers ( I to 100 nm thick) dispersed in a continuous polymer matrix, confer physical property enhancement to the polymer at a much lower ceramic content than conventionally processed glass- or mineral-reinforced polymers. These nanocomposites can be synthesized in a two-step process, with the first step being the modification of the mufti-layered particles, generally by ionic exchange of sodium or potassium ions (which exist in natural forms of mica-type silicates) with organic cations (for example, alkylammonium silicates or suitably functionaIized organosilanes). This modification step can render normally hydrophilic mica-type silicates organophilic. In a second step, a melt-processible polymer (or a monomer which is polymerized in situ) and the intercalated particles can be compatibilized to form a polymer with enhanced physical properties.
Nanocomposite materials are described in U.S. Patents 4,739,007; 4,618,528;
4,528,235; 4,874,728; 4,889,885; 4,810,734; and 5,385,776; and in WO 93/11190.
The present invention addresses the need of improving the physical properties of polymer foams by providing a polymer foam that is prepared by a process comprising the steps of: a) dispersing organophilic mufti-layered particles into a melt comprising an olefinic or styrenic polymer having polar functionality so that at least a portion of the polymer intercalates between layers of the particles; and b) expanding the polymer with a blowing agent under such conditions to form the polymer foam.
In a second aspect, the present invention is a polymer foam prepared by a process comprising the steps of: a) dispersing organophilic mufti-layered particles into a polymerizable olefinic or styrenic monomer having polar functionality so that at Least a portion of the monomer intercalates between layers of the particles; b) forming a polymer melt from the monomer; and c) expanding the polymer melt with a blowing agent under such conditions to form the polymer foam.
The polymer foam of the present invention can exhibit improved cushioning properties and enhancement in elastic recovery properties. Also, improvement in insulation and ignition resistance, superior resistance to diffusion of liquids and of gases, and enhanced impact strength can be realized in comparison to foams that are not prepared from the expansion of a suitably functionaIized polymer intercalated between the layers of an organophilic multi-layered material.
The polymer foam of the present invention can be prepared by the steps of dispersing organophilic mufti-layered particles into a melt comprising an olefinic or styrenic polymer having polar functionality so that at least a portion of the polymer intercalates between layers of the particles; and expanding the polymer with a blowing agent under such conditions to form the polymer foam. Alternatively, the organophilic mufti-layered particles can be dispersed in an olefinic or styrenic monomer or prepolymer or a combination, and the monomer or prepolymer can then be polymerized in situ prior to or concurrent with the foaming step to form the polymer foam.
Organophilic mufti-layered particles suitable for the preparation of the polymer foam can be prepared from hydrophilic phyllosilicates by methods well known in the art. Illustrative of such materials are smectite clay minerals such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite, kenyaite, and vermiculite. Other useful mufti-layered particles include ilIite minerals such as ledikite and admixtures of illites with the clay minerals named above. Other useful mufti-layered particles, particularly useful with anionic polymers, are the layered double hydroxides such as Mg6A13.4(OH)18.$(C03)i.7Hz0 (see W.T. Reichle, J. Catal., Vol. 94, p. 547 (1985), which have positively charged layers and exchangeable anions in the interlayer spaces. Other mufti-layered particles having little or no charge on the layers may be useful in this invention provided they can be intercalated with swelling agents which expand their interlayer spacing. Such materials include chlorides such as ReCl3 and FeOCl; chalcogenides such as TiS2, MoS2, and MoS3; cyanides such as Ni(CN)2;
and oxides such as H2Si~05, VSO13, HTiNb05, Cro.SVo.sS2~ Wo.zV~ a0~, Cr30g, Mo03(OH)~,, VOP04-2H~0, CaP04CH3-HBO, MnHAs04-HBO, and Ag6Mo~o033.
The hydrophilic mufti-layered particle can be rendered organophiiic by exchange of sodium, potassium, or calcium cations with a suitable material such as a water-soluble polymer, a quaternary ammonium salt, an amphoteric surface-active agent, and a choline compound, or the like. Representative examples of exchangeable water-soluble polymers include water-soluble polymers of vinyl alcohol (for example, polyvinyl alcohol)), polyalkylene glycols such as polyethylene glycol, water-soluble cellulosic polymers such as _2_ methyl cellulose and carboxymethyl cellulose, the polymers of ethylenicaIIy unsaturated carboxylic acids such as poly(acrylic acid) and their salts, and polyvinyl pyrrolidone.
Representative examples of the quaternary ammonium salts (cationic surface-active agents) which can be employed in this invention include the quaternary ammonium salts having octadecyl, hexadecyl, tetradecyI, or dodecyl groups; with preferred quaternary ammonium salts including dimethyl dihydrogenated tallow ammonium salt, octadecyl trimethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt, dihexadecyl dimethyl ammonium salt, tetradecyl trimethyl ammonium salt, and ditetradecyl dimethyl ammonium salt.
Preferred organophilic mufti-layered particles are those prepared by ion exchange of quaternary ammonium cations. A more preferred organophilic mufti-layered material is a montmorillonite clay treated with a quaternary ammonium salt, most preferably dimethyl dihydrogenated tallow ammonium salt, commercially sold as CLAYTONETM HY (a trademark of Southern Clay Products).
The organophiiic mufti-layered particles may also be prepared by the exchange of the sodium, potassium, or calcium cations with an inorganic material, a polymeric substance obtained by hydrolyzing a polymerizable metallic alcoholate such as Si{OR)4, Al(OR)3, Ge(OR)4, Si(OC~HS),~, Si(OCH3)4, Ge(OC3H~), or Ge(OCZHS)4, either alone, or in any combination. Alternatively, the inorganic material can be a colloidal inorganic compound.
Representative colloidal inorganic compounds which can be used include Si02, Sb203, Fe203, A1203, TiO~, ZrO~, and Sn02, alone, or in any combination.
The organophilic mufti-layered material may also be prepared through exchange of functionalized organosilane compounds, as disclosed in WO 93/11190, pp. 9-21.
The concentration of the intercalated mufti-layered particle in the polymer is application dependent, but is preferably not Less than 0.1 weight percent, more preferably not less than 0.5 weight percent, and most preferably not less than 1 weight percent based on the total weight of the polymer; and preferably not greater than 40 weight percent, more preferably not greater than 20 weight percent, and most preferably not greater than 10 weight percent based on the total weight of the polymer.
The polymer foam is prepared, at least in part, from an olefinic or styrenic polymer having polar functionality. As used herein, the term "polar functionality"
refers to a polymer that contains a group or groups having a dipole moment, such as anhydride, carboxylic acid, hydroxy, silane, chlorine, bromine, or ester functionality, or combinations thereof. The polymer containing polar functionality can be prepared, for example, by polymerizing a polymerizable monomer containing polar functionality, by copolymerizing a polymerizable monomer containing polar functionality with another poIymerizable monomer, or by grafting polar functionality onto a polymer backbone. The foamed dispersion may also be prepared from a polymer having polar functionality that is blended with a polymer that does not contain polar functionality.
Styrene or olefin polymers grafted with malefic anhydride or a vinyl silane, or styrene or olefin monomers copolymerized with malefic anhydride or vinyl silanes are especially suitable inasmuch as the malefic anhydride groups or silyl groups can serve to prevent re-agglomeration of the platelet particles. Preferred vinyl silanes include vinyl-Si(OR)3 where each R is independently methyl, ethyl, or propyl, more preferably methyl or ethyl, and most preferably methyl.
I5 Styrenic polymers such as those derived from styrene, oc-methyl styrene, ethyl styrene, vinyl toluene, chlorostyrene and bromostyrene, and mixtures thereof, are also suitable. These styrene monomers may be copolymerized with other ethylenically unsaturated compounds such as acrylic acid, methacrylic acid, ethacrylic acid, rnaleic anhydride, malefic acid, itaconic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitriIe, vinyl alcohol, amides, and butadiene.
Olefin polymers include polypropylene, polyethylene, and copolymers and blends thereof, as well as ethylene-propylene-dime terpolymers. Preferred olefinic polymers for the production of foam structures include polypropylene, linear high density polyethylene (HDPE), heterogeneously-branched linear low density polyethylene (LLDPE) such as DOWLEXTM
polyethylene resin (a trademark of The Dow Chemical Company), heterogeneously-branched ultra low linear density polyethylene (ULDPE) such as ATTANETM ULDPE (a trademark of The Dow Chemical Company); homogeneously-branched, linear ethylene/oc-olefin copolymers such as TAFMERTM (a trademark of Mitsui Petrochemicals Company Limited) and EXACTTM (a trademark of Exxon Chemical Company), which can be prepared as described in U.S. Patent 3,645,922; homogeneously-branched, substantially linear ethylene/ot-olefin polymers such as AFFINITYTM polyolefin plastomers (a trademark of The Dow Chemical Company) and ENGAGETM polyolefin elastomers (a trademark of DuPont Dow Elastomers ._ LLC}, which can be prepared as disclosed in U.S. Patents 5,272,236 and 5,278,272; and high pressure, free radical polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE). The more preferred olefinic polymers are the homogeneously-branched linear and substantially linear ethylene copolymers with a density (measured in accordance with ASTM D-792) of 0.85 g/cm3 to 0.965 g/cm3, preferably from 0.86 g/cm3 to 0.92 g/cm3, more preferably from 0.86 g/cm3 to 0.90 g/cm3, and most preferably from 0.86 g/cm3 to 0.88 g/cm3, a weight average molecular weight to number average molecular weight ratio (MW/Mn) from 1.5 to 3.0, a measured melt index (measured in accordance with (190/2.16)) of 0.1 g/10 minutes to 100 g/10 minutes, and a melt flow ratio {Ilolh) of to 20 (measured in accordance with ASTM D-1238 (190110)).
Preferred olefin polymers functionalized with a polar group include homogeneously-branched linear and substantially linear ethylene copolymers grafted with polar functionality, ethylene-acrylic acid (EAA) copolymers such as PRIMACORTM (a trademark of The Dow Chemical Company), ethylene-methacrylic acid (EMAA) copolymers, and ethylene-vinyl IS acetate (EVA) copolymers such as ESCORENETM polymers (a trademark of Exxon Chemical Company), and ELVAXTM (a trademark of E. I. du Pont de Nemours & Co.). More preferably, the olefin polymer functionalized with a polar group comprises a substantially linear ethylene-1-C4-C$ alkene copolymer grafted with malefic anhydride (the preparation of which is disclosed in U.S. Patent 5,346,963) or vinyl trimethoxysilane, most preferably an ethylene-1-octene copolymer grafted with malefic anhydride or vinyl trimethoxysilane and having a density of from 0.86 glcm3 to 0.88 g/cm~.
Preferably, the foam is prepared from an admixture of an olefin polymer that contains polar functionality and an olefin polymer that is not functionalized. More preferably, the weight-to-weight ratio of the nonfunctionalized olefin polymer to the olefin polymer that contains polar functionality is not greater than 10:1, most preferably not greater than 5:1, and more preferably not less than I :1, most preferably not less than 3:1.
Preferably, the concentration of the polar functional group on the polymer is not less than 0.1 weight percent, more preferably not less than 0.5 weight percent, and most preferably not less than I weight percent, based on the total weight of the styrene or olefin monomers) and the polar functional group. The preferred concentration of the polar functional group is not greater than 20 weight percent, more preferably not greater than i 5 weight percent, more preferably not greater than 10 weight percent, and most preferably not greater than 5 weight percent, based on the total weight of the polymer and the polar functional group.
VulcanizabIe and thermoplastic rubbers used in the practice of this invention may also vary widely. Illustrative of such rubbers are brominated butyl rubber, chlorinated polyolefins such as chlorinated polyethylene and chlorinated butyl rubber, fluoroelastomers, butadiene/acrylonitrile elastomers, silicone elastomers, poly(butadiene), poly(isobutylene), sulfonated ethylene-propylene-dime terpolymers, poly(chloroprene), poly(2,3-dimethyl-butadiene), poIy(butadiene-pentadiene), chlorosulfonated polyolefins such as chlorosulfonated poIy(ethylenes), and poly(sulfide) elastomers.
The organophilic multi-layered particles can be dispersed in in situ polymerized monomer or prepolymer by methods known in the art, for example, as disclosed in WO 93/11190, pp. 26-28.
The mixture may include various optional components which are additives commonly employed with polymers. Such optional components include nucleating agents, fillers, plasticizers, impact modifiers, chain extenders, colorants, mold release lubricants, antistatic agents, pigments, and fire retardants. These optional components and appropriate amounts are well known to those of ordinary skill in the art.
The dispersed preformed polymer melt or the polymer prepared in situ, can be made into a foam by any suitable means, such as those known in the art. A chemical blowing agent such as azodicarbonamide, 4,4'-oxybis(benzenesulfonyl hydrazide), or dinitrosopentamethylenetetramine, or a physical blowing agent such as carbon dioxide, CFCs, and light hydrocarbons, can be contacted with the polymer melt or reactive intermediates that contain the intercalated mufti-layered particle to form a foamable gel, which can then be extruded through a die to form a foam product. The blowing agent may be incorporated into the polymer melt or reactive intermediates by any suitable means such as extrusion, mixing, or blending. The blowing agent is preferably mixed with the melt polymer or reactive intermediates at an elevated pressure sufficient to disperse the blowing agent substantially homogeneously therein. Surprisingly, it has been discovered that the presence of the dispersed platelets can slow down the loss of incorporated gas from the foam, thereby providing a means of maintaining the integrity of the foam.
Other methods of forming a foam are described in U.S. Patent 5,340,840, from column 13, line 49 to column 14, lines I to 35, along with the relevant teachings of U.S.
Patents 4,323,528; 4,379,859; and 4,464,484. Also, see K. W. Suh and D. D.
Webb in "Cellular Materials," from Encyclopedia of Polymer Scierzce azzd Erzgineerizzg, VoI. 3, Second Edition, pp. 1-59 ( 1985, and C. P. Park in "Polyolefin Foams" from Handbook of Polymeric Foams arzd Foarzz Technology, Hanser Publishers, New York, pp. I 87-242 ( I
991 ).
The foams of the present invention exhibit useful properties, for example, enhanced yield strength and tensile modulus, even when exposed to polar media such as water or methanol; enhanced heat resistance; and enhanced impact strength as compared to the foams '10 which do not include the dispersion layered materials. The improvements in properties are obtained even though smaller amounts of the layered material are employed. It has also been surprisingly discovered that the Asker C hardness of a 0.885 glcm~ density polyolefin elastomeric resin (40 to 45) can be achieved, without substantially sacrificing resiliency or hysteresis of the 0.87 g/cm3 density resin, by adding small amounts (less than 5 parts per hundred) of an ion-exchanged organoclay to the 0.87 g/cm3 density resin grafted with a polar substituent, such as malefic anhydride or vinyl trimethoxy silane. Therefore, the desirable and unusual combination of high hardness, low hysteresis, and high resiliency can be achieved by the incorporation of the ion-exchanged organocIay material into a low density-foamed, polyoIefinic material containing polar functionality.
The following examples are for illustrative purposes only, and are not meant to limit the scope of the invention.
Example 1 - VTMS-grafted PolyoIefin Elastomer Bun Foams Containing Montmorillonite Organoclay Vinyl trimethoxy silane ( I .5 weight percent), AFFINITYTM EG 8200 resin (98.425 weight percent), and dicumyl peroxide (0.075 weight percent) were tumble blended for 30 minutes. The mixture was then compounded on a Werner-Pfleiderer ZSK-30 co-rotating twin-screw extruder that is operated under the conditions set forth in Table I.
(AFFINITYTM EG 8200 resin is a substantially linear ethylene-l-octene copolymer having a melt index of 5 g110 minutes, a density of 0.870 glcm~, an IIO/h of 7, and a MW/Mn of 2.) Zones 1 to 5 refer to extruder heater zones.
Table I
Zone #1 (C) 130 Zone #2 (C) 172 Zone #3 (C) 185 Zone #4 (C) 211 Zone #5 (C) 209 Die Temperature (C) 197 Melt Temperature (C) 225 Extruder Torque 70 Extruder RPM 100 Die Pressure (psi/kPa) 390/2690 Water Bath Temp (C) 15 The resultant polymer (AFFINITY EG 8200.g.VTMS) was used to prepared a bun formulation as set forth in Table II. CLAYTONETM HY (a trademark of Southern Clay Products} is a montmorillonite clay treated with dimethyl dihydrogenated tallow ammonium.
The coagent is SARTOMERTM 350 monomer, a trimethylolpropane trimethacrylate crossIinking coagent (a trademark of Sartomer Company}. The formulation was prepared by mixing the components in a Banbury size BR internal hatch mixer at 95°C
to 1 10°C for 4 to 5 minutes. The mixture was then sheeted off into 1/4 inch (0.6 cm) to 1/2 inch (1.3 cm) thick sheets on a roll mill heated to 80°C. About 200 g of the above formulation was placed into a chase with an opening of 5 inch x 5 inch x 0.5 inch ( 12.7 em x 12.7 cm x 1.3 cm). The material was placed in a Tetrahedron MTP-8 compression press at 120°C
for 20 minutes at 1 ton pressure (0.56 MPa), then immediately pressed in a Carver autohydraulic press (model 3895} at 175°C and 25 ton pressure ( 14 MPa) for 7 to 8 minutes.
The material was then foamed at I50°C to 160°C, using 25 tons pressure ( 14 MPa) for about 45 minutes. Foam . density was measured by first cutting the foam into 1.5 inch x 1.5 inch squares (3.8 cm' x 3.8 cm'}. The skin of the foam was then removed and the sample thickness adjusted to 0.5 inch ( 1.3 cm) using a Hobart slicer. Calipers were used to measure the dimensions of the squares. The sample was then weighed, and the density determined by dividing the mass by the volume. The static compression was determined by measuring the _g_ WO 97!31053 PCT/US97/02644 initial thickness of the sample using calipers. The sample was then compressed 50 percent using 0.25 inch (0.63 cm) spacers in a static compression set jig as described in ASTM D-395 Method B. The foam density was 0.14 g/cm3 ~ 0.01, the static compression was 62 percent ~
4; the Asker C hardness was 43 ~ 2, as measured by an Asker C durometer; the resiliency was 59 percent ~ 1, as measured in accordance with ASTM D-3574-86; and the hysteresis was 10.8 percent ~ 0.1.
Table II
Amount Component (parts per hundred resin) AFFINITYTM EG 8200.g.VTMS 100 resin Azodicarbonamide 3.0 Zinc Stearate 0.5 Zinc Oxide 1.0 IRGANOXTM 1010 antioxidant 0.1 Dicumyl Peroxide (40 percent1.0 active) Coagent 1.25 Dibutyltin dilaureate 0.01 Ti02 3.0 CLAYTONETM HY 4.5 Exam lp a 2 - VTMS-grafted Polyolefin Elastomer Bun Foams Containing Montmorillonite Organoclay The procedure for forming the bun foams that was described in Example 1 was used in this example. The formulation is set forth in Table III.
WO 97/31053 PC~'/LTS97/02644 Table III
Amount Component (parts per hundred resin) AFFINITYTM EG 8200.g.VTMS resin100 , Azodicarbonamide 3 Zinc Oxide 1 Dicumyl Peroxide 0.8 Coagent 2.5 TiOZ 3 The compression set was 65.3 percent ~ 2.0 percent; the Asker C hardness was 51; and the resiliency was 58.
Example 3 - MAH-grafted Polyolefin Elastomer Bun Foams Containing MontmoriIlonite Organoclay Malefic anhydride (MAH) grafted onto a substantially linear ethylene-I-octene copolymer was obtained from The Dow Chemical Company. (A procedure for preparing this material was disclosed in U.S. Patent 5,346,963.) The grafted material (AFFINITYT'~
EG 8200.g.MAH) contained 98.12 percent AFFINITYTM EG 8200, 1.4 percent MAH, 0.12 percent di-t-butyl peroxide, and 0.36 percent mineral oil. Bun foam formulations were prepared using the AFFINITYTM EG 8200.g.MAH and AFFINITYTM EG 8200. The formulation is set forth in Table IV. (IRGANOXTM is a trademark of Ciba-Geigy.) r Table IV
Amount Component (parts per hundred resin) AFFINITYTM EG 8200 resin 80 AFFINITYTM EG 8200.g.MAH resin20 Azodicarbonamide 2.75 Zinc Stearate 0.5 Zinc Oxide 1.0 IRGANOXTM 1010 antioxidant 0.1 Dicumyl Peroxide (40 percent 1.5 active) Coagent i .?5 TiO~ 3 CLAYTONETM HY -. 4.5 A foam was prepared from the formulation as described in Example 1. The foam density was 0.14 g/cm~ ~ 0.01; the Asker C hardness was 45 ~ 2; the resiliency was 54 percent -~- 1; and the static compression set was 80.
This invention relates to polymer foams prepared from resins having dispersed therein delaminated or exfoliated organophilic mufti-layered particles.
Nanocomposites, which are compositions comprising single layers such as silicate layers ( I to 100 nm thick) dispersed in a continuous polymer matrix, confer physical property enhancement to the polymer at a much lower ceramic content than conventionally processed glass- or mineral-reinforced polymers. These nanocomposites can be synthesized in a two-step process, with the first step being the modification of the mufti-layered particles, generally by ionic exchange of sodium or potassium ions (which exist in natural forms of mica-type silicates) with organic cations (for example, alkylammonium silicates or suitably functionaIized organosilanes). This modification step can render normally hydrophilic mica-type silicates organophilic. In a second step, a melt-processible polymer (or a monomer which is polymerized in situ) and the intercalated particles can be compatibilized to form a polymer with enhanced physical properties.
Nanocomposite materials are described in U.S. Patents 4,739,007; 4,618,528;
4,528,235; 4,874,728; 4,889,885; 4,810,734; and 5,385,776; and in WO 93/11190.
The present invention addresses the need of improving the physical properties of polymer foams by providing a polymer foam that is prepared by a process comprising the steps of: a) dispersing organophilic mufti-layered particles into a melt comprising an olefinic or styrenic polymer having polar functionality so that at least a portion of the polymer intercalates between layers of the particles; and b) expanding the polymer with a blowing agent under such conditions to form the polymer foam.
In a second aspect, the present invention is a polymer foam prepared by a process comprising the steps of: a) dispersing organophilic mufti-layered particles into a polymerizable olefinic or styrenic monomer having polar functionality so that at Least a portion of the monomer intercalates between layers of the particles; b) forming a polymer melt from the monomer; and c) expanding the polymer melt with a blowing agent under such conditions to form the polymer foam.
The polymer foam of the present invention can exhibit improved cushioning properties and enhancement in elastic recovery properties. Also, improvement in insulation and ignition resistance, superior resistance to diffusion of liquids and of gases, and enhanced impact strength can be realized in comparison to foams that are not prepared from the expansion of a suitably functionaIized polymer intercalated between the layers of an organophilic multi-layered material.
The polymer foam of the present invention can be prepared by the steps of dispersing organophilic mufti-layered particles into a melt comprising an olefinic or styrenic polymer having polar functionality so that at least a portion of the polymer intercalates between layers of the particles; and expanding the polymer with a blowing agent under such conditions to form the polymer foam. Alternatively, the organophilic mufti-layered particles can be dispersed in an olefinic or styrenic monomer or prepolymer or a combination, and the monomer or prepolymer can then be polymerized in situ prior to or concurrent with the foaming step to form the polymer foam.
Organophilic mufti-layered particles suitable for the preparation of the polymer foam can be prepared from hydrophilic phyllosilicates by methods well known in the art. Illustrative of such materials are smectite clay minerals such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite, kenyaite, and vermiculite. Other useful mufti-layered particles include ilIite minerals such as ledikite and admixtures of illites with the clay minerals named above. Other useful mufti-layered particles, particularly useful with anionic polymers, are the layered double hydroxides such as Mg6A13.4(OH)18.$(C03)i.7Hz0 (see W.T. Reichle, J. Catal., Vol. 94, p. 547 (1985), which have positively charged layers and exchangeable anions in the interlayer spaces. Other mufti-layered particles having little or no charge on the layers may be useful in this invention provided they can be intercalated with swelling agents which expand their interlayer spacing. Such materials include chlorides such as ReCl3 and FeOCl; chalcogenides such as TiS2, MoS2, and MoS3; cyanides such as Ni(CN)2;
and oxides such as H2Si~05, VSO13, HTiNb05, Cro.SVo.sS2~ Wo.zV~ a0~, Cr30g, Mo03(OH)~,, VOP04-2H~0, CaP04CH3-HBO, MnHAs04-HBO, and Ag6Mo~o033.
The hydrophilic mufti-layered particle can be rendered organophiiic by exchange of sodium, potassium, or calcium cations with a suitable material such as a water-soluble polymer, a quaternary ammonium salt, an amphoteric surface-active agent, and a choline compound, or the like. Representative examples of exchangeable water-soluble polymers include water-soluble polymers of vinyl alcohol (for example, polyvinyl alcohol)), polyalkylene glycols such as polyethylene glycol, water-soluble cellulosic polymers such as _2_ methyl cellulose and carboxymethyl cellulose, the polymers of ethylenicaIIy unsaturated carboxylic acids such as poly(acrylic acid) and their salts, and polyvinyl pyrrolidone.
Representative examples of the quaternary ammonium salts (cationic surface-active agents) which can be employed in this invention include the quaternary ammonium salts having octadecyl, hexadecyl, tetradecyI, or dodecyl groups; with preferred quaternary ammonium salts including dimethyl dihydrogenated tallow ammonium salt, octadecyl trimethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt, dihexadecyl dimethyl ammonium salt, tetradecyl trimethyl ammonium salt, and ditetradecyl dimethyl ammonium salt.
Preferred organophilic mufti-layered particles are those prepared by ion exchange of quaternary ammonium cations. A more preferred organophilic mufti-layered material is a montmorillonite clay treated with a quaternary ammonium salt, most preferably dimethyl dihydrogenated tallow ammonium salt, commercially sold as CLAYTONETM HY (a trademark of Southern Clay Products).
The organophiiic mufti-layered particles may also be prepared by the exchange of the sodium, potassium, or calcium cations with an inorganic material, a polymeric substance obtained by hydrolyzing a polymerizable metallic alcoholate such as Si{OR)4, Al(OR)3, Ge(OR)4, Si(OC~HS),~, Si(OCH3)4, Ge(OC3H~), or Ge(OCZHS)4, either alone, or in any combination. Alternatively, the inorganic material can be a colloidal inorganic compound.
Representative colloidal inorganic compounds which can be used include Si02, Sb203, Fe203, A1203, TiO~, ZrO~, and Sn02, alone, or in any combination.
The organophilic mufti-layered material may also be prepared through exchange of functionalized organosilane compounds, as disclosed in WO 93/11190, pp. 9-21.
The concentration of the intercalated mufti-layered particle in the polymer is application dependent, but is preferably not Less than 0.1 weight percent, more preferably not less than 0.5 weight percent, and most preferably not less than 1 weight percent based on the total weight of the polymer; and preferably not greater than 40 weight percent, more preferably not greater than 20 weight percent, and most preferably not greater than 10 weight percent based on the total weight of the polymer.
The polymer foam is prepared, at least in part, from an olefinic or styrenic polymer having polar functionality. As used herein, the term "polar functionality"
refers to a polymer that contains a group or groups having a dipole moment, such as anhydride, carboxylic acid, hydroxy, silane, chlorine, bromine, or ester functionality, or combinations thereof. The polymer containing polar functionality can be prepared, for example, by polymerizing a polymerizable monomer containing polar functionality, by copolymerizing a polymerizable monomer containing polar functionality with another poIymerizable monomer, or by grafting polar functionality onto a polymer backbone. The foamed dispersion may also be prepared from a polymer having polar functionality that is blended with a polymer that does not contain polar functionality.
Styrene or olefin polymers grafted with malefic anhydride or a vinyl silane, or styrene or olefin monomers copolymerized with malefic anhydride or vinyl silanes are especially suitable inasmuch as the malefic anhydride groups or silyl groups can serve to prevent re-agglomeration of the platelet particles. Preferred vinyl silanes include vinyl-Si(OR)3 where each R is independently methyl, ethyl, or propyl, more preferably methyl or ethyl, and most preferably methyl.
I5 Styrenic polymers such as those derived from styrene, oc-methyl styrene, ethyl styrene, vinyl toluene, chlorostyrene and bromostyrene, and mixtures thereof, are also suitable. These styrene monomers may be copolymerized with other ethylenically unsaturated compounds such as acrylic acid, methacrylic acid, ethacrylic acid, rnaleic anhydride, malefic acid, itaconic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitriIe, vinyl alcohol, amides, and butadiene.
Olefin polymers include polypropylene, polyethylene, and copolymers and blends thereof, as well as ethylene-propylene-dime terpolymers. Preferred olefinic polymers for the production of foam structures include polypropylene, linear high density polyethylene (HDPE), heterogeneously-branched linear low density polyethylene (LLDPE) such as DOWLEXTM
polyethylene resin (a trademark of The Dow Chemical Company), heterogeneously-branched ultra low linear density polyethylene (ULDPE) such as ATTANETM ULDPE (a trademark of The Dow Chemical Company); homogeneously-branched, linear ethylene/oc-olefin copolymers such as TAFMERTM (a trademark of Mitsui Petrochemicals Company Limited) and EXACTTM (a trademark of Exxon Chemical Company), which can be prepared as described in U.S. Patent 3,645,922; homogeneously-branched, substantially linear ethylene/ot-olefin polymers such as AFFINITYTM polyolefin plastomers (a trademark of The Dow Chemical Company) and ENGAGETM polyolefin elastomers (a trademark of DuPont Dow Elastomers ._ LLC}, which can be prepared as disclosed in U.S. Patents 5,272,236 and 5,278,272; and high pressure, free radical polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE). The more preferred olefinic polymers are the homogeneously-branched linear and substantially linear ethylene copolymers with a density (measured in accordance with ASTM D-792) of 0.85 g/cm3 to 0.965 g/cm3, preferably from 0.86 g/cm3 to 0.92 g/cm3, more preferably from 0.86 g/cm3 to 0.90 g/cm3, and most preferably from 0.86 g/cm3 to 0.88 g/cm3, a weight average molecular weight to number average molecular weight ratio (MW/Mn) from 1.5 to 3.0, a measured melt index (measured in accordance with (190/2.16)) of 0.1 g/10 minutes to 100 g/10 minutes, and a melt flow ratio {Ilolh) of to 20 (measured in accordance with ASTM D-1238 (190110)).
Preferred olefin polymers functionalized with a polar group include homogeneously-branched linear and substantially linear ethylene copolymers grafted with polar functionality, ethylene-acrylic acid (EAA) copolymers such as PRIMACORTM (a trademark of The Dow Chemical Company), ethylene-methacrylic acid (EMAA) copolymers, and ethylene-vinyl IS acetate (EVA) copolymers such as ESCORENETM polymers (a trademark of Exxon Chemical Company), and ELVAXTM (a trademark of E. I. du Pont de Nemours & Co.). More preferably, the olefin polymer functionalized with a polar group comprises a substantially linear ethylene-1-C4-C$ alkene copolymer grafted with malefic anhydride (the preparation of which is disclosed in U.S. Patent 5,346,963) or vinyl trimethoxysilane, most preferably an ethylene-1-octene copolymer grafted with malefic anhydride or vinyl trimethoxysilane and having a density of from 0.86 glcm3 to 0.88 g/cm~.
Preferably, the foam is prepared from an admixture of an olefin polymer that contains polar functionality and an olefin polymer that is not functionalized. More preferably, the weight-to-weight ratio of the nonfunctionalized olefin polymer to the olefin polymer that contains polar functionality is not greater than 10:1, most preferably not greater than 5:1, and more preferably not less than I :1, most preferably not less than 3:1.
Preferably, the concentration of the polar functional group on the polymer is not less than 0.1 weight percent, more preferably not less than 0.5 weight percent, and most preferably not less than I weight percent, based on the total weight of the styrene or olefin monomers) and the polar functional group. The preferred concentration of the polar functional group is not greater than 20 weight percent, more preferably not greater than i 5 weight percent, more preferably not greater than 10 weight percent, and most preferably not greater than 5 weight percent, based on the total weight of the polymer and the polar functional group.
VulcanizabIe and thermoplastic rubbers used in the practice of this invention may also vary widely. Illustrative of such rubbers are brominated butyl rubber, chlorinated polyolefins such as chlorinated polyethylene and chlorinated butyl rubber, fluoroelastomers, butadiene/acrylonitrile elastomers, silicone elastomers, poly(butadiene), poly(isobutylene), sulfonated ethylene-propylene-dime terpolymers, poly(chloroprene), poly(2,3-dimethyl-butadiene), poIy(butadiene-pentadiene), chlorosulfonated polyolefins such as chlorosulfonated poIy(ethylenes), and poly(sulfide) elastomers.
The organophilic multi-layered particles can be dispersed in in situ polymerized monomer or prepolymer by methods known in the art, for example, as disclosed in WO 93/11190, pp. 26-28.
The mixture may include various optional components which are additives commonly employed with polymers. Such optional components include nucleating agents, fillers, plasticizers, impact modifiers, chain extenders, colorants, mold release lubricants, antistatic agents, pigments, and fire retardants. These optional components and appropriate amounts are well known to those of ordinary skill in the art.
The dispersed preformed polymer melt or the polymer prepared in situ, can be made into a foam by any suitable means, such as those known in the art. A chemical blowing agent such as azodicarbonamide, 4,4'-oxybis(benzenesulfonyl hydrazide), or dinitrosopentamethylenetetramine, or a physical blowing agent such as carbon dioxide, CFCs, and light hydrocarbons, can be contacted with the polymer melt or reactive intermediates that contain the intercalated mufti-layered particle to form a foamable gel, which can then be extruded through a die to form a foam product. The blowing agent may be incorporated into the polymer melt or reactive intermediates by any suitable means such as extrusion, mixing, or blending. The blowing agent is preferably mixed with the melt polymer or reactive intermediates at an elevated pressure sufficient to disperse the blowing agent substantially homogeneously therein. Surprisingly, it has been discovered that the presence of the dispersed platelets can slow down the loss of incorporated gas from the foam, thereby providing a means of maintaining the integrity of the foam.
Other methods of forming a foam are described in U.S. Patent 5,340,840, from column 13, line 49 to column 14, lines I to 35, along with the relevant teachings of U.S.
Patents 4,323,528; 4,379,859; and 4,464,484. Also, see K. W. Suh and D. D.
Webb in "Cellular Materials," from Encyclopedia of Polymer Scierzce azzd Erzgineerizzg, VoI. 3, Second Edition, pp. 1-59 ( 1985, and C. P. Park in "Polyolefin Foams" from Handbook of Polymeric Foams arzd Foarzz Technology, Hanser Publishers, New York, pp. I 87-242 ( I
991 ).
The foams of the present invention exhibit useful properties, for example, enhanced yield strength and tensile modulus, even when exposed to polar media such as water or methanol; enhanced heat resistance; and enhanced impact strength as compared to the foams '10 which do not include the dispersion layered materials. The improvements in properties are obtained even though smaller amounts of the layered material are employed. It has also been surprisingly discovered that the Asker C hardness of a 0.885 glcm~ density polyolefin elastomeric resin (40 to 45) can be achieved, without substantially sacrificing resiliency or hysteresis of the 0.87 g/cm3 density resin, by adding small amounts (less than 5 parts per hundred) of an ion-exchanged organoclay to the 0.87 g/cm3 density resin grafted with a polar substituent, such as malefic anhydride or vinyl trimethoxy silane. Therefore, the desirable and unusual combination of high hardness, low hysteresis, and high resiliency can be achieved by the incorporation of the ion-exchanged organocIay material into a low density-foamed, polyoIefinic material containing polar functionality.
The following examples are for illustrative purposes only, and are not meant to limit the scope of the invention.
Example 1 - VTMS-grafted PolyoIefin Elastomer Bun Foams Containing Montmorillonite Organoclay Vinyl trimethoxy silane ( I .5 weight percent), AFFINITYTM EG 8200 resin (98.425 weight percent), and dicumyl peroxide (0.075 weight percent) were tumble blended for 30 minutes. The mixture was then compounded on a Werner-Pfleiderer ZSK-30 co-rotating twin-screw extruder that is operated under the conditions set forth in Table I.
(AFFINITYTM EG 8200 resin is a substantially linear ethylene-l-octene copolymer having a melt index of 5 g110 minutes, a density of 0.870 glcm~, an IIO/h of 7, and a MW/Mn of 2.) Zones 1 to 5 refer to extruder heater zones.
Table I
Zone #1 (C) 130 Zone #2 (C) 172 Zone #3 (C) 185 Zone #4 (C) 211 Zone #5 (C) 209 Die Temperature (C) 197 Melt Temperature (C) 225 Extruder Torque 70 Extruder RPM 100 Die Pressure (psi/kPa) 390/2690 Water Bath Temp (C) 15 The resultant polymer (AFFINITY EG 8200.g.VTMS) was used to prepared a bun formulation as set forth in Table II. CLAYTONETM HY (a trademark of Southern Clay Products} is a montmorillonite clay treated with dimethyl dihydrogenated tallow ammonium.
The coagent is SARTOMERTM 350 monomer, a trimethylolpropane trimethacrylate crossIinking coagent (a trademark of Sartomer Company}. The formulation was prepared by mixing the components in a Banbury size BR internal hatch mixer at 95°C
to 1 10°C for 4 to 5 minutes. The mixture was then sheeted off into 1/4 inch (0.6 cm) to 1/2 inch (1.3 cm) thick sheets on a roll mill heated to 80°C. About 200 g of the above formulation was placed into a chase with an opening of 5 inch x 5 inch x 0.5 inch ( 12.7 em x 12.7 cm x 1.3 cm). The material was placed in a Tetrahedron MTP-8 compression press at 120°C
for 20 minutes at 1 ton pressure (0.56 MPa), then immediately pressed in a Carver autohydraulic press (model 3895} at 175°C and 25 ton pressure ( 14 MPa) for 7 to 8 minutes.
The material was then foamed at I50°C to 160°C, using 25 tons pressure ( 14 MPa) for about 45 minutes. Foam . density was measured by first cutting the foam into 1.5 inch x 1.5 inch squares (3.8 cm' x 3.8 cm'}. The skin of the foam was then removed and the sample thickness adjusted to 0.5 inch ( 1.3 cm) using a Hobart slicer. Calipers were used to measure the dimensions of the squares. The sample was then weighed, and the density determined by dividing the mass by the volume. The static compression was determined by measuring the _g_ WO 97!31053 PCT/US97/02644 initial thickness of the sample using calipers. The sample was then compressed 50 percent using 0.25 inch (0.63 cm) spacers in a static compression set jig as described in ASTM D-395 Method B. The foam density was 0.14 g/cm3 ~ 0.01, the static compression was 62 percent ~
4; the Asker C hardness was 43 ~ 2, as measured by an Asker C durometer; the resiliency was 59 percent ~ 1, as measured in accordance with ASTM D-3574-86; and the hysteresis was 10.8 percent ~ 0.1.
Table II
Amount Component (parts per hundred resin) AFFINITYTM EG 8200.g.VTMS 100 resin Azodicarbonamide 3.0 Zinc Stearate 0.5 Zinc Oxide 1.0 IRGANOXTM 1010 antioxidant 0.1 Dicumyl Peroxide (40 percent1.0 active) Coagent 1.25 Dibutyltin dilaureate 0.01 Ti02 3.0 CLAYTONETM HY 4.5 Exam lp a 2 - VTMS-grafted Polyolefin Elastomer Bun Foams Containing Montmorillonite Organoclay The procedure for forming the bun foams that was described in Example 1 was used in this example. The formulation is set forth in Table III.
WO 97/31053 PC~'/LTS97/02644 Table III
Amount Component (parts per hundred resin) AFFINITYTM EG 8200.g.VTMS resin100 , Azodicarbonamide 3 Zinc Oxide 1 Dicumyl Peroxide 0.8 Coagent 2.5 TiOZ 3 The compression set was 65.3 percent ~ 2.0 percent; the Asker C hardness was 51; and the resiliency was 58.
Example 3 - MAH-grafted Polyolefin Elastomer Bun Foams Containing MontmoriIlonite Organoclay Malefic anhydride (MAH) grafted onto a substantially linear ethylene-I-octene copolymer was obtained from The Dow Chemical Company. (A procedure for preparing this material was disclosed in U.S. Patent 5,346,963.) The grafted material (AFFINITYT'~
EG 8200.g.MAH) contained 98.12 percent AFFINITYTM EG 8200, 1.4 percent MAH, 0.12 percent di-t-butyl peroxide, and 0.36 percent mineral oil. Bun foam formulations were prepared using the AFFINITYTM EG 8200.g.MAH and AFFINITYTM EG 8200. The formulation is set forth in Table IV. (IRGANOXTM is a trademark of Ciba-Geigy.) r Table IV
Amount Component (parts per hundred resin) AFFINITYTM EG 8200 resin 80 AFFINITYTM EG 8200.g.MAH resin20 Azodicarbonamide 2.75 Zinc Stearate 0.5 Zinc Oxide 1.0 IRGANOXTM 1010 antioxidant 0.1 Dicumyl Peroxide (40 percent 1.5 active) Coagent i .?5 TiO~ 3 CLAYTONETM HY -. 4.5 A foam was prepared from the formulation as described in Example 1. The foam density was 0.14 g/cm~ ~ 0.01; the Asker C hardness was 45 ~ 2; the resiliency was 54 percent -~- 1; and the static compression set was 80.
Claims (14)
1. A polymer foam that is prepared by a process comprising the steps of: a) dispersing an organophilic multi-layered particulate material into a melt comprising an olefinic or styrenic polymer having polar functionality so that at least a portion of the polymer intercalates between layers of the particles; and b) expanding the polymer with a blowing agent under such conditions to form the polymer foam.
2. The polymer foam of claim 1 wherein the olefinic or styrenic polymer having polar functionality contains anhydride, carboxylic acid, hydroxy, silane, chlorine, bromine, or ester functionality.
3. The polymer foam according to claim 1 or claim 2 wherein the olefinic or styrenic polymer having polar functionality is an olefinic polymer or a styrenic polymer containing a maleic anhydride group or a vinyl-Si(OR)3 group grafted thereto, wherein each R is independently methyl, ethyl, or propyl, and wherein the olefinic polymer is a polypropylene; a low density polyethylene, a linear high density polyethylene; a heterogeneously-branched, linear low density polyethylene; an ethylene-propylene-diene terpolymer; a heterogeneously-branched, ultra low linear density polyethylene; a homogeneously-branched, linear ethylene/.alpha.-olefin copolymer; a homogeneously-branched, substantially linear ethylene/.alpha.-olefin polymer; a polystyrene; or a poly-.alpha.-methyl styrene.
4. The polymer foam as in any one of claims 1 to 3 wherein the organophilic multi-layered material is a quaternary ammonium salt of montmorillonite.
5. The polymer foam of claim 4 wherein the quaternary ammonium salt is di-methyl di-hydrogenated tallow ammonium salt, octadecyl trimethyl ammonium salt, dioctadecyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt, dihexadecyl dimethyl ammonium salt, tetradecyl trimethyl ammonium salt, or ditetradecyl dimethyl ammonium salt.
6. The polymer foam as in any one of claims 1 to 5 wherein the melt further comprises an olefinic or styrenic polymer that does not contain polar functionality.
7. The polymer foam of claim 6 wherein the olefin polymer that does not contain polar functionality is a homogeneously-branched, linear ethylene/.alpha.-olefin copolymer and a homogeneously-branched, substantially linear ethylene/.alpha.-olefin polymer having a density of from 0.85 g/cm3 to 0.965 g/cm3, a M w/M n of 1.5 to 3.0, a melt index of 0.1 to 100 g/10 minutes, and an I10/I2 of from 6 to 20.
8. The polymer foam as in any one of claims 1 to 7 wherein the organophilic multi-layered particles comprise from 1 to 10 weight percent of the polymer melt, based on the weight of the polymers.
9. The polymer foam of claim 8 wherein the polymer melt comprises a mixture of a heterogeneously-branched, substantially linear ethylene-1-octene copolymer that is not functionalized with a polar group, and a heterogeneously-branched substantially linear ethylene-1-octene copolymer grafted with maleic anhydride or vinyl trimethoxysilane.
10. The polymer foam of claim 9 wherein the polymer melt has a density of from 0.86 g/cm3 to 0.88 g/cm3.
11. The polymer foam of claim 10 wherein the weight-to-weight ratio of the nonfunctionalized copolymer to the grafted copolymer is in the range of 1:1 to 10:1.
12. The polymer foam of claim 11 wherein the weight-to-weight ratio of the nonfunctionalized copolymer to the grafted copolymer is in the range of 3:1 to 5:1.
13. The polymer foam as in any one of claims 1, 4, and wherein the melt comprises an olefin polymer having polar functionality which is an ethylene-ethylene acrylic acid copolymer, an ethylene-ethylene vinyl acetate copolymer, or an ethylene-ethylene methacrylic acid copolymer.
14. A polymer foam prepared by a process comprising the steps of: a) dispersing organophilic multi-layered particles into a polymerizable olefinic or styrenic monomer having polar functionality so that at least a portion of the monomer intercalates between layers of the particles;
b) forming a polymer melt from the monomer; and c) expanding the polymer melt with a blowing agent under such conditions to form the polymer foam.
b) forming a polymer melt from the monomer; and c) expanding the polymer melt with a blowing agent under such conditions to form the polymer foam.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1220796P | 1996-02-23 | 1996-02-23 | |
| US60/012,207 | 1996-02-23 | ||
| PCT/US1997/002644 WO1997031053A1 (en) | 1996-02-23 | 1997-02-20 | Dispersions of delaminated particles in polymer foams |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2247194A1 CA2247194A1 (en) | 1997-08-28 |
| CA2247194C true CA2247194C (en) | 2005-11-29 |
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ID=35520648
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002247194A Expired - Fee Related CA2247194C (en) | 1996-02-23 | 1997-02-20 | Dispersions of delaminated particles in polymer foams |
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| Country | Link |
|---|---|
| CA (1) | CA2247194C (en) |
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- 1997-02-20 CA CA002247194A patent/CA2247194C/en not_active Expired - Fee Related
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