CA1169991A - Filled and plasticized blends of linear low density polyethylene - Google Patents
Filled and plasticized blends of linear low density polyethyleneInfo
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- CA1169991A CA1169991A CA000383343A CA383343A CA1169991A CA 1169991 A CA1169991 A CA 1169991A CA 000383343 A CA000383343 A CA 000383343A CA 383343 A CA383343 A CA 383343A CA 1169991 A CA1169991 A CA 1169991A
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Abstract
ABSTRACT OF THE DISCLOSURE
Filled thermoplastic compositions useful, eg., as sound-deadening sheeting for automotive carpet are obtained by blending about 5-55% by weight of ethylene/.alpha.-olefin copolymer, the .alpha.-olefin containing from 4 to 10 carbon atoms; about 2-12% by weight of plasticizer selected from the group consisting of processing oils, epoxidized oils, polyesters, polyethers and polyether esters; about 40-90%
by weight of filler; and optionally elastomeric polymers.
Filled thermoplastic compositions useful, eg., as sound-deadening sheeting for automotive carpet are obtained by blending about 5-55% by weight of ethylene/.alpha.-olefin copolymer, the .alpha.-olefin containing from 4 to 10 carbon atoms; about 2-12% by weight of plasticizer selected from the group consisting of processing oils, epoxidized oils, polyesters, polyethers and polyether esters; about 40-90%
by weight of filler; and optionally elastomeric polymers.
Description
3~
TITLE
Filled and Plasticized Blends Of Linear Lo~ Densitv Polvethylene BACXGROUND OF THE INVENTION
Field of the Invention This invention relates to filled polymer blends and, more specifically, it relates to ~illed blends of ethylene/a-olefin interpolymers modified with plasticizer.
Description of the Prior Art The use of processing oils and other plas-ticizers with natural rubber or snythetic rubber-like compounds containing sulfur, accelerators, carbon black and other additives customarily used in the ru~ber industry is well known. In some instances in order to obtain very high tensile strength values, fillers are omitted. On the other hand, it is known that styrene/butadlene rubber (SBR) compounds, such as are used to adhere jute secondary backings to carpets, can readily hold up to 80~ by weight or more of calcium carbonate filler. Vulcanization or curing enhances blend strength.
For thermo~lastic elastomeric uses, it is desirable both to avoid curing and to employ fillers to reduce blend costs, as well as to increase blend density.
~1 Industrial noise and its control are items o~increasing~concern to governmental, environmental, and industrial organizations. Governmental agencies ~are establishing noisP lLmits to which workers may be exposed to protect their health.
I ~ ` :
From an aesthetic standpoint, noise also presents ~roblems~ Advertisem:ents for "quiet riding"
automo~iles are ubiquitous. Manufacturers are ~attempting~to make other vehicles quiet as well --includin~ campers, trailers, buses, trucks, and AD-505lA
:: :
: ~ .
~ ~ .
~ ~ .
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off-road-use farm vehicles.
It has long been known that interposing mass between a sound source and the area to be kept quiet is an effective means for attaining sound 5 deadening. A sheet of lead is thin, flexible, often highly effective, but costly. The challenge, then, is to attain a dense, thin, flexible sheet which can be interposed between a source of noise and the area to be quietened.
Sheets of thermoplastics or of rubberlike materials have long been used as sound-deadening means.
To make the sheets flexible, dense, strong, and inexpensive has posed a challenge to compounders for many years. For some uses, such as automobile carpet 15 underla~ment, the sound-deadening sheet must also be moldable.
Schwartz U.S. Patent 3,904,456 is related to a method for inhibiting transmission of airborne noise by interPosing in the air space between the 20 noise source and ~he location to be insulated a thin, dense, normally self-supporting film or sheet composed essentially of from about 10 to about 40% by weight of ethylene/vinyl acetate copolymer having an average vinyl acetate content of from about 10 to about 42%
25 by weight and a glass transition temperakure of at least about 30C below the average ambient temperature in the air space, and from about 60 to about 90% by weight of inorganic filler materials, such as sulfates, carbonates, oxides, etc. of ~arium, calciu~, cadmium, 30 etc., effective to produce an overall density greater than at least 2 grams per cubic centimeter.
German Patent Application No. 2,319,431 dis-closes sound-deadening composites suitable for use in automobiles which consist of a highly filled polymer 35 sheet (for example, 300-1200 or even up to 1500 parts .
s~
of filler per 100 parts of polymer) which on its backside is provided with a filler material sheet, e.gO, a polymer foam. Suitable polymers for use are disclosed to be terpolymers of ethylene, propyl-5 lene and a nonconjugated diene (EPDM), polyvinylchloride (PVC), mixed polymers of ethylene and vinyl ace~ate (EVA), styrene-butadiene mixed pol~mers (SBR) and mixtures of these materials with thermoplastic polymers, such as polystyrene and polyolefins.
Rosenfelder U.S. Patent 3,203,921 discloses the use of compositions consisting essentially of 73-88% by weight of a homo- or copolymer of ethylene (which can be ethylene~vinyl acetate or ethylene/
ethyl acrylate copolymer), 2-7% by weight of an 15 aliphatic paraffinic hydrocarbon mineral oil and 10-20% by weight of a mineral filler (for example, calcium carbonate, barium sulfate, etc.) for preparing blow-molded objects such as dolls.
Schumacher and Yllo U.S. Patent 4,131,798 20 discloses compositions consisting essentially of 5-50~ by weight of ethylene interpolymer (e.g., ethy-lene/vinyl acetate copolymer), 2-15% by weight of processing oil, and 50-90~ by weight of filler.
These compositions have utility when formed as 25 sound-deadening sheet and to have particular utility as a bac~side coating on automotive carpets.
Belgian Patent NoO 694,890 entitled "Surface Hardening Plastics Based on Ethylene/Propylene Elasto-mers" discloses blends of ethylene/propylene copolymer, 30 mineral oil, filler and a drying oil for use as a surface hardening mastic, where the copolymer contains 25-75 mole percent propylene (about 33-32 weight per-cent). These blends axe claimed to be useful in sealing mastics in buildings and metal constructions.
JapanesePatent Publication No. 042-235/78 (Japanese AP~?lication No. 118114/76) discloses hot mel~ c ~ ositions c ~ rising an e~hylene/a-olefin copolymer, a hydro OE kon oligomer, a hindered ester, l-lO percent by weight of colloidal sllica and microcrystalline wax. Although these compositions contain mainly olefinic compounds, it is asserted that flexibility and internal loss are maintained while adhesion to olefinic-type film is prevented. The compositions are disclosed to be useful for vibration damping.
U.S. Patent 3,963,802 is related to blends of certain ethylene copolymers and segmented copolyether ester elastomers in specific proportions. Suitable ethylene copolymers are disclosed as those having one or more comonomers selected from the group consisting of alpha-olefins and nonconjugated diolefins, said copolymer having a melting point not greater than 85C. A suitable copolyether ester is disclosed as consisting of 15-95 percent by weight of short chain ester units and 5-85 percent by weight of long chain ester units, said copolyether ester having a melting point of at least 100C. It is disclosed that the copolyether ester elastomer is mad~ softer~ with retention of toughness and other physical properties, by blending with the ethylene copalymer. It is further disclosed that from l to 30 percent ~y weight of fillers and pigments (e.g., very finely divided silica, alumina, or calcium carbonate) may be incorporated in the blend to increase the toughness and temperature resistance.
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According to the present invention, there is provided a composition consisting essentially of ~(a) from about 5 to about 55 percent by weight o~ at least one copolymer o ethylène with at least ~ 4 -one ~-olefin comonomer containing from 4 to 10 carbon atoms, the ethylene content of said copolymer being from about 75 to about 9~% by weight, the comonomer content of said copolymer being from about 2 to about 25 percent by weight, and the melt index of said copolymer being from about 0.1 to about 150, (b) from about 2 to about 12 percent by weight of at least one plasticizer selected from the group consisting of pro-cessing oils, epoxidized oils, polyester, polyethers and polyether esters; (c) from about 40 to about 90 percent by weight of filler; and (d) from 0 to about 27% by weight o elastomeric polymer.
Further provided according to the present invention are the above compositions in the form of a sound-deadening sheet~
Still further provided according to the present invention are aarpets and especially auto-motive carpets having a backside coating consisting essentially of the above compositions.
As used herein, the term "consisting essentially of" means that the named ingredients are essential, however, other ingredients which do not prevent the advantages of the present invention from being realized can also be included.
Detailed Description of the Inv6ntion _ __ . _ _ It has been found that inclusion of a plasticizer in filled blends of ethylene/~-olefin copolymers and filler allows the preparation of blends containing considerably higher filler levels than can be attained in corresponding binary blends of ethylene/~-olefin copolymers and filler.
Flexible, nonexuding blends based on ethylene/~-olefin copolymers containing very high filler levels can be prepared employing certain -~
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plasticizers according to the present invention. Incontrast, highly filled plasticized blends based on either conventional high-density or conventional low-density polyethylene homopolymer are of little apparent 5 utility, exhibiting excessive brittleness, poor elongation, and/or plasticizer exudation.
The ethylene/~-olefin copolymers suitable for the composition of the present invention include copolymers with at least one a-olefin comonomer 10 selected from the group consisting of ~-olefins con-taining from four to ten carbon atoms. Preferably the - comonomer contains from four to eight carbon atoms. The ethylene/a-ole~in copolymers of the cornposition of the present invention are typically manufactured at a 15 synthesis pressure of less than 5000 psia using transition element catalysts. Processes suitable for manufacturing these copolymers are described in detail in U.S.
Patent ~,076,698 and U.S. Patent 4,163,831.
The ethylene content of the copolymer is from 20 about 75 tv about 98 percent by weight, and the u-olefin comonomer content is from about 2 to about 25 percent by weight. The preferred ethylene and comonomer levels are from about 80 to about 96 percent by weight and from about 4 to about 20 percent by weight, respectively. A
25 mixture of two or more ethylene copolymers can ~lso be used in the blends of the present invention in place of a single copolymer, provided the ~-olefin comonomer content of the mixture (expressed in weight ~) is within the above-indicated range. The most preferred 30 comonomer level is from about 6 weight percent to about 16 weight percent. In this range, blends exhibit a combination of tensile properties and flexibility well suited for use as a sound-deadening sheet or for use as carpet backing. Stiffer blends can be obtained 35 by reducing the comonomer content in the copolymer below about 6 weight percent. However, as comonomer , ~ 3~ ~
content is reduced, elongation decreases and plasticizer compatibility problems might arise. Comonomer content above 16 weight percent results in blends which are less stiff and have lower tensile strength, while 5 their elongation i~ increased.
Melt index of the copolymer can range from about 0.~ to about 150. The preferred range is from about 0.5 to about 30, wherein physical properties, principally elongation, are at higher levels. Melt 10 index range of from about 1 to about 10 are most pre-ferred to maintain strength.
Generally from about 5 to about 55% by weight of ethylene/~-olefin copolymer is employed in the composition of the present invention, preferably 15 from about 10 to about 35% by weight, and most preferably from about 15 to about 25% by weight.
The plasticizer ingredient of the present invention can be selected from one of several groups.
The first group is the group known as processing oils.
20 Three types of processing oils are known--paraffinic, aromatic~ and naphthenic. None of these are pure;
the yrades identify the major oil-type present.
Aromatic oils tend to l'bleed" from the blends of the present invention. Bleeding is normally not 25 desirable, but could be useful as specialty appli-cations, for example, in concrete forms where mold release characteristics are valued.
- Naphthenic and paraffinic oils are non-bleeding in the formulations of the present invention 30 when used in proper ratios and are thus preferable for uses such as automotive carpet backing.
Processing oils are also subdivided by viscosity range~ "Thin" oils can be as low as 100-; 500 SUS (Saybolt Universal Seconds) at 100F (38C).
35 "~eavy" oils can be as high as 6000 SUS at 100F (38C~.
~, Processing oils, especially naphthenic and paraffinicoils w;th viscosity of from about 100 to 6000 SUS at 100F (38C) are preferred.
The second group of plasticizers that are 5 efective in the practice of the present invention is the group comprising epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil.
The third group of plasticizers that are effective in the practice of the present invention 10 are polyesters which, .in general are liquid condensation products of a polybasic acid and a polyol. The term "liquid" in the context of the present invention is used to mean pourable at room temperature. The acid component is most often a saturated aliphatic dibasic acid or an 15 aromatic dibasic acid; adipic acid, azelaic acid, phthalic acid, sebacic acid, and glutaric acid, or mixtures of these acids are commonly used. The polyol can be an aliphatic polyol or a poly-oxyalkylene polyol, such as ethylene glycol, propylene glycol, 1,4-- and 1,3-butane 20 glycol, diethylene glycol, and polyethylene glycol.
Preferred polyester compositions would consist of an acid component of which greater than 50% by weight are aliphatic dibasic acids, and a polyol camponent of aliphatic polyol or even more præerably aliphatic gl~ol. ~st pxeferred ccmpositions 25 ~re based on adipic or azelaic acid, and propylene glycol or the 1,3- or 1,4~hutane glycol. The molecular weight of these plasticizers can vary from a low of a few hundred up to a high o about 10,000. The molecular weight of commercial products is seldom specified; however, 30 typically in the trade, the molecular weight range of the product is classified as low, medium, or high. The preferred range for purposes of this invention is that classified as m~dium.
Mixtures of polyesters or eFoxidized oils~th h~xxar-35 bon oils are also effective plasticizers in the present invention. One objective of using such a mixture is .....
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to couple the high efficiency of the relatively high cost polyester or epoxidized oil with the low cost of the hydrocarbon oil. The cost/performance of a compound plasticized with such a mixture can be improved signif-icantly for a given application because properties can betailored more precisely, or filler levels can be increased.
Actually certain advantages in the performance of the blends of the present invention are obtained as will be discussed below, when such a mixture is used as the plasticizer. These polyester plasticizers and their use in filled ethylene interpolymer compositions are described in simultaneously filed Canadian Patent Applica-tion No. 383 342 of M.C. Coughlin.
In general, both the epoxidized oils and the polyesters are more "efficient" than processing oils in plasticizing filled ethylene/~-olefin inter-polymers; i.e., when used at the same weight percent, they produce blends that are more flexible and have higher percent elongation than the corresponding blends containing processing oil as the plasticizer.
Where a mixture of the polyester plasticizer and a hydrocarbon oil is employed, the relative propOr-tions of the two components can be varied over a wide range depending upon performance objectives.
~ixtures containing 50% or less of the polyester are preferred for economic reasons, and most preferred are those containing 20% or less of the polyester.
A fourth group of plasticizers, polyethers and polyether esters, are also effective plasticizers in blends of the ethylene/~-olefin copolymers and fillers of the present invention. In general, poly-ethers are oligomers or polymers of alkylene oxides;
polymers of ethylene or propylene oxide are the most common types available commercially. Polyethers can be prepared by polymerization of aldehydes using ~2~r~ ~
i various types of catalysts, or by acid or base catalyzed polymeri~ation of an alkylene oxide, for example. Polyethers can be terminated by hydroxyl groups to form the diol (glycol) or, in the case of 5 adducts of alkylene oxides with glycerol, for example, the triol, and-so orth. The hydroxyl terminated polyether can ~lso be reacted with an acid, fatty acids such as lauric and stearic acids are commonly used, to form the ester; the most common examples of 10 these compounds are the mono and diesters of poly-ethylene or polypropylene glycol. The molecular weight o polyethers may range up to those typical of high polymars.
Preferred polyether compositions in the 15 practice of this invention are those consisting of the polyols based on random and/or block copolymers of ethylene oxides and propylene oxides. The copolymer polyols provide better performance in terms of efficiency in compounds of the present invention containing very 20 high levels of illerO
Mixtures of the polyether or the polyether ester plasticizers with either a polyester plasticizer or a hydrocarbon porcessing oil can also be used in the practice of this invention. The advantage of 25 polyether/polyester com~ination is the lower cost since the polyethers are cheaper than the polyesters.
Combinations of polyether and processing oil are also cheaper because of the lower cost of the oil.
The relative proportions of the two com-30 ponents in a polyether/polyester combination will beadjusted according to the efficiency of the system based on property requirements and costO Those based on polyester primarily will not be as stiff and will be more expensive, for example, than those based 35 primarily on a polyether or polyether ester.
Where a mixture of the polyether or poly-ether ester and a hydrocarbon oil is employed~ the relative proportions used will again depend upon cost and property re~uirements. Since the polyethers are 5 more expensive than the processing oils, mixtures containing 50~ or less of the polyethers are preferredO
As referred to above, a mixture of processing oil, on the one hand, and epoxidized oil or polyester or polyether or polyether ester, or any combination 10 thereof, on the other hand, can also be used very effectively as the plasticizer for ~he compositions of the present invention. In fact, such a two- or moxe component plasticizer system, comprising from about 50 to about 95 percent by weight of processing 15 oil, gives higher ~ensile elongation than can be obtain-ed using either plasticizer alone at the same levelO
Maximum elongation i5 achieved using a mixture of processing oil and polyester or polyether or polyether ester or any combination thereof comprising from about 20 50 to about 80 percent by weight of processing oil.
The amount of plasticizer(s) in the composi-tion of the present invention is from about 2 to about 12~ by weight, preferably from about 3 to about 10%
~- by weight. Most preferably the amount of plasticizer - ~5 is from about 4 to 8~ by weight.
The third essential ingredient of the com-` position of the present invention is the filler. The percentage of ~iller that can be included in the composi-tion of the present invention on a weight basis is 30 primarily a function of the density of the fill~r.
Particle size of the filler has some effect. Fine particle size fillers generally have a tendency to result in higher blend viscosities; and they are also more expensive. The use of fine filler, especially 35 at high filler loading, results in a smoother extrudate sur~ace when molten blend is extruded through a die orifice. The attendant benefits of using fine ~: `i'' 11 particle size filler in filled polymer blends are described in U.S. Patent 4 263 195, issued on April 21, 1981. No. 9 "Whiting"* (calcium carbonate) which has been used extensively in the present compositions (about 95% through 325 mesh) represents a viable midpoint in coarseness, availability and cost.
Examples of suitable fillers are calcium carbonate, barium sulfate, hydrated alumina, clay, magnesium carbonate, calcium sulfate, silica, flyash, cement dust, wood flour, ground rice hulls and mixtures thereof.
Most preferred fillers are calcium carbonate, barium sulfate, hydrated alumina, and mixtures thereof.
The amount of filler present in the composition of the present invention is from about 40% to about 90 by weight, preferably from about 50 to about 85% by weight. Most preferably, when using a filler of medium density, such as calcium carbonate or hydrated alumina, the amount of filler is from about 65 to about 80% by weight, and when using a filler of higher density, such as barium sulfate, the amount of filler is from about 70 to about 85% by weight.
Hydrated alumina can also be used as the filler to obtain blends which are flame retardant.
Polymers, both homo- and copolymers, other than the one referred to above, can also be used to some extent in combination with the above specified ~ polymers without signi~icantly interfering with the -~ advantages obtained by the present invention. Similarly, other ingredients can also be added to the compositions of the present invention by a compounder in order to obtain some desired effect, such as reduction of cost, or enhancement of physical properties. Accordingly, extender or modifying resins, waxes, foaming agents, crosslinking agents7 antioxidants, flame retardant agents, tackifying ` resins, etc. that are widely used, can be included in the compositions of the present invention.
* denotes trade mark 12 ~
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~ 3~3 ~
Elastome-ic polymers are of interest as modifying resins ~or the blends of the present invention.
They exhibit good compatibility in the blends and can be useful for modifying the flexibility or other physical propertiesv The blends of the present invention can contain from 0 to about 27~ by weight of an elastomer or a mixture ~f elastomers, preferably from about l to about 17~ by weight, and most preferably from about 2 to about 12% by weight~ ~Iooney viscosity of the elasto-mer is prefexably in the range of from 20 to 90.Thermoplastic elastomers (e.g., ethylene-propylene rubber, styrene-butadiene-styrene, polyurethane, etc.) or vulcanizable elastomers (e.g., styrene-butadiene rubber, ethylene/propylene/diene terpolymer ~EPDM), chlorosulfonated polyethylene, etc.) can be used.
Preferred elastomers are ethylene-propylene rubber and EPDM rubber in which the ethylene content should range from about 20 percent by weight to about 80 per-cent by weight. The diene comonomer (in EPDM) is usually methylene norbornene, ethylidene norbornene, dicyclopentadiene or 1,4-hexadiene, although othex dienes may be used, and the concentration of the diene is usually less than about ~ percent by weight. When ~ulcanizable elastomers are used, they are added in the nonvulcanized state;, if desired, the resulting compound can be cured in a subsequent operation to produce a product with increased tensile strength and improved high temperature performance.
The blends of the present invention are thermoplastic in nature and therefore can be recycled after processing. The recycled material may also contain textile fibers, jute, etc. present in the ~rim obtained during production of the finished product (e.g., back-coated automotive carpet).
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A commercially sized batch-type Banbury* or equi~ta-lent intenslve mixer is entirely suitable for preparing the compositions of the present invention. A Farrel* continuous mixer ("FCM") is also an exce]lent mixing device. In either instance, dry ingredients are charged in routine fashion. It is convenient in most cases to inject the plasticizer compo-nent directly into the mixing chamber of either unit as per widely used practice with this type of equipment. When more than one plasticizer is used, and where any one of the plas-ticizers is present in a small amount ~less than about 10weight percent of the total plasticizer mixtllre), the plasti-cizers should be preblended before addition to the other ingredients of the present invention. This will facilitate uniform dis-tribution of each plasticizer component in the final composition and thus ensure that optimum properties are obtained. If desired, -the copolymer and the plasticizer(s~
can be precompounded as a "Master batch" in a suitable inten-sive mixing device (e.g., Banbury mixer or screw extruder).
This "Masterbatch" can then be compounded with the filler and the other remaining ingredients to produce the final compo-sition. A mix cycle of about 3 minutes is generally adequate for the Banbury mixer at an operating temperature usually between 325 and 375F. The operating rate for the FCM unit generally will fall within ranges predicted by literature prepared by the Farxel Company, Ansonia, Connecticut. Again, temperatures between 325 and 375F. are effective. In both cases, a very low plasticizer level, say about 2-3~ may require higher temperatures, while plasticizer levels above about 7% may mix well at lower mixer temperatures. While not evaluated, it is expected that other devices for compounding ;~ of viscous mixes (MI of 0.1 to 20~ s~ould be entirely satis-factory--but in any case, prototype trials in advance are ;; desirable.
Once blends are mixed, routine commercial practices may be used, such as underwater melt cutting plus drying or use of sheeting plus chopping methods, to produce a final ~ pelletized product.
- Primary use for the compositions of the present * denotes trade mark -- .
' :
invention will probably be in the sheeting field, particu-larly for low-cost, dense, sound-deadening structures. Out-standing characteristics such as improved "hand", "drape,"
reduced stif~ness, and reduced thickness of the extruded sheeting result from the compositions of the present inventionO
The hlends of the present invention can readily be extruded onto a substrate, such as an automotive carpet, or can be extruded or calendered as unsupported film or sheet.
Depending upon the equipment used, and the compounding tech-niques employed, it is possible to extrude wide ranges o~film thickness, from below 20 mils to above 100 mils. This then provides industry with an opportunity to vary the amount of sound deadening to be attained by varying film thickness, density of blends, ratio of iller load to binder, and similar techniques well known in the art.
The sound-deadening sheet produced may be used in various ways:
When applied to automotive carpet, blends described are an effective and economic means to deaden sound, while also simultaneously serving as a moldable support or the carpet.
When used in sheet form, the blends can be installed in other areas of an automobile, truck, bus, etc., ; 25 such as side panels, door panels, roofing areas, etc.
In sheet Eorm, blends may be used as drapes or hangings to shield or -to surround a noisy piece of factory equipment such as a loom, a forging press, etc.
In laminated sheet Eorm, blends, faced wi-th another material, might be used to achieve both a decorative and a functional use--such as dividing panels in an open-format oEice.
~ he application of the compositions o~ the present invention in carpets, and particularly in automotive carpets, is essentially identical to the methods as already described in U.S. Patent 4,191,798, , . ~, The following examples are given for the purpose of illustrating the present invention. All parts and percentages are by weight unless otherwise specified.
Comparative Exam~les 1-3 These ex~mples show the increasing difficulty encountered in making highly filled binary blends using ethylene/a-olefin copolymer as the sole binder~ A11 ingredients were premixed in a one-gallon can by being shaken manually for about 0.5 minute. The material was then charged to a labora~ory-sized Banbury inten-sive mixer. Mix conditions used were fluxing for about 3 minutes at a temperature of about 325-375F. Composi-tions and physical properties are summarized in Table 1. Increasing the filler (CaC03) level to 60~ from 50 reduced elongation by about 95~. A further filler increase to 70~ resulted in a mixture which no longer would flux in a Banbury mixer, even after about 10 minutes of mixing time. The product discharged from the mixer aq uncompounded, dry ingredients.
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COMPOSITION AND PHYSICAL PROPERTIES OF
BINARY BLENDS OF ETHYLENE/~-O~EFI~ COPOLYMER
AND CALCIUM CARBONATE
In~redients Ex. Cl Ex. C2 Ex. C3 .
Ethylene/~-olefin ~1(1) 50 40 3~
~9"W~iting"t2) 50 60 70 Physical Pro~erties Sp. Gr. of Blend(3) 1.37 1.51 Tensile Strength, psi( ) 1654 1841 Tensile Strength, kPa11,40312,692 (4) DID
Elongation, % 487 27 NOT
FLUX
Thic~ness o~ Strip mils 63 66 mm 1.60 1.68 Stiffness of Strip, g.(5) 320 390 ~; .
(1) "~owlex"*2045; Dow Chemical Company; ethylene/
a-olefin copolymer (aboutl~ octene o~no~) ~l.I. = 1.14, Density = 0.913
TITLE
Filled and Plasticized Blends Of Linear Lo~ Densitv Polvethylene BACXGROUND OF THE INVENTION
Field of the Invention This invention relates to filled polymer blends and, more specifically, it relates to ~illed blends of ethylene/a-olefin interpolymers modified with plasticizer.
Description of the Prior Art The use of processing oils and other plas-ticizers with natural rubber or snythetic rubber-like compounds containing sulfur, accelerators, carbon black and other additives customarily used in the ru~ber industry is well known. In some instances in order to obtain very high tensile strength values, fillers are omitted. On the other hand, it is known that styrene/butadlene rubber (SBR) compounds, such as are used to adhere jute secondary backings to carpets, can readily hold up to 80~ by weight or more of calcium carbonate filler. Vulcanization or curing enhances blend strength.
For thermo~lastic elastomeric uses, it is desirable both to avoid curing and to employ fillers to reduce blend costs, as well as to increase blend density.
~1 Industrial noise and its control are items o~increasing~concern to governmental, environmental, and industrial organizations. Governmental agencies ~are establishing noisP lLmits to which workers may be exposed to protect their health.
I ~ ` :
From an aesthetic standpoint, noise also presents ~roblems~ Advertisem:ents for "quiet riding"
automo~iles are ubiquitous. Manufacturers are ~attempting~to make other vehicles quiet as well --includin~ campers, trailers, buses, trucks, and AD-505lA
:: :
: ~ .
~ ~ .
~ ~ .
~ .
off-road-use farm vehicles.
It has long been known that interposing mass between a sound source and the area to be kept quiet is an effective means for attaining sound 5 deadening. A sheet of lead is thin, flexible, often highly effective, but costly. The challenge, then, is to attain a dense, thin, flexible sheet which can be interposed between a source of noise and the area to be quietened.
Sheets of thermoplastics or of rubberlike materials have long been used as sound-deadening means.
To make the sheets flexible, dense, strong, and inexpensive has posed a challenge to compounders for many years. For some uses, such as automobile carpet 15 underla~ment, the sound-deadening sheet must also be moldable.
Schwartz U.S. Patent 3,904,456 is related to a method for inhibiting transmission of airborne noise by interPosing in the air space between the 20 noise source and ~he location to be insulated a thin, dense, normally self-supporting film or sheet composed essentially of from about 10 to about 40% by weight of ethylene/vinyl acetate copolymer having an average vinyl acetate content of from about 10 to about 42%
25 by weight and a glass transition temperakure of at least about 30C below the average ambient temperature in the air space, and from about 60 to about 90% by weight of inorganic filler materials, such as sulfates, carbonates, oxides, etc. of ~arium, calciu~, cadmium, 30 etc., effective to produce an overall density greater than at least 2 grams per cubic centimeter.
German Patent Application No. 2,319,431 dis-closes sound-deadening composites suitable for use in automobiles which consist of a highly filled polymer 35 sheet (for example, 300-1200 or even up to 1500 parts .
s~
of filler per 100 parts of polymer) which on its backside is provided with a filler material sheet, e.gO, a polymer foam. Suitable polymers for use are disclosed to be terpolymers of ethylene, propyl-5 lene and a nonconjugated diene (EPDM), polyvinylchloride (PVC), mixed polymers of ethylene and vinyl ace~ate (EVA), styrene-butadiene mixed pol~mers (SBR) and mixtures of these materials with thermoplastic polymers, such as polystyrene and polyolefins.
Rosenfelder U.S. Patent 3,203,921 discloses the use of compositions consisting essentially of 73-88% by weight of a homo- or copolymer of ethylene (which can be ethylene~vinyl acetate or ethylene/
ethyl acrylate copolymer), 2-7% by weight of an 15 aliphatic paraffinic hydrocarbon mineral oil and 10-20% by weight of a mineral filler (for example, calcium carbonate, barium sulfate, etc.) for preparing blow-molded objects such as dolls.
Schumacher and Yllo U.S. Patent 4,131,798 20 discloses compositions consisting essentially of 5-50~ by weight of ethylene interpolymer (e.g., ethy-lene/vinyl acetate copolymer), 2-15% by weight of processing oil, and 50-90~ by weight of filler.
These compositions have utility when formed as 25 sound-deadening sheet and to have particular utility as a bac~side coating on automotive carpets.
Belgian Patent NoO 694,890 entitled "Surface Hardening Plastics Based on Ethylene/Propylene Elasto-mers" discloses blends of ethylene/propylene copolymer, 30 mineral oil, filler and a drying oil for use as a surface hardening mastic, where the copolymer contains 25-75 mole percent propylene (about 33-32 weight per-cent). These blends axe claimed to be useful in sealing mastics in buildings and metal constructions.
JapanesePatent Publication No. 042-235/78 (Japanese AP~?lication No. 118114/76) discloses hot mel~ c ~ ositions c ~ rising an e~hylene/a-olefin copolymer, a hydro OE kon oligomer, a hindered ester, l-lO percent by weight of colloidal sllica and microcrystalline wax. Although these compositions contain mainly olefinic compounds, it is asserted that flexibility and internal loss are maintained while adhesion to olefinic-type film is prevented. The compositions are disclosed to be useful for vibration damping.
U.S. Patent 3,963,802 is related to blends of certain ethylene copolymers and segmented copolyether ester elastomers in specific proportions. Suitable ethylene copolymers are disclosed as those having one or more comonomers selected from the group consisting of alpha-olefins and nonconjugated diolefins, said copolymer having a melting point not greater than 85C. A suitable copolyether ester is disclosed as consisting of 15-95 percent by weight of short chain ester units and 5-85 percent by weight of long chain ester units, said copolyether ester having a melting point of at least 100C. It is disclosed that the copolyether ester elastomer is mad~ softer~ with retention of toughness and other physical properties, by blending with the ethylene copalymer. It is further disclosed that from l to 30 percent ~y weight of fillers and pigments (e.g., very finely divided silica, alumina, or calcium carbonate) may be incorporated in the blend to increase the toughness and temperature resistance.
~~b~
According to the present invention, there is provided a composition consisting essentially of ~(a) from about 5 to about 55 percent by weight o~ at least one copolymer o ethylène with at least ~ 4 -one ~-olefin comonomer containing from 4 to 10 carbon atoms, the ethylene content of said copolymer being from about 75 to about 9~% by weight, the comonomer content of said copolymer being from about 2 to about 25 percent by weight, and the melt index of said copolymer being from about 0.1 to about 150, (b) from about 2 to about 12 percent by weight of at least one plasticizer selected from the group consisting of pro-cessing oils, epoxidized oils, polyester, polyethers and polyether esters; (c) from about 40 to about 90 percent by weight of filler; and (d) from 0 to about 27% by weight o elastomeric polymer.
Further provided according to the present invention are the above compositions in the form of a sound-deadening sheet~
Still further provided according to the present invention are aarpets and especially auto-motive carpets having a backside coating consisting essentially of the above compositions.
As used herein, the term "consisting essentially of" means that the named ingredients are essential, however, other ingredients which do not prevent the advantages of the present invention from being realized can also be included.
Detailed Description of the Inv6ntion _ __ . _ _ It has been found that inclusion of a plasticizer in filled blends of ethylene/~-olefin copolymers and filler allows the preparation of blends containing considerably higher filler levels than can be attained in corresponding binary blends of ethylene/~-olefin copolymers and filler.
Flexible, nonexuding blends based on ethylene/~-olefin copolymers containing very high filler levels can be prepared employing certain -~
. .
~ 3~ ~
plasticizers according to the present invention. Incontrast, highly filled plasticized blends based on either conventional high-density or conventional low-density polyethylene homopolymer are of little apparent 5 utility, exhibiting excessive brittleness, poor elongation, and/or plasticizer exudation.
The ethylene/~-olefin copolymers suitable for the composition of the present invention include copolymers with at least one a-olefin comonomer 10 selected from the group consisting of ~-olefins con-taining from four to ten carbon atoms. Preferably the - comonomer contains from four to eight carbon atoms. The ethylene/a-ole~in copolymers of the cornposition of the present invention are typically manufactured at a 15 synthesis pressure of less than 5000 psia using transition element catalysts. Processes suitable for manufacturing these copolymers are described in detail in U.S.
Patent ~,076,698 and U.S. Patent 4,163,831.
The ethylene content of the copolymer is from 20 about 75 tv about 98 percent by weight, and the u-olefin comonomer content is from about 2 to about 25 percent by weight. The preferred ethylene and comonomer levels are from about 80 to about 96 percent by weight and from about 4 to about 20 percent by weight, respectively. A
25 mixture of two or more ethylene copolymers can ~lso be used in the blends of the present invention in place of a single copolymer, provided the ~-olefin comonomer content of the mixture (expressed in weight ~) is within the above-indicated range. The most preferred 30 comonomer level is from about 6 weight percent to about 16 weight percent. In this range, blends exhibit a combination of tensile properties and flexibility well suited for use as a sound-deadening sheet or for use as carpet backing. Stiffer blends can be obtained 35 by reducing the comonomer content in the copolymer below about 6 weight percent. However, as comonomer , ~ 3~ ~
content is reduced, elongation decreases and plasticizer compatibility problems might arise. Comonomer content above 16 weight percent results in blends which are less stiff and have lower tensile strength, while 5 their elongation i~ increased.
Melt index of the copolymer can range from about 0.~ to about 150. The preferred range is from about 0.5 to about 30, wherein physical properties, principally elongation, are at higher levels. Melt 10 index range of from about 1 to about 10 are most pre-ferred to maintain strength.
Generally from about 5 to about 55% by weight of ethylene/~-olefin copolymer is employed in the composition of the present invention, preferably 15 from about 10 to about 35% by weight, and most preferably from about 15 to about 25% by weight.
The plasticizer ingredient of the present invention can be selected from one of several groups.
The first group is the group known as processing oils.
20 Three types of processing oils are known--paraffinic, aromatic~ and naphthenic. None of these are pure;
the yrades identify the major oil-type present.
Aromatic oils tend to l'bleed" from the blends of the present invention. Bleeding is normally not 25 desirable, but could be useful as specialty appli-cations, for example, in concrete forms where mold release characteristics are valued.
- Naphthenic and paraffinic oils are non-bleeding in the formulations of the present invention 30 when used in proper ratios and are thus preferable for uses such as automotive carpet backing.
Processing oils are also subdivided by viscosity range~ "Thin" oils can be as low as 100-; 500 SUS (Saybolt Universal Seconds) at 100F (38C).
35 "~eavy" oils can be as high as 6000 SUS at 100F (38C~.
~, Processing oils, especially naphthenic and paraffinicoils w;th viscosity of from about 100 to 6000 SUS at 100F (38C) are preferred.
The second group of plasticizers that are 5 efective in the practice of the present invention is the group comprising epoxidized oils such as epoxidized soybean oil and epoxidized linseed oil.
The third group of plasticizers that are effective in the practice of the present invention 10 are polyesters which, .in general are liquid condensation products of a polybasic acid and a polyol. The term "liquid" in the context of the present invention is used to mean pourable at room temperature. The acid component is most often a saturated aliphatic dibasic acid or an 15 aromatic dibasic acid; adipic acid, azelaic acid, phthalic acid, sebacic acid, and glutaric acid, or mixtures of these acids are commonly used. The polyol can be an aliphatic polyol or a poly-oxyalkylene polyol, such as ethylene glycol, propylene glycol, 1,4-- and 1,3-butane 20 glycol, diethylene glycol, and polyethylene glycol.
Preferred polyester compositions would consist of an acid component of which greater than 50% by weight are aliphatic dibasic acids, and a polyol camponent of aliphatic polyol or even more præerably aliphatic gl~ol. ~st pxeferred ccmpositions 25 ~re based on adipic or azelaic acid, and propylene glycol or the 1,3- or 1,4~hutane glycol. The molecular weight of these plasticizers can vary from a low of a few hundred up to a high o about 10,000. The molecular weight of commercial products is seldom specified; however, 30 typically in the trade, the molecular weight range of the product is classified as low, medium, or high. The preferred range for purposes of this invention is that classified as m~dium.
Mixtures of polyesters or eFoxidized oils~th h~xxar-35 bon oils are also effective plasticizers in the present invention. One objective of using such a mixture is .....
~j ~ 3~
to couple the high efficiency of the relatively high cost polyester or epoxidized oil with the low cost of the hydrocarbon oil. The cost/performance of a compound plasticized with such a mixture can be improved signif-icantly for a given application because properties can betailored more precisely, or filler levels can be increased.
Actually certain advantages in the performance of the blends of the present invention are obtained as will be discussed below, when such a mixture is used as the plasticizer. These polyester plasticizers and their use in filled ethylene interpolymer compositions are described in simultaneously filed Canadian Patent Applica-tion No. 383 342 of M.C. Coughlin.
In general, both the epoxidized oils and the polyesters are more "efficient" than processing oils in plasticizing filled ethylene/~-olefin inter-polymers; i.e., when used at the same weight percent, they produce blends that are more flexible and have higher percent elongation than the corresponding blends containing processing oil as the plasticizer.
Where a mixture of the polyester plasticizer and a hydrocarbon oil is employed, the relative propOr-tions of the two components can be varied over a wide range depending upon performance objectives.
~ixtures containing 50% or less of the polyester are preferred for economic reasons, and most preferred are those containing 20% or less of the polyester.
A fourth group of plasticizers, polyethers and polyether esters, are also effective plasticizers in blends of the ethylene/~-olefin copolymers and fillers of the present invention. In general, poly-ethers are oligomers or polymers of alkylene oxides;
polymers of ethylene or propylene oxide are the most common types available commercially. Polyethers can be prepared by polymerization of aldehydes using ~2~r~ ~
i various types of catalysts, or by acid or base catalyzed polymeri~ation of an alkylene oxide, for example. Polyethers can be terminated by hydroxyl groups to form the diol (glycol) or, in the case of 5 adducts of alkylene oxides with glycerol, for example, the triol, and-so orth. The hydroxyl terminated polyether can ~lso be reacted with an acid, fatty acids such as lauric and stearic acids are commonly used, to form the ester; the most common examples of 10 these compounds are the mono and diesters of poly-ethylene or polypropylene glycol. The molecular weight o polyethers may range up to those typical of high polymars.
Preferred polyether compositions in the 15 practice of this invention are those consisting of the polyols based on random and/or block copolymers of ethylene oxides and propylene oxides. The copolymer polyols provide better performance in terms of efficiency in compounds of the present invention containing very 20 high levels of illerO
Mixtures of the polyether or the polyether ester plasticizers with either a polyester plasticizer or a hydrocarbon porcessing oil can also be used in the practice of this invention. The advantage of 25 polyether/polyester com~ination is the lower cost since the polyethers are cheaper than the polyesters.
Combinations of polyether and processing oil are also cheaper because of the lower cost of the oil.
The relative proportions of the two com-30 ponents in a polyether/polyester combination will beadjusted according to the efficiency of the system based on property requirements and costO Those based on polyester primarily will not be as stiff and will be more expensive, for example, than those based 35 primarily on a polyether or polyether ester.
Where a mixture of the polyether or poly-ether ester and a hydrocarbon oil is employed~ the relative proportions used will again depend upon cost and property re~uirements. Since the polyethers are 5 more expensive than the processing oils, mixtures containing 50~ or less of the polyethers are preferredO
As referred to above, a mixture of processing oil, on the one hand, and epoxidized oil or polyester or polyether or polyether ester, or any combination 10 thereof, on the other hand, can also be used very effectively as the plasticizer for ~he compositions of the present invention. In fact, such a two- or moxe component plasticizer system, comprising from about 50 to about 95 percent by weight of processing 15 oil, gives higher ~ensile elongation than can be obtain-ed using either plasticizer alone at the same levelO
Maximum elongation i5 achieved using a mixture of processing oil and polyester or polyether or polyether ester or any combination thereof comprising from about 20 50 to about 80 percent by weight of processing oil.
The amount of plasticizer(s) in the composi-tion of the present invention is from about 2 to about 12~ by weight, preferably from about 3 to about 10%
~- by weight. Most preferably the amount of plasticizer - ~5 is from about 4 to 8~ by weight.
The third essential ingredient of the com-` position of the present invention is the filler. The percentage of ~iller that can be included in the composi-tion of the present invention on a weight basis is 30 primarily a function of the density of the fill~r.
Particle size of the filler has some effect. Fine particle size fillers generally have a tendency to result in higher blend viscosities; and they are also more expensive. The use of fine filler, especially 35 at high filler loading, results in a smoother extrudate sur~ace when molten blend is extruded through a die orifice. The attendant benefits of using fine ~: `i'' 11 particle size filler in filled polymer blends are described in U.S. Patent 4 263 195, issued on April 21, 1981. No. 9 "Whiting"* (calcium carbonate) which has been used extensively in the present compositions (about 95% through 325 mesh) represents a viable midpoint in coarseness, availability and cost.
Examples of suitable fillers are calcium carbonate, barium sulfate, hydrated alumina, clay, magnesium carbonate, calcium sulfate, silica, flyash, cement dust, wood flour, ground rice hulls and mixtures thereof.
Most preferred fillers are calcium carbonate, barium sulfate, hydrated alumina, and mixtures thereof.
The amount of filler present in the composition of the present invention is from about 40% to about 90 by weight, preferably from about 50 to about 85% by weight. Most preferably, when using a filler of medium density, such as calcium carbonate or hydrated alumina, the amount of filler is from about 65 to about 80% by weight, and when using a filler of higher density, such as barium sulfate, the amount of filler is from about 70 to about 85% by weight.
Hydrated alumina can also be used as the filler to obtain blends which are flame retardant.
Polymers, both homo- and copolymers, other than the one referred to above, can also be used to some extent in combination with the above specified ~ polymers without signi~icantly interfering with the -~ advantages obtained by the present invention. Similarly, other ingredients can also be added to the compositions of the present invention by a compounder in order to obtain some desired effect, such as reduction of cost, or enhancement of physical properties. Accordingly, extender or modifying resins, waxes, foaming agents, crosslinking agents7 antioxidants, flame retardant agents, tackifying ` resins, etc. that are widely used, can be included in the compositions of the present invention.
* denotes trade mark 12 ~
.
~ 3~3 ~
Elastome-ic polymers are of interest as modifying resins ~or the blends of the present invention.
They exhibit good compatibility in the blends and can be useful for modifying the flexibility or other physical propertiesv The blends of the present invention can contain from 0 to about 27~ by weight of an elastomer or a mixture ~f elastomers, preferably from about l to about 17~ by weight, and most preferably from about 2 to about 12% by weight~ ~Iooney viscosity of the elasto-mer is prefexably in the range of from 20 to 90.Thermoplastic elastomers (e.g., ethylene-propylene rubber, styrene-butadiene-styrene, polyurethane, etc.) or vulcanizable elastomers (e.g., styrene-butadiene rubber, ethylene/propylene/diene terpolymer ~EPDM), chlorosulfonated polyethylene, etc.) can be used.
Preferred elastomers are ethylene-propylene rubber and EPDM rubber in which the ethylene content should range from about 20 percent by weight to about 80 per-cent by weight. The diene comonomer (in EPDM) is usually methylene norbornene, ethylidene norbornene, dicyclopentadiene or 1,4-hexadiene, although othex dienes may be used, and the concentration of the diene is usually less than about ~ percent by weight. When ~ulcanizable elastomers are used, they are added in the nonvulcanized state;, if desired, the resulting compound can be cured in a subsequent operation to produce a product with increased tensile strength and improved high temperature performance.
The blends of the present invention are thermoplastic in nature and therefore can be recycled after processing. The recycled material may also contain textile fibers, jute, etc. present in the ~rim obtained during production of the finished product (e.g., back-coated automotive carpet).
:..
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A commercially sized batch-type Banbury* or equi~ta-lent intenslve mixer is entirely suitable for preparing the compositions of the present invention. A Farrel* continuous mixer ("FCM") is also an exce]lent mixing device. In either instance, dry ingredients are charged in routine fashion. It is convenient in most cases to inject the plasticizer compo-nent directly into the mixing chamber of either unit as per widely used practice with this type of equipment. When more than one plasticizer is used, and where any one of the plas-ticizers is present in a small amount ~less than about 10weight percent of the total plasticizer mixtllre), the plasti-cizers should be preblended before addition to the other ingredients of the present invention. This will facilitate uniform dis-tribution of each plasticizer component in the final composition and thus ensure that optimum properties are obtained. If desired, -the copolymer and the plasticizer(s~
can be precompounded as a "Master batch" in a suitable inten-sive mixing device (e.g., Banbury mixer or screw extruder).
This "Masterbatch" can then be compounded with the filler and the other remaining ingredients to produce the final compo-sition. A mix cycle of about 3 minutes is generally adequate for the Banbury mixer at an operating temperature usually between 325 and 375F. The operating rate for the FCM unit generally will fall within ranges predicted by literature prepared by the Farxel Company, Ansonia, Connecticut. Again, temperatures between 325 and 375F. are effective. In both cases, a very low plasticizer level, say about 2-3~ may require higher temperatures, while plasticizer levels above about 7% may mix well at lower mixer temperatures. While not evaluated, it is expected that other devices for compounding ;~ of viscous mixes (MI of 0.1 to 20~ s~ould be entirely satis-factory--but in any case, prototype trials in advance are ;; desirable.
Once blends are mixed, routine commercial practices may be used, such as underwater melt cutting plus drying or use of sheeting plus chopping methods, to produce a final ~ pelletized product.
- Primary use for the compositions of the present * denotes trade mark -- .
' :
invention will probably be in the sheeting field, particu-larly for low-cost, dense, sound-deadening structures. Out-standing characteristics such as improved "hand", "drape,"
reduced stif~ness, and reduced thickness of the extruded sheeting result from the compositions of the present inventionO
The hlends of the present invention can readily be extruded onto a substrate, such as an automotive carpet, or can be extruded or calendered as unsupported film or sheet.
Depending upon the equipment used, and the compounding tech-niques employed, it is possible to extrude wide ranges o~film thickness, from below 20 mils to above 100 mils. This then provides industry with an opportunity to vary the amount of sound deadening to be attained by varying film thickness, density of blends, ratio of iller load to binder, and similar techniques well known in the art.
The sound-deadening sheet produced may be used in various ways:
When applied to automotive carpet, blends described are an effective and economic means to deaden sound, while also simultaneously serving as a moldable support or the carpet.
When used in sheet form, the blends can be installed in other areas of an automobile, truck, bus, etc., ; 25 such as side panels, door panels, roofing areas, etc.
In sheet Eorm, blends may be used as drapes or hangings to shield or -to surround a noisy piece of factory equipment such as a loom, a forging press, etc.
In laminated sheet Eorm, blends, faced wi-th another material, might be used to achieve both a decorative and a functional use--such as dividing panels in an open-format oEice.
~ he application of the compositions o~ the present invention in carpets, and particularly in automotive carpets, is essentially identical to the methods as already described in U.S. Patent 4,191,798, , . ~, The following examples are given for the purpose of illustrating the present invention. All parts and percentages are by weight unless otherwise specified.
Comparative Exam~les 1-3 These ex~mples show the increasing difficulty encountered in making highly filled binary blends using ethylene/a-olefin copolymer as the sole binder~ A11 ingredients were premixed in a one-gallon can by being shaken manually for about 0.5 minute. The material was then charged to a labora~ory-sized Banbury inten-sive mixer. Mix conditions used were fluxing for about 3 minutes at a temperature of about 325-375F. Composi-tions and physical properties are summarized in Table 1. Increasing the filler (CaC03) level to 60~ from 50 reduced elongation by about 95~. A further filler increase to 70~ resulted in a mixture which no longer would flux in a Banbury mixer, even after about 10 minutes of mixing time. The product discharged from the mixer aq uncompounded, dry ingredients.
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COMPOSITION AND PHYSICAL PROPERTIES OF
BINARY BLENDS OF ETHYLENE/~-O~EFI~ COPOLYMER
AND CALCIUM CARBONATE
In~redients Ex. Cl Ex. C2 Ex. C3 .
Ethylene/~-olefin ~1(1) 50 40 3~
~9"W~iting"t2) 50 60 70 Physical Pro~erties Sp. Gr. of Blend(3) 1.37 1.51 Tensile Strength, psi( ) 1654 1841 Tensile Strength, kPa11,40312,692 (4) DID
Elongation, % 487 27 NOT
FLUX
Thic~ness o~ Strip mils 63 66 mm 1.60 1.68 Stiffness of Strip, g.(5) 320 390 ~; .
(1) "~owlex"*2045; Dow Chemical Company; ethylene/
a-olefin copolymer (aboutl~ octene o~no~) ~l.I. = 1.14, Density = 0.913
(2) Calcium Carbonate, as commercial ground limestone;
Georgia Marble Company.
Georgia Marble Company.
(3) Referred to water.
(4) Tensile strength and elongation measurements made on Instron Tester using ASTM Method D1708 at crosshead speed of 2 in. (5.1 cm)/min. Samples are 00876 in. (2.23 cm.) X 0.187 in. (0.47 cm.) in size, at strip thickness shown in ta~le.
~` 35 ~; * Denotes trade mark ~ . . .
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.............. :;.. C:.. :.. ;a:.. :.. : .. : .... . ..
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Table 1 footnotes (cont'd.)
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Table 1 footnotes (cont'd.)
(5) Stiffness of strip measured by placing a 1 in. x
6 in. (2.54 cm. x 15;2 cm.) strip on a platform scale and measuring the force required to make the ends of the test strip meet at room temperature.
Strips were prepared by molding the material in a heated Pasadena press @ 175C.
, .~ 25 ~; :
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Exam~les 1 and 2 and Comparative Examples 4 and 5 The blends of these examples were prepared and their physical prop~rties were determined in the same manner as those of Comparative Examples 1-3.
Compositions and physical properties are summarized in Table 2. Examples 1 and 2 demonstrate that, by use of an appropriate plasticizer, highly filled (in these examples, 72.5~ CaCO3) ethylene/~-olefin copolymers exhibiting useful propertie~ can be produced. ~ithout plasticizer, blends at only 70% filler cannot be successfully compounded in a Banbury mixer (Example C3).
With plasticizer~ blends at 72.5% filler loading (Ex. 1 and Ex. 2) exhibit comparable elongation and better flexibility than binary blends of polymer/filler at only 60~ loading (Ex. C2).
Example~4 illustrates what happens when the ethylene/a~olefin copolymer, in a blend with filler and processing oil pl sticize~ is replaced with low-density polyethylene homopolymer. The resulting blend exhibits 20- about 75% lower elongation and is very brittle, failing catastrophically in the crease test. Moreover, the blend exudes plasticizer freely, with oil droplets visible on the surface after only one day of storage at room conditions.
Example C5 illustrates what happens when the ethylene/a-olefin copol~mer is replaced with high-density polyethylene homopolymer. The resulting blend has low elongation and is extremely brittle, failing in the crease test and also breaking into two pieces in the "stiffness" test.
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COMPOSITION A~D PHYSICAL PROPERTIES OF
ETHYLENE POLYMER-CALCIUM
S CARBONATE--PROCESSING bI1 BLENDS
Ingredients Ex. 1 Ex. 2 Ex. C4 Ex. C5 Ethylene/~-olefin ~1 20.2 ~thylene/a-olefin ~2(~ 20.2 Polyethylene ~1(2) __ -_ 20.2 --Polyethylene ~2(3) __ __ _ 20.2 ~9 Whiting 72.5 72.5 72.5 72.5 Naphthenic Oil(4) 7,3 7,3 7~3 7.3 Ph~sical Properties 15 Sp. Gr. of Blend 1.77 1.78 1.78 1.78 Tensile Strength, psi 717 737 578 879 kPa4943 5081 3986 6060 Elongation, % 34 21 5 10 Thickness o~ S:trip mils ~0 60 59 63 - mm 1~52 1.52 1.50 1.60 Stiffness of Strip, g.157 179 1~8 BR~XE IN
. TEST
~~ (5) ~ass Pass Fa 1 Fail Plasticizer Exudati:on' None None ~eavy None .
~: 25 (1) "DNGA" 7344~ Union Carbide Company; ethylene~a-olefin copolymer (about 5.~% butene comono~er) M.I. = 1.8, Density = 0.922 g./ccO
(2) "Alathon~ 20; Du Pont Comp~ny; Low Densi~y Polyethy-lene Homopolymer; M.I. = 1.9, Density -- 0.920 . i , (3) "Alathon" 7835; Du Pont Company; ~iyh Density Polyethylene Homopolymer; M.I. = 3.0, Density =0.960.
(4) "Clrcosol"*4240; Sun Petxoleum Products Company.
The composition for the oil as given by ~he *penote~s t~ade maxk ~ ~ .
. ` .
: ~ :
, '~
: ' 35~9~
Table 2 footnotes ~cont'd.) supplier is 39% naphthenic carbon, 40% paraffinic carbon, and 21~ aromatic carbon.
(5) The crease test is performed by folding a 1" X 6"
strip at ambient temperature back upon itself and pinching or pressing the folded area flat. (This corresponds to folding the sample over a mandrel of zero diameter)~ If a clean break occurs, with the strip splitting into separate pieces, the sample fails the test. If the sample does not ~separate into two pieces, it passes the test.
.20 ,, ~ 25 :
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~' Examples 3 to 5 Examples 3 to S illustrate the effect on blend properties of using an epoxidized oil or liquid polyester as the plasticizer in either total or partial rPplacement of the processing oil plasticizer. Results are presented in Table 3.
In Example 3, 100% replacement of the naphthenic oil with the epoxidized oil results in a sixfold increase in elongation and a 60% reduction in stiffness.
In ~xample 4, 100% replacement o~ the naphthenic oil with the liquid polyester results in an eightfold increase in elongation and a 65~ reduction in stiffness.
Example 5 illustrates the effect of replacing 50% of the naphthenic oil in the blend with the liquid polyester. Elongation is increased tenfold and stiff-ness-is reduced 62~. This example also illustrates an interesting and unexpected effect: a blend containing a one/one mixture of processing oil and liquid polyester exhibits higher elongation than the blends containing either plasticizer used alone. (Compare Examples 5, 4, and 1.) It becomes apparent from these examples that ~; the selection of the plasticizer (or combination of plasticizers~ in the practice of the present invention offers the user significant latitude in obtaining physical properties appropriate or his particular end-use or application.
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:
COMPOSITION A~D PHYSICAL PROPERTIES OF
BLENDS OF ETHYLENE/u~OLEFIN COPOLY-MER -CALCIUM CARBONATE PLASTICIZER
5 In~redients Ex. 3 Exo 4 Ex. 5 ~x. 1 E-thylene/a-olefin ''l20.220.220.2 20.2 #9 "~7hiting" 72.5 72.5 72.5 72.5 Epoxidized Oil(l) 7.3 Liquid Polyester(2) _- 7.3 3.65 -_ Naphthenic Oil(3) -- -- 3.65 7.3 Physical Properties Sp. Gr. of Blend 1.76 1.801.82 1077 Tensile Strength, psi 400 471 453 717 kPa2758 3247 3123 4943 Elongation, % 217289 . 369 34 ~ Thickness of Strip - mils ~9 58 58 60 mm 1.50 --1.47-1_47 1.52 Stif~ness of Strip, g. 62 55 60 157 (1) "Paraplex"*G-62; Rohm & Haas Company; epoxidized : ~ 25 soybean oil.
(2) "Santicizer'~ 429; Monsanto Company; medium molecular weight conde~sation product of aliphatic dibasic acid and glycol, specific gr~avity l.l, acid num~er 2.2 mg KOH/g.
(3) "Circosol" 4240; Sun Oil Company ~ * Denotes trade:m~rk :j : 35 .
q~3 Example5 6 and 7 Example 6 shows the effect of replacing part of the ethylene/~-olein polymer in a blend with an elastomeric polymer, ethylene/propylene/diene monomer (EPDM) rubber. The resulting blend, as shown in Table 4, exhibits a twentyfold increase in elongation and a 45~
reduction in stiffness. (Compare Example 6 and Example 1.) More or less elastomer can be incorpora~ed depending on the particular physical properties desired. Elasto-meric polymer can also be effectively incorporated inblends plasticized with epoxidized oil or liquid poly~
ester, polyether or polyether ester. Example 7 is an elastomer containing blend plasticized with a liquid polyester.
;
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. ..
CO~OSITION AND PHYSICAL PROPERTIES OF BLEND5 OF ETHYLENE/~-OLEFIN COPOLYMER-EPDM RU3BER-CALCIUM CARBONATE-PLASTICIZER _ _ 5 In~redients Ex. 6 ~x. 7 Ex Ethylene/~-olefin ~110.1. 10.1 20.2 EPDM Rubber(l) 10.1 10.1 ~9 "Whiting" 72.5 72.5 72.5 Naphthenic Oil~2) 7.3 - -- 7.3 Liquid Polyester(3) ---- 7 3 ~~~~
Physcial Properties Sp~ Gr. of Blend 1.78 1.79 1.77 Tensile Strength, psi 490 398 717 kPa 3378 2744 4943 Elongation, ~ 670 510 34 Thickness of Strip mils 60 60 60 mm 1.52 1.52 1.52 20 Stiffness o~ Strip, g. 86 29 15t ~' ~ (1) "Nordel"*1560 hydrocarbon rubber; E. I. du Pont de ;~ Nemours and Company; sulfur curable pol~mer based on ;~ ethylene/propylene/1,4-hexadiene.
(2) "Circosol" 4240.
~` 25 (3) "Santicizer" 429.
~:, * Denotes trade mark ~ ' .
, ~ 30 ' :~:
: ~ 25 . .
;~,:
Strips were prepared by molding the material in a heated Pasadena press @ 175C.
, .~ 25 ~; :
30:
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Exam~les 1 and 2 and Comparative Examples 4 and 5 The blends of these examples were prepared and their physical prop~rties were determined in the same manner as those of Comparative Examples 1-3.
Compositions and physical properties are summarized in Table 2. Examples 1 and 2 demonstrate that, by use of an appropriate plasticizer, highly filled (in these examples, 72.5~ CaCO3) ethylene/~-olefin copolymers exhibiting useful propertie~ can be produced. ~ithout plasticizer, blends at only 70% filler cannot be successfully compounded in a Banbury mixer (Example C3).
With plasticizer~ blends at 72.5% filler loading (Ex. 1 and Ex. 2) exhibit comparable elongation and better flexibility than binary blends of polymer/filler at only 60~ loading (Ex. C2).
Example~4 illustrates what happens when the ethylene/a~olefin copolymer, in a blend with filler and processing oil pl sticize~ is replaced with low-density polyethylene homopolymer. The resulting blend exhibits 20- about 75% lower elongation and is very brittle, failing catastrophically in the crease test. Moreover, the blend exudes plasticizer freely, with oil droplets visible on the surface after only one day of storage at room conditions.
Example C5 illustrates what happens when the ethylene/a-olefin copol~mer is replaced with high-density polyethylene homopolymer. The resulting blend has low elongation and is extremely brittle, failing in the crease test and also breaking into two pieces in the "stiffness" test.
': ~
~ 35 ,.,~
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COMPOSITION A~D PHYSICAL PROPERTIES OF
ETHYLENE POLYMER-CALCIUM
S CARBONATE--PROCESSING bI1 BLENDS
Ingredients Ex. 1 Ex. 2 Ex. C4 Ex. C5 Ethylene/~-olefin ~1 20.2 ~thylene/a-olefin ~2(~ 20.2 Polyethylene ~1(2) __ -_ 20.2 --Polyethylene ~2(3) __ __ _ 20.2 ~9 Whiting 72.5 72.5 72.5 72.5 Naphthenic Oil(4) 7,3 7,3 7~3 7.3 Ph~sical Properties 15 Sp. Gr. of Blend 1.77 1.78 1.78 1.78 Tensile Strength, psi 717 737 578 879 kPa4943 5081 3986 6060 Elongation, % 34 21 5 10 Thickness o~ S:trip mils ~0 60 59 63 - mm 1~52 1.52 1.50 1.60 Stiffness of Strip, g.157 179 1~8 BR~XE IN
. TEST
~~ (5) ~ass Pass Fa 1 Fail Plasticizer Exudati:on' None None ~eavy None .
~: 25 (1) "DNGA" 7344~ Union Carbide Company; ethylene~a-olefin copolymer (about 5.~% butene comono~er) M.I. = 1.8, Density = 0.922 g./ccO
(2) "Alathon~ 20; Du Pont Comp~ny; Low Densi~y Polyethy-lene Homopolymer; M.I. = 1.9, Density -- 0.920 . i , (3) "Alathon" 7835; Du Pont Company; ~iyh Density Polyethylene Homopolymer; M.I. = 3.0, Density =0.960.
(4) "Clrcosol"*4240; Sun Petxoleum Products Company.
The composition for the oil as given by ~he *penote~s t~ade maxk ~ ~ .
. ` .
: ~ :
, '~
: ' 35~9~
Table 2 footnotes ~cont'd.) supplier is 39% naphthenic carbon, 40% paraffinic carbon, and 21~ aromatic carbon.
(5) The crease test is performed by folding a 1" X 6"
strip at ambient temperature back upon itself and pinching or pressing the folded area flat. (This corresponds to folding the sample over a mandrel of zero diameter)~ If a clean break occurs, with the strip splitting into separate pieces, the sample fails the test. If the sample does not ~separate into two pieces, it passes the test.
.20 ,, ~ 25 :
~ ~:
:~ 30 : :
.~ :
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~' Examples 3 to 5 Examples 3 to S illustrate the effect on blend properties of using an epoxidized oil or liquid polyester as the plasticizer in either total or partial rPplacement of the processing oil plasticizer. Results are presented in Table 3.
In Example 3, 100% replacement of the naphthenic oil with the epoxidized oil results in a sixfold increase in elongation and a 60% reduction in stiffness.
In ~xample 4, 100% replacement o~ the naphthenic oil with the liquid polyester results in an eightfold increase in elongation and a 65~ reduction in stiffness.
Example 5 illustrates the effect of replacing 50% of the naphthenic oil in the blend with the liquid polyester. Elongation is increased tenfold and stiff-ness-is reduced 62~. This example also illustrates an interesting and unexpected effect: a blend containing a one/one mixture of processing oil and liquid polyester exhibits higher elongation than the blends containing either plasticizer used alone. (Compare Examples 5, 4, and 1.) It becomes apparent from these examples that ~; the selection of the plasticizer (or combination of plasticizers~ in the practice of the present invention offers the user significant latitude in obtaining physical properties appropriate or his particular end-use or application.
.
;`~
:
COMPOSITION A~D PHYSICAL PROPERTIES OF
BLENDS OF ETHYLENE/u~OLEFIN COPOLY-MER -CALCIUM CARBONATE PLASTICIZER
5 In~redients Ex. 3 Exo 4 Ex. 5 ~x. 1 E-thylene/a-olefin ''l20.220.220.2 20.2 #9 "~7hiting" 72.5 72.5 72.5 72.5 Epoxidized Oil(l) 7.3 Liquid Polyester(2) _- 7.3 3.65 -_ Naphthenic Oil(3) -- -- 3.65 7.3 Physical Properties Sp. Gr. of Blend 1.76 1.801.82 1077 Tensile Strength, psi 400 471 453 717 kPa2758 3247 3123 4943 Elongation, % 217289 . 369 34 ~ Thickness of Strip - mils ~9 58 58 60 mm 1.50 --1.47-1_47 1.52 Stif~ness of Strip, g. 62 55 60 157 (1) "Paraplex"*G-62; Rohm & Haas Company; epoxidized : ~ 25 soybean oil.
(2) "Santicizer'~ 429; Monsanto Company; medium molecular weight conde~sation product of aliphatic dibasic acid and glycol, specific gr~avity l.l, acid num~er 2.2 mg KOH/g.
(3) "Circosol" 4240; Sun Oil Company ~ * Denotes trade:m~rk :j : 35 .
q~3 Example5 6 and 7 Example 6 shows the effect of replacing part of the ethylene/~-olein polymer in a blend with an elastomeric polymer, ethylene/propylene/diene monomer (EPDM) rubber. The resulting blend, as shown in Table 4, exhibits a twentyfold increase in elongation and a 45~
reduction in stiffness. (Compare Example 6 and Example 1.) More or less elastomer can be incorpora~ed depending on the particular physical properties desired. Elasto-meric polymer can also be effectively incorporated inblends plasticized with epoxidized oil or liquid poly~
ester, polyether or polyether ester. Example 7 is an elastomer containing blend plasticized with a liquid polyester.
;
:
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.
. ..
CO~OSITION AND PHYSICAL PROPERTIES OF BLEND5 OF ETHYLENE/~-OLEFIN COPOLYMER-EPDM RU3BER-CALCIUM CARBONATE-PLASTICIZER _ _ 5 In~redients Ex. 6 ~x. 7 Ex Ethylene/~-olefin ~110.1. 10.1 20.2 EPDM Rubber(l) 10.1 10.1 ~9 "Whiting" 72.5 72.5 72.5 Naphthenic Oil~2) 7.3 - -- 7.3 Liquid Polyester(3) ---- 7 3 ~~~~
Physcial Properties Sp~ Gr. of Blend 1.78 1.79 1.77 Tensile Strength, psi 490 398 717 kPa 3378 2744 4943 Elongation, ~ 670 510 34 Thickness of Strip mils 60 60 60 mm 1.52 1.52 1.52 20 Stiffness o~ Strip, g. 86 29 15t ~' ~ (1) "Nordel"*1560 hydrocarbon rubber; E. I. du Pont de ;~ Nemours and Company; sulfur curable pol~mer based on ;~ ethylene/propylene/1,4-hexadiene.
(2) "Circosol" 4240.
~` 25 (3) "Santicizer" 429.
~:, * Denotes trade mark ~ ' .
, ~ 30 ' :~:
: ~ 25 . .
;~,:
Claims (44)
1. A thermoplastic composition consisting essentially of (a) from about 5 to about 55% by weight of at least one copolymer of ethylene with at least one .alpha.-olefin comonomer said comonomer containing from 4 to 10 carbon atoms, the ethylene content of said copolymer being from about 75 to about 98% by weight, the comonomer content of said copolymer being from about 2 to about 25% by weight, and the melt index of said copolymer being from about 0.1 to about 150;
(b) from about 2 to about 12% by weight of at least one plasticizer selected from the group consisting of processing oils, epoxidized oils, polyesters, polyethers and polyether esters; (c) from about 40 to about 90% by weight of filler; and (d) from 0 to about 27%
by weight of elastomeric polymer.
(b) from about 2 to about 12% by weight of at least one plasticizer selected from the group consisting of processing oils, epoxidized oils, polyesters, polyethers and polyether esters; (c) from about 40 to about 90% by weight of filler; and (d) from 0 to about 27%
by weight of elastomeric polymer.
2. THe composition of Claim 1 wherein said elastomeric polymer is present in an amount of 0% by weight.
3. The composition of Claim 2 wherein (a) said ethylene/.alpha.-olefin copolymer is present in an amount of from about 10 to about 35% by weight; (b) said plasticizer is present in an amount of from about 3 to about 10% by weight; and (c) said filler is present in an amount of from about 50 to about 85%
by weight.
by weight.
4. The composition of Claim 3 wherein the .alpha.-olefin comonomer contains from 4 to 8 carbon atoms, the ethylene content of the ethylene/.alpha.-olefin copolymer is from about 80 to about 96% by weight, the comonomer content is from about 4 to about 20% by weight, and the melt index of said copolymer is from about 0.5 to about 30.
5. The composition of Claim 4 wherein said filler is selected from the group consisting of calcium carbonate, barium sulfate, hydrated alumina, clay, magnesium carbonate, calcium sulfate, silica, flyash, cement dust, wood flour, ground rice hulls and mixtures thereof.
6. The composition of Claim 5 wherein said filler is selected from the group consisting of calcium carbonate, barium sulfate, hydrated alumina and mixtures thereof.
7. The composition of Claim 5 wherein said plasticizer is selected from the group consisting of processing oils.
8. The composition of Claim 7 wherein said processing oil is selected from the group consisting of naphthenic and paraffinic oils.
9. The composition of Claim 8 wherein said plasticizer is a mixture of (.alpha.) processing oil and (.beta.) epoxidized oil or polyester or polyether or polyether ester or any combination thereof, wherein said process-ing oil is present in an amount of from about 50 to about 95 percent by weight.
10. The composition of Claim 9 wherein said processing oil is present in an amount of from about 50 to about 80 percent by weight.
11. The composition of Claim 5 wherein said plasticizer is selected from the group consisting of polyesters.
12. The composition of Claim 11 wherein said polyester is a liquid condensation product of (.alpha.) dibasic acid selected from the group consisting of saturated aliphatic dibasic acids and aromatic dibasic acids and (.beta.) polyol selected from the group consisting of aliphatic polyols and polyoxyalkylenepolyols.
13. The composition of Claim 12 wherein greater than 50 percent by weight of the acid component of said polyester is selected from aliphatic dibasic acids and the polyol component is selected from aliphatic glycols.
14. The composition of Claim 5 wherein said plasticizer is selected from the group consisting of polyethers.
15. The composition of Claim 14 wherein said polyether is selected from polyols based on random and block copolymers of ethylene oxides or propylene oxides.
16. The composition of Claim 5 wherein said plasticizer is selected from the group consisting of polyether esters.
17. The composition of Claim 16 wherein said polyether ester is selected from esters of polyols based on polymers or copolymers of ethylene oxides or propylene oxides.
18. The composition of Claim 5 wherein said plasticizer is selected from the group consisting of epoxidized oils.
19. The composition of Claim 18 wherein said epoxidized oil is selected from the group consisting of epoxidized soybean oil and epoxidized linseed oil.
20. The composition of Claim 5 wherein (a) said ethylene/.alpha.-olefin copolymer is present in an amount of from about 15 to about 25 percent by weight; (b) said plasticizer is present in an amount of from about 4 to about 8 percent by weight; and (c) when said filler is calcium carbonate or hydrated alumina the amount of filler is from about 65 to about 80 percent by weight, and when said filler is barium sulfate the amount of filler is from about 70 to about 85 percent by weight.
21. The composition of Claim 20 wherein the ethylene content of the ethylene/.alpha.-olefin copolymer is from about 84 to about 94 percent by weight, the comonomoner content is from about 6 to about 16 percent by weight, and the melt index of said copolymer is from about 1 to about 10.
22. The composition of Claim 21 wherein the comonomer is butene.
23. The composition of Claim 21 wherein the comonomer is octene.
24. The composition of any one of Claim 1, Claim 5 and Claim 9 in the form of a sound-deadening sheet.
25. The composition of any one of Claim 12, Claim 14 and Claim 16 in the form of a sound-deadening sheet.
26. The composition of Claim 18 or Claim 20 in the form of a sound-deadening sheet.
27. The composition of Claim 22 or Claim 23 in the form of a sound deadening sheet.
28. A carpet having a backside coating con-sisting essentially of the composition of any one of Claim 1, Claim 5 and Claim 9.
29. A carpet having a backside coating con-sisting essentially of the composition of any one of Claim 12, Claim 14 and Claim 16.
30. A carpet having-a backside coating con-sisting essentially of the composition of Claim 18 or Claim 20.
31. A carpet having a backside coating con-sisting essentially of the composition of Claim 22 or Claim 23.
32. An automotive carpet having a backside coating consisting essentially of the composition of any one of Claim 1, Claim 5 and Claim 9.
33. An automotive carpet having a backside coating consisting essentially of the composition of any one of Claim 12, Claim 14 and Claim 16.
34. An automotive carpet having a backside coating consisting essentially of the composition of Claim 18 or Claim 20.
35. An automotive carpet having a backside coating consisting essentially of the composition of Claim 22 or Claim 23.
36. The composition of any one of Claim 4, Claim 7 and Claim 9 containing from 0 to about 27% by weight of elastomeric polymer.
37. The composition of any one of Claim 12, Claim 15, and Claim 17 containing from 0 to about 27% by weight of elastomeric polymer.
38. The composition of Claim 19 or Claim 21 containing from 0 to about 27% by weight of elastomeric polymer.
39. The composition of any one of Claim 4, Claim 7 and Claim 9 containing from about 1 to about 17%
by weight of elastomeric polymer selected from the group consisting of styrene-butadiene rubber, polyisobutylene, ethylene/propylene rubber, and terpolymer of ethylene, propylene and a diene monomer.
by weight of elastomeric polymer selected from the group consisting of styrene-butadiene rubber, polyisobutylene, ethylene/propylene rubber, and terpolymer of ethylene, propylene and a diene monomer.
40. The composition of any one of Claim 12, Claim 15 and Claim 17 containing from about 1 to about 17%
by weight of elastomeric polymer selected from the group consisting of styrene-butadiene rubber, polyisobutylene, ethylene/propylene rubber, and terpolymer of ethylene, propylene and a diene monomer.
by weight of elastomeric polymer selected from the group consisting of styrene-butadiene rubber, polyisobutylene, ethylene/propylene rubber, and terpolymer of ethylene, propylene and a diene monomer.
41. The composition of Claim 19 or Claim 21 containing from about 1 to about 17% by weight of elasto-meric polymer selected from the group consisting of styrene butadiene rubber, polyisobutylene, ethylene/
propylene rubber, and terpolymer of ethylene, propylene and a diene monomer.
propylene rubber, and terpolymer of ethylene, propylene and a diene monomer.
42. The composition of any one of Claim 1, Claim 7 and Claim 9 containing from about 2 to about 12%
by weight of elastomeric polymer selected from the group consisting of ethylene/propylene rubber and terpolymers of ethylene, propylene and a diene monomer, wherein the ethylene content is from about 20 to about 80% by weight and the diene content is from 0 to about 5% by weight, said dienes being selected from the group consisting of methylene norbornene, ethylidene norbornene, dicyclo-pentadiene and 1,4-hexadiene.
by weight of elastomeric polymer selected from the group consisting of ethylene/propylene rubber and terpolymers of ethylene, propylene and a diene monomer, wherein the ethylene content is from about 20 to about 80% by weight and the diene content is from 0 to about 5% by weight, said dienes being selected from the group consisting of methylene norbornene, ethylidene norbornene, dicyclo-pentadiene and 1,4-hexadiene.
43. The composition of any one of Claim 12, Claim 15 and Claim 17 containing from about 2 to about 12%
by weight of elastomeric polymer selected from the group consisting of ethylene/propylene rubber and terpolymers of ethylene, propylene and a diene monomer, wherein the ethylene content is from about 20 to about 80% by weight and the diene content is about 0 to about 5% by weight, said dienes being selected from the group consisting of methylene norbornene, ethylidene norbornene, dicyclo-pentadiene and 1,4-hexadiene.
by weight of elastomeric polymer selected from the group consisting of ethylene/propylene rubber and terpolymers of ethylene, propylene and a diene monomer, wherein the ethylene content is from about 20 to about 80% by weight and the diene content is about 0 to about 5% by weight, said dienes being selected from the group consisting of methylene norbornene, ethylidene norbornene, dicyclo-pentadiene and 1,4-hexadiene.
44. The composition of Claim 19 or Claim 21 containing from about 2 to about 12% by weight of elasto-meric polymer selected from the group consisting of ethylene/propylene rubber and terpolymers of ethylene, propylene and a diene monomer, wherein the ethylene con-tent is from about 20 to about 80% by weight and the diene content is from 0 to about 5% by weight, said dienes being selected from the group consisting of methylene norbornene, ethylidene norbornene, dicyclo-pentadiene and 1,4-hexadiene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17678380A | 1980-08-11 | 1980-08-11 | |
| US176,783 | 1980-08-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1169991A true CA1169991A (en) | 1984-06-26 |
Family
ID=22645797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000383343A Expired CA1169991A (en) | 1980-08-11 | 1981-08-06 | Filled and plasticized blends of linear low density polyethylene |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5759941A (en) |
| CA (1) | CA1169991A (en) |
| ZA (1) | ZA815482B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0443319Y2 (en) * | 1987-11-27 | 1992-10-13 | ||
| JP2002256117A (en) * | 2001-03-05 | 2002-09-11 | Asahi Denka Kogyo Kk | Resin composition |
| JP2002256118A (en) * | 2001-03-05 | 2002-09-11 | Asahi Denka Kogyo Kk | Resin composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5838304B2 (en) * | 1975-09-29 | 1983-08-22 | 株式会社トクヤマ | Polyolefin resin engineering process |
| JPS592687B2 (en) * | 1976-12-28 | 1984-01-20 | 旭化成株式会社 | Tape-shaped products and knitted or woven products using the same |
-
1981
- 1981-08-06 CA CA000383343A patent/CA1169991A/en not_active Expired
- 1981-08-10 ZA ZA815482A patent/ZA815482B/en unknown
- 1981-08-11 JP JP12485281A patent/JPS5759941A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5759941A (en) | 1982-04-10 |
| JPH0160055B2 (en) | 1989-12-20 |
| ZA815482B (en) | 1983-03-30 |
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