CA2259529C - Method of processing polyethylene and polyethylene/elastomer blends - Google Patents
Method of processing polyethylene and polyethylene/elastomer blends Download PDFInfo
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Abstract
Melt processed linear polyethylenes which may optionally contain an elastomer are shown to exhibit improved processability through the addition of certain surfactants. Among the melt processing parameters improved are reduced head pressure, reduced torque, reduced motor load, reduced or eliminated melt fracture, or combinations of these parameters. The surfactants can be chosen from a non-aromatic sulfonate or sulfate salt wherein a cation of the salt is selected from the group consisting of Na, K, Li, and other alkali cations and quaternary ammonium cations, said surfactant being essentially free of halogens.
Description
WO 98105711 PCTlUS97/13856 METHOD OF PROCESSING POLYETHYLENE AND
POLYETHYLENE/ELA.STOMER BLENDS
BACKGROUND
Linear polyolefins as well as linear polyethylene blends with elastomers, in particular, linear polyethylenes and/or elast:omer blends, may be dii~cult to melt process. Specifically, due to a low shear sensitivity when compared to highly branched polyethylenes, the linear polyethylenes and/or elastomer blends can require more extruder power to pump an equivalent amount of polymer melt. The 1o presence of the elastomer does not necessarily improve the processability of linear polyethylenes. As a result, higher extruder head pressures, higher torque, greater motor loads, and the like can develop, as compared to the highly branched materials.
Increases such as higher motor load, head pressure and/or torque can place undesirable, unacceptable, or unattainable requirements on specific machinery.
As for instance, a specific extruder having a specific motor power and gearing, will reach a maximum of motor load, or head pressure, under certain melt temperature conditions for a given polymer being proce sed. If a polymer or polymer blend is introduced to such an extruder which has such a higher requirement for power in at least one component, such as a polymer having higher molecular weight and/or narrower molecular weight distribution and,~or lower shear sensitivity, the extruder will reach a maximum of one or several of these parameters, and be therefore limited in its ability to pump/perform at a similar level to the performance expected/demonstrated with a highly branched or broader molecular weight distribution polymer such as traditional high pressure low density polyethylenes. In the alternative, if melt processing machinery is to be used for certain production/extrusion, and it is not so limited, the prospect of using more power or increasing head pressure for a more difficult to extrude material, while achievable, the user of the machinery would prefer to conserve power.
3o Additionally, linear polyethylenes and elastomeric blends thereof may exhibit other imperfections during extrusion, specifically blown film extrusion, that may be undesirable, such as melt fracture. These imperfections are undesirable from a quality standpoint. For instance, melt fracture, also known as "shark skin"
or "orange peel", can lead to poorer optical properties and/or diminished film physical properties that are generally unacceptable.
The introduction of linear Ziegler-Natta catalyzed polyethyienes in the late '70s and early '80s and extruder owner's attempts to use these poiyethylenes in machines that had been previously used to extrude free radical initiated, highly branched, high pressure produced low density polyethylenes provided the early manifestations of these problems. The advent of metallocene catalyzed linear 1o polyethylenes in the '90s, has continued the trend towards polymers that when fabricated into for instance films, offer for example, better physical properties and/or manufacturing economics, but have higher power requirements and/or greater tendency to exhibit melt fracture in the blown film process.
Linear polyethylenes therefore have been the subject of a good deal of effort to eliminate or reduce such problems. Some of the attempts included regearing extruders, designing new and more efficient screws and dies, increasing the power train, addition of expensive fluoroelastomeric processing aids and the like. In nearly every instance, the cost involved has not been inconsequential, as well as the inconvenience. But such costs have been born, due to the desirability of 2o physical properties and/or downgaging possible with the linear polyethylenes.
GB 1,104,662 suggests addition of the salt of alkyl benzene sulfonic acids to polyolefins that purportedly gives a beneficial effect on melt extrusion behavior of the polyolefin. The purported effect is the reduction of the occurrence of "shark skin" or "orange peel". Both alkali and alkaline earth metal salts of alkyl benzene sulfonic acids are purported to be effective. The document is devoid of any identification of the polyethylene, such as molecular weight distribution (MWD), or composition distribution breadth index (CDBI).
GB 1,078,738 suggests that addition of an "external lubricant" to high molecular weight polyolefins can, purportedly, reduce occurrence of melt fracture.
3o Suggested as external lubricants are salts of monovalent to tetravalent metals, and saturated or unsaturated carboxylic acids containing IO to 50 carbon atoms.
POLYETHYLENE/ELA.STOMER BLENDS
BACKGROUND
Linear polyolefins as well as linear polyethylene blends with elastomers, in particular, linear polyethylenes and/or elast:omer blends, may be dii~cult to melt process. Specifically, due to a low shear sensitivity when compared to highly branched polyethylenes, the linear polyethylenes and/or elastomer blends can require more extruder power to pump an equivalent amount of polymer melt. The 1o presence of the elastomer does not necessarily improve the processability of linear polyethylenes. As a result, higher extruder head pressures, higher torque, greater motor loads, and the like can develop, as compared to the highly branched materials.
Increases such as higher motor load, head pressure and/or torque can place undesirable, unacceptable, or unattainable requirements on specific machinery.
As for instance, a specific extruder having a specific motor power and gearing, will reach a maximum of motor load, or head pressure, under certain melt temperature conditions for a given polymer being proce sed. If a polymer or polymer blend is introduced to such an extruder which has such a higher requirement for power in at least one component, such as a polymer having higher molecular weight and/or narrower molecular weight distribution and,~or lower shear sensitivity, the extruder will reach a maximum of one or several of these parameters, and be therefore limited in its ability to pump/perform at a similar level to the performance expected/demonstrated with a highly branched or broader molecular weight distribution polymer such as traditional high pressure low density polyethylenes. In the alternative, if melt processing machinery is to be used for certain production/extrusion, and it is not so limited, the prospect of using more power or increasing head pressure for a more difficult to extrude material, while achievable, the user of the machinery would prefer to conserve power.
3o Additionally, linear polyethylenes and elastomeric blends thereof may exhibit other imperfections during extrusion, specifically blown film extrusion, that may be undesirable, such as melt fracture. These imperfections are undesirable from a quality standpoint. For instance, melt fracture, also known as "shark skin"
or "orange peel", can lead to poorer optical properties and/or diminished film physical properties that are generally unacceptable.
The introduction of linear Ziegler-Natta catalyzed polyethyienes in the late '70s and early '80s and extruder owner's attempts to use these poiyethylenes in machines that had been previously used to extrude free radical initiated, highly branched, high pressure produced low density polyethylenes provided the early manifestations of these problems. The advent of metallocene catalyzed linear 1o polyethylenes in the '90s, has continued the trend towards polymers that when fabricated into for instance films, offer for example, better physical properties and/or manufacturing economics, but have higher power requirements and/or greater tendency to exhibit melt fracture in the blown film process.
Linear polyethylenes therefore have been the subject of a good deal of effort to eliminate or reduce such problems. Some of the attempts included regearing extruders, designing new and more efficient screws and dies, increasing the power train, addition of expensive fluoroelastomeric processing aids and the like. In nearly every instance, the cost involved has not been inconsequential, as well as the inconvenience. But such costs have been born, due to the desirability of 2o physical properties and/or downgaging possible with the linear polyethylenes.
GB 1,104,662 suggests addition of the salt of alkyl benzene sulfonic acids to polyolefins that purportedly gives a beneficial effect on melt extrusion behavior of the polyolefin. The purported effect is the reduction of the occurrence of "shark skin" or "orange peel". Both alkali and alkaline earth metal salts of alkyl benzene sulfonic acids are purported to be effective. The document is devoid of any identification of the polyethylene, such as molecular weight distribution (MWD), or composition distribution breadth index (CDBI).
GB 1,078,738 suggests that addition of an "external lubricant" to high molecular weight polyolefins can, purportedly, reduce occurrence of melt fracture.
3o Suggested as external lubricants are salts of monovalent to tetravalent metals, and saturated or unsaturated carboxylic acids containing IO to 50 carbon atoms.
Sulfonates corresponding to the fatty acid salts are also said to be suitable.
However, stearates, palmitates and oleates are exemplified. This document indicates an equivalence of metal salts of mono to tetra-valent metals.
JP A 59-176339 suggests that when polyolefins are narrowed in MWD or given higher molecular weight, poor fluidit~r results which in turn gives rise to melt fracture. The solution suggested is addition of fluorinated compounds including potassium salts of fluoroalkylsulfonic acids. These potassium salts are said to exhibit preferable temperature dependence when compared to other cations such as sodium, calcium, lithium and ammonium. The polyolefin/salt combination is said to to be effective at 230° C or higher.
DE 2823507 suggests molding or calendered objects of ethylene polymers and propylene polymers containing alkalai or alkaline earth mono sulfonates from the group alkyl sulfonates, alkenyl sulfonate;s, alkylaryl sulfonates and succinic acid dialkyl ester sulfonates. Sodium or calcium mono sulfonates are preferred. A
suggested benefit is purported to be outstanding separation of the polymer from calendering rolls.
JP 58-212429 (60-106846) suggest, polyethylene compositions consisting of 70-95 weight parts of ethylene homopolymer or ethylene alpha-olefin copolymer with a density of at least 0.94 g/cm3; 5-30 weight parts of at least one of low 2o density polyethylene (high pressure), ethylene vinyl acetate, ionomer, and ethylene alpha-olefin copolymer (density not exceeding 0.935 g/cm3); 0.01-5 weight parts of magnesium salt or calcium salt of alkylsull:onic acid or alkylbenzenesulfonic acid;
and 0.05-0.5 weight parts of at least one substance selected from the group which includes dibenzylidene sorbitol or its nuclear substituted derivative. The combination is said to be especially useful in air-cooled inflation film.
US 4,829,116 suggests polyolefin molding compositions purportedly having no surface defects that includes a fluorine-containing polymer together with a wax, preferred polyolefins are said to be ethylene copolymers with 1-olefins which contains 3-10 carbon atoms. The fluorine containing compounds are 3o preferably copolymers of vinylidene fluoride and hexafluoropropylene or terpolymers of these monomers with tetra fluoroethylene. Among the suitable CA 02259529 1999-O1-04 _ 96803 a.PCT
However, stearates, palmitates and oleates are exemplified. This document indicates an equivalence of metal salts of mono to tetra-valent metals.
JP A 59-176339 suggests that when polyolefins are narrowed in MWD or given higher molecular weight, poor fluidit~r results which in turn gives rise to melt fracture. The solution suggested is addition of fluorinated compounds including potassium salts of fluoroalkylsulfonic acids. These potassium salts are said to exhibit preferable temperature dependence when compared to other cations such as sodium, calcium, lithium and ammonium. The polyolefin/salt combination is said to to be effective at 230° C or higher.
DE 2823507 suggests molding or calendered objects of ethylene polymers and propylene polymers containing alkalai or alkaline earth mono sulfonates from the group alkyl sulfonates, alkenyl sulfonate;s, alkylaryl sulfonates and succinic acid dialkyl ester sulfonates. Sodium or calcium mono sulfonates are preferred. A
suggested benefit is purported to be outstanding separation of the polymer from calendering rolls.
JP 58-212429 (60-106846) suggest, polyethylene compositions consisting of 70-95 weight parts of ethylene homopolymer or ethylene alpha-olefin copolymer with a density of at least 0.94 g/cm3; 5-30 weight parts of at least one of low 2o density polyethylene (high pressure), ethylene vinyl acetate, ionomer, and ethylene alpha-olefin copolymer (density not exceeding 0.935 g/cm3); 0.01-5 weight parts of magnesium salt or calcium salt of alkylsull:onic acid or alkylbenzenesulfonic acid;
and 0.05-0.5 weight parts of at least one substance selected from the group which includes dibenzylidene sorbitol or its nuclear substituted derivative. The combination is said to be especially useful in air-cooled inflation film.
US 4,829,116 suggests polyolefin molding compositions purportedly having no surface defects that includes a fluorine-containing polymer together with a wax, preferred polyolefins are said to be ethylene copolymers with 1-olefins which contains 3-10 carbon atoms. The fluorine containing compounds are 3o preferably copolymers of vinylidene fluoride and hexafluoropropylene or terpolymers of these monomers with tetra fluoroethylene. Among the suitable CA 02259529 1999-O1-04 _ 96803 a.PCT
waxes enu nerated are alkylsulfates or alkyl sulfonates containing straight chain or branched ('$ to CZa alkyl radicals and an allt:alai metal ion, preferably a sodium ion.
Th~;re is a need therefore for a relatively inexpensive, easily implemented solution tc the processing problems outlined above. Such a solution should also include a material that when included in blown film extrusion of linear polyethyle yes andlor linear polyethylene-elastorner blends, will readily melt or incorporate into the melted polyethylene, and not adversely affect physical properties not be e;ctractable, or negatively impact organoleptics of the film.
Specifical! ~r, there is a commercial need for a material that may be eaaily 1.o incorpora~. ~ into po!yethylenes and polyethylene elastomer blends, that will reduce or elintina to the increased power requirement (e.g. motor load and cr torque), increased '.lead pressure, and melt fracture.
St'MM_~ 2Y
'T'1 a present invention is directed to such a material, a certain group of i5 surfactant s, and methods of their use which when incorporated into a linear polyethyl~:.ne or linear polyethylene elastomer blends, can reduce or eliminate proeessin; problems such as melt fracture, increased motor load, increased torque, and comt~'nations thereof and may thereby iincrease potential production rates.
Ire certain embodiments of the present invention a method of processing zo polyethyl~:nes comprising selecting a lines~r polyethylene, from a group such as linear loo r density polyethylene (LLDPE), metallocene LLDPE (mLLDPE), high density p~~lyethylene (HDPE), plastomers, ultra high molecular weight high density polyethyl:ne (1;J~F~MW-APE), medium density polyethylenes (MDPE), or combinations thereof, adding an elastomer~ selected from the group consisting of z5 styrene t~.rtadiene styrene (SBS); styrene isoprene styrene (STS); styrene ethylene butadiene: styrene (SEBS); styrene ethylene propylene styrene (SEPS); and combina~ :ans thereof and adding a surfactant. The surfactant being an aliphatic sulfonatE~ salt having a cation selected from the group wnsisting of Na, I~, and Li.
An amo~.~nt of the surfactant should be added that will be sufficient to improve the 30 melt prc cessability of the polyethylene or polyethylenelelastomer blend.
'The combinan ion of polyethylenes and 96H034. E'Cr surfactant or surfactants and optionally an ela~.stomer or elastomers is then used to melt proce ~s the combination into a useful article, such as a film. blow molded part, and the lik ~.
Th ~ polyethylenes may be conventional Ziegler-Natta (Z-;~ catalyzed materials ! oat generally have a molecular weight distribution characterized by the ratio of w~;ight average molecular weight to the number average molecular weight (bi""lM~ , bove about 4, or the polyethylenes may be metallocene catalyzed, and will then 1~ 3ve an approximate M"J~f~, of less than 3, preferably less than 2. ~, and a z-average :molecular weight (M~ divided by R~i", (M~l~l~tW) not exceeding 2.
l0 Al ~o contemplated are compositions of a polyethylene having an Mw~:~in less than ., and optionally an elastomer or elastomers and an alkali metal alkyl sulfonate -~r sulfate wherein the alkyl group has 6-30 carbon atoms. where the surfactant is present in the polyethylene or polyethylene elastomer blend in a range of from 0.')05 to 1 weight percent based on the total weight of the polyethylene or is blend. TI'S a surfactant should ideally be substantially non-extractable from the final fabricated article.
'TW~se and other features, aspects, and advantages of the present invention will beca; ne better understood with reference to the following description and appended rlaima.
2o DESCRI;'Tr~N
In certain embodiments of the present invention, methods of and compositi.ms far reducing or eliminating; a) melt fracture; b) torque; c}
increased head pre:~sure; d) increased motor load, e) combinations thereof, and the like, during the; melt processing of polyethyienes, polyethylene elastomer blends and 25 other pol'. olefins are contemplated. These ernbodiments include both corwentional Z-N ancG metallocene catalyzed polyet;hylenes(the latter hereinafter "m-polyethylc nes), and their combination with certain surfactants and optionally an elastomer that when so combined achieve the stated melt processing improvestuents. The combination of polyethylenes and surfactants are particularly 3o well suite 3 to melt processing and fabrication. into films, especially blown films, blow mol:ed articles, and the like, while reducing or eliminating one or more of the WO 98/05711 - PCTlI1S97/1385b processability problems discussed above and generally without being extractable from the final fabricated article.
Following is a detailed description of certain preferred combinations of polyethylenes and surfactants and optionally an elastomer and methods of using the combinations in melt processing into useful articles. Those skilled in the art will appreciate that numerous modifications to these preferred embodiments can be made without departing from the scope of the invention. For example: Although methods of improving melt processing of m-polyethylenes or m-polyethylene elastomer blends into films are exemplified, they will have numerous other uses and to the films may be formed from other polyolefins or combinations of polyethylenes.
To the extent this description is specific, it is solely for the purpose of illustrating preferred embodiments of the invention and should not be taken as limiting the present invention to these specific embodiments.
DEFIhTITIONS
torque - horse power/rpm motor load - amps head pressure - Kpa (psi) The Encyclopedia of Polymer Science and Technology, Vol. 8, John Wiley & Sons, (1968) pp. 573-575 indicates that for a given polymer, processed at a 2o constant melt temperature, there exists a critical shear rate in the melt fabrication process. Melt processing of the polymer below this critical shear rate will result in a smooth extrudate surface while processing the polymer above it will result in a rough extrudate surface. The observed roughness is commonly referred to as "melt fracture" but may also be described by other terms such as "sharkskin" or "orange peel". For a given polymer, the critical shear rate increases as the melt processing temperature of the polymer increases.
The extent of extrudate roughness will vary depending upon the shear rate at which the polymer is processed. At shear rates just above the critical value, the extrudate roughness normally results in a loss of surface gloss and is typically called "sharkskin". At higher shear rates, the extrudate exhibits periodic areas of roughness followed by areas of smoothness in a more or less regular pattern.
This phenomenon is normally described as "cycl.ic melt fracture". At very high shear rates, the extrudate may become grossly distorted resulting in a what is commonly called "continuous melt fracture".
In general, linear polyethylenes, particularly those with high average molecular weights and/or narrow molecular weight distributions, tend to be more prone to the formation of melt fracture than highly branched polyethyienes, such as conventional LDPE made by high pressure polymerization.
The presence of melt fracture in a fabricated article can lead to poorer optical properties and is generally aesthetically unacceptable. Attempts to to eliminate melt fracture in articles fabricated from linear polyethylenes by either reducing the processing shear rate (reduced production rate) or by increasing the processing temperature (increased melt temperature) are generally not commercially viable. In addition, changes in die design to reduce the shear rate (e.g., use of wider die gaps) can result in other problems such as excessive orientation leading to unbalanced article properties. Although fluoroelastomeric processing additives have been used to eliminate sharkskin in linear polyethylenes under certain processing conditions, their u:>e is expensive due to the high cost of the fluoroelastomer.
2o POLYETHYLENES
The polyethylenes contemplated in certain embodiments of the present invention, include ethylene alpha-olefin copolymers. By copolymers we intend combinations of ethylene and one or more. alpha-olefins. In general the alpha-olefins comonomers can be selected from those having 3 to 20 carbon atoms.
Specifically the combinations may include ethylene 1-butene; ethylene 1-pentene;
ethylene 4-methyl-I-pentene; ethylene 1-hexene; ethylene 1-octene; ethylene decene; ethylene dodecene; ethylene, 1-but.ene, 1-hexene; ethylene, 1-butene, I-pentene; ethylene, I-butene, 4-methyl-1-p~entene; ethylene, 1-butene, 1-octene;
ethylene, 1-hexene, 1-pentene; ethylene, 1-hexene, 4-methyl-1-pentene;
ethylene, 1-hexene, 1-octene; ethylene, I-hexene, decene; ethylene, I-hexene, dodecene;
ethylene, propylene, I-octene; ethylene, 1-octene, I-butene; ethylene, I-octene, 1-pentene; ethylene, 1-octene, 4-methyl-1-pentene; ethylene, 1-octene, 1-hexene;
ethylene, 1-octene, decene; ethylene, 1-octene, dodecene; combinations thereof, and the like permutations. The comonomer or comonomers will be present in the copolymers in the range of from about 0.1 to about 40 mole percent. The actual amount of comonomers will generally define the density range.
Density ranges contemplated to be useful include 0.86-0.97 g/cc and all portions and constituents of the range. Specifically included are the 0.86 -0.91 S
g/cc (plastomers) 0.916-0.925 (LLDPE), 0.926-0.940 (MDPE), and 0.941-0.970 (HDPE). Melt indices contemplated include 0.001-30, preferably 0.5 to 5.0 for to blown films, and 0.3-10 for blow molding, and all members of these ranges (melt index in dg/min or g/10 minutes).
Polyethylenes that are produced using metallocene catalysts include ionizing activators as well as alumoxanes.
Included in the embodiments contemplated are those where either m polyethylenes and Z-N polyethylenes may be blended with each other and/or with other components such as LDPE, (highly branched, high pressure free radical polymerized) and other ethylene copolymers such as ethylene vinyl acetate (EVA), ethylene n-butyl acrylate (EnBA), ethylene methyl acrylate (EMA}, ethylene ethyl acrylate (EEA), ethylene acrylic acid (EAA), ethylene methacrylic acid (EMAA), 2o and ionomers of the acids, terpolymers such as ethylene, vinyl acetate methyl acrylate; ethylene, methyl acylate, acrylic acid; ethylene, ethyl acrylate, acrylic acid;
ethylene, methyl acrylate, methacrylic acid; ethylene, methylacrylate, methacrylic acid; and the like.
The polyethylene eiastomer combinations described above, in combination with the surfactants described below, will be substantially free of propylene polymers such as polypropylene homopolymers and copolymers. By substantially free we intend that Less than 5 wt. % of the total polymer will be a propylene based polymer, preferably less than 3%, more preferably less than 1%, most preferably to totally free of propylene polymers.
3o Also contemplated are mufti-layer blown film extrusions where one or more of the layers can include a polyethylene/surfactant or 96BG34.?CT
polyethylec:elelastomersJsurfaetant combination, Such e~ctrusion may inci,rde a linear poh~ethylene layer, a heat seal layer, a barrier (gas atidlor vapor) layer, rxycle or regind layer or combinations thera~of.
So~~ne of these blend components may affect processing variables in a s po3itive n~anner, in which case the inven~rion contemplated will include some portion of the below discussed surfactants, possibly less than with an unblended material.
laic ~st polyethylenes will contain various additives well itnow~n to those of ordinary s'~:ill in the art, including, but not luruted to slip, anti-block, anti-oxidants, ~o anti-fogs, acid neutralizers, UV inhibitor.., anti-static agents, pigments, dyes, release ag~:mts, fungicides, algecides, bactericides, and the like.
As used in this application, the processing temperature of pr~lyethy~lene in the blown r~lm process wi31 generally he in the range of 300 - 450° F
(149-232° C), preferably 35G - 410° C (177-210° C), a point generally above the melting point of 1s the poly~tliylene and below its degradation ~~r decomposition temperatu:e.
This is generally the temperature of the melt exiting the die, but may be measured at any point doa nstream of the screw elements. The processing temperature will be understood.' by those of ordinary skill to ~~ary generally by the melt fabrication technique, and within a fabrication technique, processing temperature can vary by 2o the type ~:.:.f processing equipment, or by specific requirements of a particular manufactu rer.
SL'RFAC'~~.'ANTS
Tt~ a surfactants contemplated include aliphatic sulfonate salts where the canon is o~~e of. Li, Na, K Sodium salts being preferred. The surfactants may also ~5 be describ~;d as alkali metal aliphatic sulfonates where the aliphate group is a C6 to C30 alkyl group, preferably C8 to C20, more preferably C12 to C18, The alkyl group mail be chosen from the group consisting of branched or straight chain alkenyl, bwanched or straight chain hydroxyl substituted alkyl, and combinations thereof ~freferred are combinations of branched or straight chain alkenyls and 3a branched ~ rr straight chain 96H034.PCT
hydroxyl s ~bstituted alkyf alkalai metal sulfates or sulfonates, of these the scdiurrt combinarc n is most preferred.
On . class of surfactants that arc preferred in this application are a-olefin suL°onates. As stated in the Kirk-C~thmer Encyclopedia of Chemical T
achnology, 5 Vol. 2?, J~ ~hn W'iley & Sons, (1983), pg. 35:?, a-olefin sulfonates are produced by reaction o ' a-oleixn with S03 in air followed by neutralization with a base to produce t!1e corresponding salt. The sodium salts are the mast preferred.
Commerci.3 ct-olefin sulfonates are a mi~rnare of alkene suifonates and hydroxy allcane sulf mates. The position of the double bond in alkene sulfonates as well as to the hydrox v1 group in hydraxy alkane sulfonates varies along the carbon chain of the alkyl ~ oup.
Mr-e detailed description of the surfa.otants follows.
Thn surfactant includes those, of the c;eneral formulae:
I,) ~R~ SO~~vh Ml is selected from the group consisting of~
Li, Na, K, R1 is selected from the group consisting of branched or straight chain mono or dl unsaturated alkenyl, branchad or straight chain hydroxyl substituted alkyl, and combinations thereof, 9GH034.PC'r ~ ~~herein the carbon number of said R1, ranges from 6 to 30; and ~ herein said surfactant is present in mid combination in a range of up t ~ 1.0 weight percert, preferably 0,005 to 1.0 weight percent, more preferably O.OI to 0.5, most preferably 0.03 to 0 35 weight percent brsed on the total weight of the cornbination.
Or a ~~urfactant represented by one of the formulae:
IL) ~R SO~~M
M1 is selected from the group consisting of Li, Na, K, and other rations.
R1 is selected from the group consisting of:
branched or straight chain mono or dl unsaturated alkenyl;
branched or straight chain hydroxyl substituted alkyl, arid combinations thereof, ' '~' ~"~ CA 02259529 1999-O1-04 -968034.PCi' ~Nherein said surfactant is present in said combination up to 1.0 weight percent, preferably in a range of 0.005 to 1.0 weight percent. more ;preferably 0.01 to 0.5, most pre:Ferably 0.03 to 0.35 weight percent Sased on the total weight of the combination.
The surfactant or surfactants should he substantially or essentially free of halogens. By substantially or essentially free of halogens we intend that the surfactant n olecules will have preferably no h;rlogen.
The surfactants comtemplated, whether a mixture or a single surfactant should have a melting point less than 240° C. preferably 23a°
C., more preferably to 220° C., me ~~t preferably 2I0° C.
The surfactants may be present in the polyethylene combination up to 1.0 weight pere~.nt, in the range of from 0.05-1.C~ weight percent, preferably 0.01-0.5, more prefer ~~bly 0.03- 0.35 weight percent (including all elements in these ranges}
based on th~:~ total weight of the combination. The amount and type of surfactant is present will ietermine the effect on the melt processing characteristics, for instance as shown be i ow, smaller amounts at about 0. 3 5 wt% ox below preferably 0.25°~0, more prefer ably 0.10 wt%, or below, will primarily function to reduce melt fracture, whi.!e amourrts above that level, up to the indicated higher levels will begin to also redm. a head pressures, torque, motor load or combinations thereof.
While dfl greater amo~..nts than the 0.5 levels may be used, adverse extrusion effects may result such a ~ grew slippage.
Thos: of ordinary skill will appreciate ':hat at higher levels, generally above 0.1 weight percent, the surfactant or a combination of surfactants will be ei~'ective in reducing c' of only melt fracture, but motor Ioad, torque, head pressure and the 2s like by at leant 5% for one or more ef these variables. Generally at lower levels than 0.1 weight percent the reductions of these motor load, torque and head pressure parameters will be less, but the :surfactants will be effective in reducing melt fracture.
The mechanism of melt fracture reduction is believed to involve the s formation of a layer of surfactant on the internal metal surfaces of key components of the melt processing equipment. This layer effectively increases the velocity of molten polymer at the metal interface 'thereby minimizing the polymer flow distortions that occur as the molten polyn:~er exits the melt processing equipment which typically results in melt fracture. The use of a relatively high concentration to of surfactant, e.g. 0.5 weight percent, will generally result in a faster rate of metal surface coating and, therefore, a more rapid rate of reduction in melt fracture of the final fabricated article. At lower surfactant levels, the metal surface coating rate, and the corresponding melt fracture reduction rate, will be slower.
It should be noted that when discussing the weight percent of surfactant, 1s we intend that this be based on the total weight of the surfactant and polyethylene (or polyethylene blend). If other constituents are included the amount of surfactant should be then calculated on a parts per hundred parts of polyethylene basis.
Likewise if a blend constituent (with the linear m-polyethylene) assists in improving processability, then the contemplated arr~ount of surfactant will be that level 2o sufficient to achieve the intended effect, e.g. reduction of one or more of melt fracture,. motor load, torque, or head pressure.
For example, blends of one or more of the above surfactants may be used to achieve the desired results, as well as combinations of polyolefin waxes and/or fluoroelastomers and/or fluoropolymers with one or more surfactants. For instance 2s one or more of the surfactants listed above may be combined with a polyethylene wax in ratios from 10-90 and 90-10 and all elements in and between these ranges, and a similar combination with fluoroelastomers and/or fluoropolymers is also contemplated, as well as surfactant/polyethylene wax/fluoroelastomer combinations.
3o If the polyethylene composition o:r the film made therefrom contain the optional elastomer or elastomers, the thermoplastic elastomeric films of certain embodiments of the present invention comprise a blend of at least two copolymers.
One copolymer is an elastomeric block copolymer containing blocks of a monoalkenyl arene copolymer and a conjugated diene polymer. The second component is selected from a group of highly amorphous thermoplastic ethylene copolymers having the primary characteristic of low crystallinity and low density (such as m-plastomers and/or m-LLDPE). Optional ingredients which may also be included in the polymer blends of the present invention include small amounts of conventional anti-block concentrates and slip agents, as well as antioxidants and stabilizers.
1o THE ELASTOMERIC BLOCK COPOLYMER
The elastomeric block copolymers contemplated for use herein are known materials having blocks of monoalkenyl arene polymer and blocks of conjugated diene polymer. The polymer blocks have the general configuration:
A-B-A
and are arranged such that there are at least two monoalkenyl arene polymer end blocks A and at a least one elastomeric conjugated dime mid block B. These polymer blocks may optionally be hydrogenated to eliminate the unsaturation in the mid block B. The monoalkenyl arene copolymer blocks comprise from 8% to about 55% by weight of the block copolymer. The molecular weight of the block copolymer is such that its melt index is less than about 100 as determined by ASTM Method D 1238 entitled "Standard Test Method for Flow Rates of Thermoplastics by Extrusion Plastomer" Condition E.
The term "monoalkenyl arene" includes those particular compounds of the benzene series such as styrene and its analogues and homologues including o-methyl styrene and p-methyl styrene, p-tent-butyl styrene, 1,3 dimethyl styrene, p methyl styrene in other ring aikylated styrenes, particularly ring methylated styrenes, and other monoaikenyl polycyciic aromatic compounds such as vinyl naphthalene, vinyl anthrycene and the like. For the present invention, the preferred monoalkenyl arenes are monovinyl, monocyclic arenes such as styrene and p methyl styrene, styrene being particularly preferred.
It is important to embodiments of present invention that the amount of monoalkenyl scene not exceed an amount of 55%, nor comprise an amount less than 8% by weight of the copolymer. Preferred amounts of monoalkenyl scene in the block copolymer are from 25% to 35%. Optionally, the monoalkenyl scene will s , be in an amount of about 30%. If a monoalkenyl scene is used in excess of weight percent, the block copolymer is too stiff for the instant blends. The elastomeric block copolymers are optionally "oil extended" which is the addition of a hydrocarbon oil and allows for improved processability and soRer films. The oils are optionally added to the commercial elastomeric copolymers in amounts of 10 between 10% t0 40%.
The block B comprises homopoiymers of conjugated diene monomers, copolymers of two or more conjugated dienes, and copolymers of one or more of the dienes with a monoalkenyl scene as long as the blocks B are predominantly conjugated diene units. The conjugated dienes preferably used herein contain from 15 4 to 8 carbon atoms. Examples of such suitably conjugated diene monomers include: 1,3 butadiene (butadiene); 2-methyl-1,3 butadiene; isoprene; 2,3 dimethyl-1,3 butadiene; 1,3 pentadiene (piperylene); 1,3 hexadiene; combinations thereof, and the like. Hydrogenation of the unsaturated elastomer (Block B) results in a saturated tri-block copolymer (A-B-A).
2o For the instant films, the preferred monoalkenyl scene polymer is polystyrene; and the preferred conjugated diene polymers are polybutadiene and polyisoprene, especially preferred being polybutadiene. The preferred elastomeric block copolymers are commercially available as linear tri-block copolymers (A-B-A) from the Shell Chemical Company, Polymers Division, Houston, Texas, under the trade name KRATON and from Dexco Polymers of Houston, Texas, under the family trademark VECTOR. Especially preferred are the linear tri-block copolymers having polystyrene end blocks and a polybutadiene mid-block (S-B-S).
Most commercially preferred are oil extended polymers such as ICRATON D 2104 having a melt index of about 7 as determined by ASTM Method D 1238, Condition E and VECTOR 7400D, having a melt index of about 8.
The thermoplastic elastomeric films of the present invention may contain from about 20%-70% by weight of the elastomeric block copolymer; preferably from about 45%-65%; especially preferred being from about 50%-65% based on the total weight of polyethylene, and elastomer. The percentages herein are based on the total weight of the elastomeric film composition. As indicated, commercial grades of elastomeric block copolymers can be oil extended and the oil portion is not calculated as part of the percentage herein. To firrther enumerate the elastomer, linear polyethylene (m-plastomer and/or m-LLDPE) the two parts (polyethylene/elastomer) can be present in a ratio of 1:4-2:1; preferably 1:2-2:1.
1o The thermoplastic eiastomeric films of the present invention may be used in a wide variety of applications where thin, elastic material would be useful.
Such films are particularly useful as low cost elastic members for disposable wearing apparel such as diapers; training pants, feminine hygiene devices, medical gowns, gathered laminate garments, non-woven head bands, sports apparel, bandages and protective clothing.
FILM PROPERTIES
Other final product variables or parameters that are included are discussed below.
The addition of suffcient levels of surfactant to a polyethylene should 2o generally be "property neutral" that is, the surfactant addition should not substantially diminish any important finished product property such as haze, impact resistance, gloss, tear resistance, modulus, and the like.
The surfactant should have a melting point not generally greater than 30°
C, preferably 25° C, more preferably 20° C, most preferably 15° C above the processing temperature of the linear polyethylene. The surfactant is generally and preferably molten at the processing temperature of the polyethylene. The processing temperature will be well understood by those of ordinary skill in the art and will diffier by melt fabrication technique, e.g. blown film and blow molding temperatures will vary. Also the melt processing temperature can be characterized 3o by the melt temperature itself rather than the extruder zone temperatures.
EXTR.ACTABILITY
Extractability of the surfactant from the polyethylene-surfactant matrix should be no more than 7% (wt) of the total surfactant in either water (at 100° C
for 3 hrs.) or 95°/JS% ethanoUwater (at 55° C for 4 hrs.), preferably not more than 3 5% (wt.), more preferably not more than 4% (wt.), all based on not more than wt. % of surfactant in the polyethylene.
EXAMPLES
E~cam 1R a 1 An antioxidant stabilized metallocene catalyzed linear low density to polyethylene resin (m-LLDPE), Exceed''" ECD 102 of the following nominal properties (a 1 melt index, 0.917 gm/cc density, ethylene 1-hexene copolymer available from Exxon Chemical Co., Houston, TX, USA), is used in this example.
To the ganular m-LLDPE resin (Example 1 ) is added 0.25 wt% BioTerge~ AS-90B Beads (a sodium C 14-C 16 ~Pha olefin sulfonate available from Stepan Co., 15 Northfield, IL, USA). A control sample (Comparative example C 1 ) is prepared by adding 0.08 wt% Dynamar'''~ FX-9613 (a fluoroelastomeric processing aid available from 3M Co., St. Paul, MN, USA) to a separate portion of the ganular m-LLDPE resin. Both portions are compounded and pelletized on a Werner Pfleiderei twin screw extruder.
2o The two pelletized formulations are extruded into film on a 2.5 inch (6.35 cm) Egari tubular blown film extnader. The extruder has a 24/1 length/diameter ratio, Sterlex~ barrier LLDPE screw and is equipped with a 6 inch (15.25 cm) diameter annular die with a 0.030 inch (0.076 cm) die gap. The temperature profile used ranged from 325 to 410°F ( 162-210° C). Observed melt temperatures 25 ranged from 432 to 438°F (222-225° C). Extruder screw rpm is set to achieve approximately 120 lbs (54.5 kg)/hr of polymer output. Under these conditions, the estimated shear rate is approximately 430 sec' 1. The extruded film gauge was nominally 0.0015 inch (38 microns) with a layflat of approximately 24 inches (61 cm).
The extrusion sequence for each formulation is as follows. The film line is purged with an LDPE masterbatch containing approximately 4 wt% diatomaceous earth antiblock (A1 product from Exxon Chemical Co., Houston, TX, USA).
Next, a portion of the m-LLDPE resin, to which no BioTerge~ AS-90B or DynamarTM FX-9613 is added, is extruded into film. Samples of the film are inspected to ensure complete melt fracture. Finally, the test formulation is extruded into film. Periodic samples of the film are taken and the portions which display visible melt fracture, characterized by patterns of irregular flow known as sharkskin, are measured in the transverse direction of the film. The % melt fracture to is calculated based upon the total layflat width of the film.
The data in Table 1 demonstrates that 0.25 wt% BioTerge~ AS-90B used in Example 1 substantially eliminates melt fracture in the m-LLDPE film. The elapsed time for this substantial elimination of melt fracture is nearly the same amount of time needed for 0.08 wt% DynamarTM FX-9613 (Comparative example CI) to eliminate melt fracture. At the end of each run, the extruder rpm is increased until the motor load limit is reached (93 rpm) and melt fracture-free film is maintained for each formulation (680 sec-1 ). A sample with neither FX-9613 nor AS-90B never achieves melt fracture free performances.
This is as expected since extrusion shear under these conditions results in a rate above the critical shear rate for this m-LLDPE. In the absence of the surfactant or fluoroelastomer, this will cause melt fracture in the resulting film.
Table 1 Melt Fracture Elapsed Example Example 1 Time C 1 (w/ 0.25 wt%
(w/ 0.08 AS-90B
wt%
min _ 0 =__ , 5 Table 1A
Example OutputAS-90B FX-961:3Head Die Motor (lb./hr)Conc. Conc. Pressure PressureLoad wt%) (wt% si ) si am s 1 120 None None 56?0. 4340. 57.7 1 120 0.25% None 4794. 3670. 45.0 C 1 115 None None 4945. 4008. 54.2 C1 115 None 0.08% ~ 3701. 3098. 46.8 j In addition, the extruder head pressure, die pressure and motor load measured during the extrusion of Example I was reduced by approximately 15 to l0 22 % when compared to the same m-LLDPE resin without BioTerge~ AS-90B.
Comparative example C1 showed reductions in the range of 14 to 25% when compared to the same m-LLDPE resin without DynamarTM FX-9613.
Based upon this example, 0.25 wt % of the BioTerge~ AS-90B provides equivalent performance to 0.08 wt % Dynamar~ FX-9613 in reduction of melt 15 fracture, head pressure, die pressure and motor load in Exceed~ ECD102 m-LLDPE.
Example 2 The m-LLDPE resin used is the same as that of Example 1. The granular m-LLDPE resin is split into two portions. The first portion, which contained no SUEtSTITUTE SHEET (RULE 26;
processing aid previously discussed (e.g. BioTerge~ AS-90B or FX-9613) and pelletized on a Werner Pfleiderer 57 mm twin screw extruder (Comparative example C2). To the second portion of m-LLDPE is added 0.06 wt% BioTerge~
AS-90B beads followed by compounding/pelletization on the same twin screw 5 extruder (Example 2).
The two formulations are extruded into film using the same extruder as in Example 1. The temperature profile used ranged from 325 to 400°F (162-204° C).
Observed melt temperatures range from 432 to 439°F (222-226° C). Extruder screw rpm is held constant at 74 rpm to achieve approximately 140 lbs/hr of to polymer output. Under these conditions, the estimated shear rate is approximately 500 sec-l. The extrusion sequence is as follows: A1, Comparative example C2, Example 2.
The elimination of melt fracture is measured using the same method as in Example 1. In addition, extruder measurements of head pressure, die pressure and 15 motor load are taken periodically.
The data in Table 2 demonstrates that 0.06 wt% BioTerge~ AS-90B used in Example 2 reduces melt fracture in the m-LLDPE film to approximately 1%
within an hour and completely eliminates it within 1.5 hours. As expected, the rate of elimination of melt fracture is slower when a lower concentration of BioTerge~
2o AS-90B is used. By contrast, the m-LLDPE resin which contains no BioTerge~
AS-90B yielded film which was completely melt fractured. Even at this low concentration, the BioTerge~ AS-90B reduced the extruder head pressure, die pressure and motor load by 6 - 7%. At the end of the run, the extruder rpm was increased until the motor load limit was reached (96 rpm) and the Example 2 formulation maintained melt fracture-free film (630 sec-1).
Table 2 Example ElapsedAS-90B Head Die Motor Melt Time Conc. PressurePressureLoad Fracture min wt% si 'i si am s C2 94 0 5709 4520 57.4 100 2 0 0.06 5?71 4592 57.5 100 2 30 0.06 5601 4392 55.0 18 2 57 0.06 5462 4338 54.4 1 2 86 0.06 5314 4220 53.6 0 Example 3 The antioxidant stabilized plastomer used in this example was an ExaciTM
3128 (a 1.2 melt index, 0.900 gm/cc density, ethylene 1-butene copolymer available from Exxon Chemical Co., 1-louston, TX, USA). The pelletized metallocene plastomer resin was split into two portions. The first portion, which contained no processing aid, was tested directly (Comparative example C3). To the second portion of metallocene plastom~er was added 0.06 wt% BioTerge~ AS
l0 90B beads followed by compounding/pelletization on a Werner Pfleiderer 57 mm twin screw extruder (Example 3).
The two formulations were extrudc;d into film using the same extruder and test sequence as Example 2. The temperature profile used ranged from 300 to °F (149-202° C). Observed melt temperatures ranged from 413 to 417°F (212-16 214° C). Extruder screw rpm was :held constant at 52 rpm to achieve approximately 120 lbs/hr of polymer output. Under these conditions, the estimated shear rate was approximately 430 sec' 1.
The data in Table 3 demonstrates i:hat 0.06 wt% BioTerge~ AS-90B used in Example 3 completely eliminates melt fracture within 33 minutes. By contrast, 2o the metallocene plastomer resin which contained no BioTerge~ AS-90B yielded films which was completely melt fractured. The observed reductions in extruder head pressure, die pressure and motor load ranged from 10 to 14%. At the end of the run, the extruder rpm was increased until the motor load limit was reached (64 rpm) and the Example 3 formulation maintained melt fracture-free films (520 sec-t ).
Table 3 Example ElapsedAS-90B Head Die Motor Melt Time Conc. PressurePressureLoad Fracture min wt% si si am s C3 30 0 6047 4555 62.3 100 C3 56 0 6045 4543 63.0 100 3 0 0.06 5979 4521 60.7 100 3 33 0.06 5503 4131 57.4 0 3 59 0.06 5225 3920 55.9 0 ~ ~
Example 4 An antioxidant stabilized Z-N catalyzed linear low density polyethylene resin (I,LDPE), Escorene~ LL1001 (a 1.0 melt index, 0.918 gm/cc density, ethylene 1-butene copolymer available from Exxon Chemical Co., Houston, TX, to USA), is used in this example. The granular LLDPE resin is split into two portions. The first portion, which contained no processing aid, is pelletized on a Weiner Pfleider 57mm twin screw extruder and then tested directly (Comparative example C4). To the second portion of LLDPE was added 0.06 wt% BioTerge~
AS-90B beads followed by compounding / pelletization on a Werner Pfleiderer 57 mm twin screw extruder (Example 4).
The two formulations were extruded into film using the same extruder and test sequence as Example 2. The temperature profile used ranged from 233 to °F ( 112-211 ° C). Observed melt temperatures ranged from 434 to 440°F (223-227° C). Extruder screw rpm was held constant at 69 rpm to achieve 2o approximately 147 Ibs/hr of polymer output. Under these conditions, the estimated shear rate was approximately 525 sec-1 The data in Table 4 demonstrates that 0.06 wt% BioTerge~ AS-90B used in Example 4 reduced melt fracture in the LLDPE film to approximately 24%
within an hour. By contrast, the LLDPE resin which contained no BioTerge~ AS-90B yielded film which was completely melt fractured. The observed reductions in extruder head pressure, die pressure and motor load ranged from 8 to 15%. Melt fracture was completely eliminated after 155 minutes. At the end of the run, the extruder rpm was increased up to the limit of bubble stability (105 rpm) and the Example 4 formulation maintained melt fracture-free film (700 sec-1).
1e 4 Example ElapsedAS-90BB Head Die Motor Melt Time Conc. PressurePressureLoad Fracture mlil Wt% St S1 Bin S
C4 39 0 4877 3724 48.9 100 4 0 0.06 4733 3597 45.3 100 4 41 0.06 4451 3471 41.8 45 4 56 0.06 4419 3423 41.7 24 An antioxidant stabilized metallocene catalyst produced plastomer, Exact~
1o 4049 (a 4.5 melt index, 0.873 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co., Houston, Texas, USA) is used in this example. A pelletized form of the copolymer is introduced into a BrabendeT Plasti-cordec melt mixer which was heated to 193° C. Typically, 50-60 g of material is introduced at a rotation speed of 40 RPM. Upon complete melting, the torque remains essentially invariant with time and is used as the base value. Subsequently, a measured amount of sodium alpha olefin sulfonate (Bio Terge~ AS-90B beads - product of Stepan Co., Northfield, Illinois, USA) is added. The torque is again measured at 40 RPM and compared with the base torque value. In this particular example, a torque reduction (12%) is observed at 0.5 wt% of the Bio Terge~ AS-90B beads.
At higher levels of the Bio Terge~ AS-90B beads, further reductions are noted.
For example, at a 3.0 wt% addition, the torque is reduced by >35%. To insure that complete mixing has occurred, the rotation speed is increased to 100 RPM for five minutes. The material is dumped from the Brabender, cut into small pieces, and allowed to cool to room temperature.
The material is foamed in sheets via conventional compression molding techniques (PHI Co.). 2" x 2" x 0.02" pads are formed using the following conditions: 2 minute preheat at 193° C, followed by a 3 minute press cycle at 29 tons (193° C) and finally a 4 minute cooling to room temperature again at 29 tons press~ue.
The tensile properties of all materials are measured on a computer controlled Instron tensile tester (Model 5565). In most instances, little to moderate s improvement in tensile properties are measured.
The films containing Bio Terge°~ AS-90B beads are optically clear and homogeneous.
Following the mixing procedure of Example 5 using again the Exact~ 4049 to copolymer, a 3.0 wt% of a calcium alpha olefin sulfonate material (product of Stepan Co., Northfield, Illinois, USA) was introduced into the copolymer melt.
In this particular instance, the torque was not reduced. Expanding the range of the calcium-based material from 1.0 to 5.0 wt%, again showed no reduction in torque.
Compression-molded pads were produced (as in example 5). An 15 examination of the films showed that the calcium alpha olefin sulfonate was not mixed and, in fact, a large number of specks, i.e. heterogeneous regions, were observed, illustrating poor dispersion and mixing.
Example 5 is repeated using an antioxidant stabilized metallocene catalyst 2o synthesized plastomer, Exact~ 3033 (a 1.2 melt index, 0.900 g/cc density, ethylene butene hexene terpoIymer produced by Exxon Chemical Co., Houston, Texas, USA). Two concentrations (0.5 and 3.0 wt%) of the Bio Terge'~ AS-90B beads are evaluated. The lower and higher concentrations produced a torque reduction of 28 and >35%, resp~tively.
2s The compression-molded films were optically clear and homogeneous, indicating excellent dispersion and mixing.
E~c~ple 8 Example 7 is repeated substituting the sodium alpha olefin sulfonate with 3.0 wt% calcium alpha olefin sulfonate. No torque reduction is measured. The 3o compression-molded films are heterogeneous with a large number of specks randomly distributed throughout the film, illustrating poor dispersion and mixing.
Example 9 Example 5 is repeated using an antioxidant stabilized metallocene catalyst produced plastomer, Exact~ 3028 (a 1.2 melt index, 0.900 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co., Houston, Texas, USA.
5 Three concentrations (0.5, 1.0 and 3.0 wt%) of the Bio Terge~ AS-90B beads are evaluated. The data in Table 5 demonstrates that as the concentration is increased the torque is reduced.
Table 5 Sodium Alpha Olefin Sulfonate Torque Reduction (wt%) (%) 0.5 21 1.0 27 3.0 35 to Example 10 Example S is repeated using an antioxidant stabilized metaIlocene catalyst produced plastomer, Exact~ 3025 (a 1.2 melt index, 0.910 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co., Houston, Texas, USA). Two concentrations (0.5 and 3.0 wt%) of the Bio Terge AS-90B beads are evaluated.
15 The date in Table 6 demonstrates that as the concentration is increased the torque is reduced.
Table 6 Sodium Alpha Olefin Sulfonate Torque Reduction __ (wt%) (%) 0.5 25 3.0 30 Example 11 20 Example 5 is repeated using a physical mixture of antioxidant stabilized metallocene catalyst produced plastomers. In this example, the Exact~ 4049 copolymer and Exact~ 3033 terpolymer are melt mixed in a 93:8 wt ratio and subsequently, 0.5 wt% of the Bio Terge'~ AS-90B beads were added. A 12%
torque reduction is measured.
Example 5 procedure is repeated using F.xact~ 4049 and Exact~ 3033 rM
materials with a wide range of fluorocarbon-based materials (Fluorad Fluorochemical Surfactants produced by 3M, St. Paul, MN, USA). All materials s used were free of solvents) using comrentional drying procedures prior to melt mixing. The data in Table 7 describes the products used in this example as well as their chemical structures and the measured torque reductions at 193° C
at a 0.5 wt% concentration. The data demonstrates that no torque reductions are observed for both the potassium and ammonium perfluoroallcyl sulfonates. However, a Io range of torque reductions are observed which is dependent on the specific fluorocarbon structure.
Table 7 Fluorocarboq-Based Mad 3M. ProductType Description Torque Reduction-Torqnt:.
;. Nutober Euictm 4049 Reduction.-(%) - Erict~
.
"/.
'., FC-93 AnionicAmmonium 0 0 rlyuoroalkvl sulfonates FC-95 AnionicPotassium perfluoroalkyl0 0 and FC-98 sulfonates. 0 0 FC-99 AnionicAmine pertluoroallryl35 35 sulfonates FC-100 AmphoterFl~rinated alkyl6 6 is am hoteric mixture FC-I20 AnionicAmmonium 0 25 rfluoroalkvl sulfonates FC-I29 AnionicPotassium fluorinated7 7 alkyl carhoxvlates FC-135 CatiorueFluorinated alkyl17 58 quaternary ammonium iodides FC-143 AnionicAmmonium perfluoralkylI7 34 CaTbOXVlateS
FC-431 NonionicFluorinated alkyl37 30 esters FC-740 NonionicFluorinated alkyl~ 12 ~ _ esters 8 Example 5 procedure is repeated using sodium and calcium dodecylbenzene sulfonate materials. The former material is a product of the Witco Corp., Houston, Texas, USA and the latter material is a product of Stepan Co., North&eld, Illinois, USA. The data in Table 8 shows that the calcium-based material provides no reduction in the torque, while the sodium-based material provides only a relatively modest reduction (or no enhancement).
Table 8 DodecylbenzeneProduct DesignationConcentrationTorque Sulfonate (%) Reduction (%
Sodium Witconate 90 3.0 11 Sodium Witconate LX 3.0 6 Sodium Witconate SK 3.0 0 Calcium E erimental Product1.0 0 Calcium E erimental Product3.0 0 Calcium Experimental 5.0 J 0 Product ~
1o Examnles 14-18 Table 9 shows the description of samples used in these examples and summarizes the process data. Examples 14 and 17 are the comparative control samples . All materials were fabricated on a 3/4" Haake Rheocord extruder, Model E in the cast mode. The screw was a 15/5/5, 24:1 L/D with 15° tip. The polymer was extruded through a 4" tape die and wound through a stacked calendar assembly to the winder. All polymers were preblended and compounded on a 1 "
MPM single screw (24:1L/D) compounding extruder at a melt temperature of -190°C prior to film extrusion. Each example contained 25,000-30,000 ppm silica antiblock and -2000 ppm erucamide slip. All materials were cast extruded through 2o a 20 mil die gap at -190°C melt. Materials used consisted of Exact 4049 (4.5 MI;
0.873 density ethylene-butane copolymer), a metallocene plastomer produced by Exxon Chemical Co., Houston, Texas, USA; Vector 7400 D, an 8.0 MI/0.930 density SBS (31/69/ SB ratio) produced by Dexco Co., Houston, TX USA; and 3.0 wt% of a sodium alpha olefin sulfonate (Bio-Terge~ AS-90B beads produced by Stepan Co., Northfield, Illinois, USA as in example 1 ); and 3.0 wt% of calcium alpha olefin sulfonate, also produced by Stepan Co.
As can be seen, the sodium alpha olefin sulfonate drastically reduces the torque requirements when comparing samples 14 and 15 (> 2X). This same trend ~ was also evident when comparing samples 17 and 18, the Exact~ /SBS blends.
In all fow cases, the film exhibited good melt quality and homogenization. This was not the case when comparing sample 15 (calcium alpha olefin sulfonate). The film quality was very poor with numerous unmelted gels, even after raising the melt temperature from 190-240°C. It also did not compare with the sodium alpha olefin ~o sulfonate concerning torque reductions.
Table l 0 summarizes the test results for examples I4-I 8. Tensile testing was performed according to ASTM D-882 on a United Six Station tensile tester, model 7V 1. Tear results were obtained from an Elmendorf tear tester according to ASTM D-1922.
The hysteresis testing procedure used-is described as follows. This method is an Exxon variation of a procedure described by E.L, DuPont and Co. in its brochure on its polyester urethane elastic product, T-722A. In the variation used herein, 1 inch X 6 inch strips are subjected to a strain rate of 150% or 200%
with a jaw gap separation of 2" and cross head speed of ZO"/min. The hysteresis stress/-2o strain curve is plotted on a chart also traveling at 20"/minute. Both the extension and retraction cross head speeds (20"/min) were the same and performed on an Instron model 1123. The film was held for 60 seconds at maximum extension and then retracted and held for 30 seconds relaxation prior to the next cycle.
This was repeated 2 1/2 times. Key pieces of information that are extracted from these stress/strain plots are the maximum force (modulus) of each cycle, the residual set or permanent set (the degree of deformation as measured by the point of stress divided by total strain/cycle), and the unload force of contractive power as measured from the last retraction cycle at various elongations. Generally, five specimens were tested for each sample, with mean values over these samples 3o developed.
As can be seen, there are substantially no detrimental effects) to physical s properties with the addition of surfactants. In fact, there appears to be slight improvement to the elastic properties as compared to the control comparisons (example 14 and 17).
Table 9 Process Summary Exam I~ (1) ::14 .15. 16(2)I7 18 r:
Formulation Exact 4049 100 97 97 30 27 Vector 7400D 70 70 Na oc-olefin Sulfonate 03 03 Ca a-olefin Sulfonate 03 Extruder RPM ~ 32 32 32 32 32 Ext. FidPSI ~ 650 620 560 730 580 Die PSI 100 100 100 100 100 Ext. To ue -G 2600 1200 2100 2300 700 Ext. Melt C 191 193 231 191 193 Gau a mils 2.0 1.9 2.3 2.6 3.6 Line Speed (fpm) - X17- r1' r -15 12 ~
to (1) % excludes slip and AB addition via masterbatch (2) Poor extrusion, melt quality. Numerous-unmelted particles.
Table 10 1V~D Pronertv Summarv(1) >Test I4: 15 16 I7 ' I8 Formulation Exact 4049 100 97 97 30 27 Vector 70 70 Na a-olefin Sulfonate 03 03 Ca a-olefin Sulfonate 03 Tensiles Yld SI 287 287 233 165 160 Yld Elon % 11.8 11.8 11.5 6.6 6.4 Ult.Tns SI 2780 3260 2740 1900 1520 Brk Elon % 630 670 730 630 660 Tear mil 34.7 33.3 23.2 19.1 26.3 H steresis 150% ext Set 23.9 21.8 20.0 9.8 7.3 Modulus 1 560 500 460 405 510 Modulus 2 500 440 410 350 450 Unload at 50% 6 10 19 110 150 Unload at 100% (g) 140 i30 130 19~ 260 ~ ~ J
(1) MD= Machine Direction s Examples 19-26 Table 11 shows the description of samples used in these examples and summarizes the process data at both standard rates and maximum rates. Examples 19-22 are the control comparatives. Those samples describe a new grade under to development by Exxon Chemical Co., of Houston, TX, USA referred to as APT-3.
This is an advanced performance terpolymer having an MI of 2.2 and density of 0.898. Exact 4151 (2.2 MI, 0.896 density, metallocene ethylene, butene copolymer) is the precursor grade. Advanced Performance Terpolymers are characterized as having improved processability vs. their precursor counterpart in 15 the blown film process, i.e. lower motor load and torque requirements and improved bubble stability attributes. In these embodiments of the present invention, surfactant addition in the amount of 0.05, 0.1, 0.25 and 0.5 weight percents are added to APT-3 and compared to the control (APT-3) and base precursor grade (Exact 4151 ) with and without slip/antibiock addition. The slip 2o used was Kemamide E erucamide (produced by Witco, Inc., Memphis, TIC, the antiblock (AB) was ABT-2500 Talc (produced by Specialty Minerals, Los Angeles, CA) and the fluoroeiastomeric process aid (PPA) used in some of the formuiations was Viton A (produced by E.I. Dupont, Wilmington, DE). The surfactant used is a sodium alpha olefin sulfonate (Bio-Terge~ AS-90B produced by Stepan Co., Northfield, Illinois USA as in example 1). Prior to film extnision, all materials were compounded on a Werner and Pfleiderer ZSK-57 mm twin screw extruder at a melt temperature between 410-420°F (210-216° C).
The materials were then fabricated into films on a 2.5" Egan blown film line. This is a 24:1 LID
extruder powered by a 40 HP DC drive. Maximum screw RPM's is 115, thus to capable of producing a maximum torque of 0.35 HP/Rev. The barrel is liquid cooled and consists of 3 temperature zones and 5 pressure ports. The screw is a 24:1 L/D SterleX low work barrier screw having a 0.050" barrier undercut with a Maddock mixing device at the end of the screw also having a 0.050" undercut.
The die is a 6" Uniflo lower pressure bottom fed spiral mandrel die with a 60 mil die gap. The air ring is a 6" dual lip Uniflo design. Screenpack =
20/40/80/20.
Blow up Ratio (BUR) = 2.5. Temperature profile was as follows:
girl Z1 Brl Z2 B Z3 Dies/A~~ters 280° F 375° F 345° F 365° F-~
(138° C) (191° C) (174° C) (185° C) Each material was extruded at standard rates (~-7 lbs/in die/hr) and 2o maximum rates with all pertinent process data recorded on a data logger.
Each material was run until lined out as demonstrated via data logger (~1 hr/sampIe).
The maximum rate was defined as either the point of bubble instability (BS) motor load (ML) or maximum RPM's (RPM). Bubble instability criteria used was as follows:
~ bubble fluttering ~ gauged ~10%
~ edge wrinkles after adjustments to the collapsing frame.
If any of these criteria was met, the rate was backed off until a stable condition could be maintained as indicated by the data logger (steady state).
As can be seen, surfactant addition has little to no effect on process at low rates. The real effect occurs between 0.25-0.50 weight percent levels. At 0.5 weight percent level there is an ~20% reduction in motor load compared to APT-and ~30% reduction when compared to the precursor material. Effects on torque also follow this trend with an ~30 and ~40% reduction, respectively. Low level surfactant (0.05-0.1 weight %) improves rate production slightly. Between 0.25-0.5 weight %, the rate is increased substantially due to the reduced motor load and lower melt. At 0.5 weight % level, rate production was increased by >25%
compared to APT-3 w/o surfactant and >45% when compared to the precursor.
to No pumping efficiency (lbs/RPM) is lost between 0.05-0.25 weight %.
Between 0.25-0.5 weight % there is a drop off, but this is of little consequence if there is available extruder RPM.
Surfactant addition to Exxpol~ metalIocene grades and APT grades can have a substantial effect on processability especially in monolayer blown film Z5 production where motor load and torque requirements can be limiting factors.
These advantages are also seen in conventional Z-N catalyzed LLDPE production.
Table 12 summarizes physical property test results and as can be seen, no detrimental effects can be attributed to the addition of surfactant. All tests were performed according to the appropriate ASTM standard method.
2o Table 13 illustrates no adverse surface sealing effects can be attributed to the addition of surfactant. Hot tack comparisons of Exact 4151, APT-3 w/o surfactant and APT-3 w/surfactant are virtually identical as demonstrated.
In addition, organoleptic testing by a certified odor and taste facility show no adverse effects for food packaging applications.
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Th~;re is a need therefore for a relatively inexpensive, easily implemented solution tc the processing problems outlined above. Such a solution should also include a material that when included in blown film extrusion of linear polyethyle yes andlor linear polyethylene-elastorner blends, will readily melt or incorporate into the melted polyethylene, and not adversely affect physical properties not be e;ctractable, or negatively impact organoleptics of the film.
Specifical! ~r, there is a commercial need for a material that may be eaaily 1.o incorpora~. ~ into po!yethylenes and polyethylene elastomer blends, that will reduce or elintina to the increased power requirement (e.g. motor load and cr torque), increased '.lead pressure, and melt fracture.
St'MM_~ 2Y
'T'1 a present invention is directed to such a material, a certain group of i5 surfactant s, and methods of their use which when incorporated into a linear polyethyl~:.ne or linear polyethylene elastomer blends, can reduce or eliminate proeessin; problems such as melt fracture, increased motor load, increased torque, and comt~'nations thereof and may thereby iincrease potential production rates.
Ire certain embodiments of the present invention a method of processing zo polyethyl~:nes comprising selecting a lines~r polyethylene, from a group such as linear loo r density polyethylene (LLDPE), metallocene LLDPE (mLLDPE), high density p~~lyethylene (HDPE), plastomers, ultra high molecular weight high density polyethyl:ne (1;J~F~MW-APE), medium density polyethylenes (MDPE), or combinations thereof, adding an elastomer~ selected from the group consisting of z5 styrene t~.rtadiene styrene (SBS); styrene isoprene styrene (STS); styrene ethylene butadiene: styrene (SEBS); styrene ethylene propylene styrene (SEPS); and combina~ :ans thereof and adding a surfactant. The surfactant being an aliphatic sulfonatE~ salt having a cation selected from the group wnsisting of Na, I~, and Li.
An amo~.~nt of the surfactant should be added that will be sufficient to improve the 30 melt prc cessability of the polyethylene or polyethylenelelastomer blend.
'The combinan ion of polyethylenes and 96H034. E'Cr surfactant or surfactants and optionally an ela~.stomer or elastomers is then used to melt proce ~s the combination into a useful article, such as a film. blow molded part, and the lik ~.
Th ~ polyethylenes may be conventional Ziegler-Natta (Z-;~ catalyzed materials ! oat generally have a molecular weight distribution characterized by the ratio of w~;ight average molecular weight to the number average molecular weight (bi""lM~ , bove about 4, or the polyethylenes may be metallocene catalyzed, and will then 1~ 3ve an approximate M"J~f~, of less than 3, preferably less than 2. ~, and a z-average :molecular weight (M~ divided by R~i", (M~l~l~tW) not exceeding 2.
l0 Al ~o contemplated are compositions of a polyethylene having an Mw~:~in less than ., and optionally an elastomer or elastomers and an alkali metal alkyl sulfonate -~r sulfate wherein the alkyl group has 6-30 carbon atoms. where the surfactant is present in the polyethylene or polyethylene elastomer blend in a range of from 0.')05 to 1 weight percent based on the total weight of the polyethylene or is blend. TI'S a surfactant should ideally be substantially non-extractable from the final fabricated article.
'TW~se and other features, aspects, and advantages of the present invention will beca; ne better understood with reference to the following description and appended rlaima.
2o DESCRI;'Tr~N
In certain embodiments of the present invention, methods of and compositi.ms far reducing or eliminating; a) melt fracture; b) torque; c}
increased head pre:~sure; d) increased motor load, e) combinations thereof, and the like, during the; melt processing of polyethyienes, polyethylene elastomer blends and 25 other pol'. olefins are contemplated. These ernbodiments include both corwentional Z-N ancG metallocene catalyzed polyet;hylenes(the latter hereinafter "m-polyethylc nes), and their combination with certain surfactants and optionally an elastomer that when so combined achieve the stated melt processing improvestuents. The combination of polyethylenes and surfactants are particularly 3o well suite 3 to melt processing and fabrication. into films, especially blown films, blow mol:ed articles, and the like, while reducing or eliminating one or more of the WO 98/05711 - PCTlI1S97/1385b processability problems discussed above and generally without being extractable from the final fabricated article.
Following is a detailed description of certain preferred combinations of polyethylenes and surfactants and optionally an elastomer and methods of using the combinations in melt processing into useful articles. Those skilled in the art will appreciate that numerous modifications to these preferred embodiments can be made without departing from the scope of the invention. For example: Although methods of improving melt processing of m-polyethylenes or m-polyethylene elastomer blends into films are exemplified, they will have numerous other uses and to the films may be formed from other polyolefins or combinations of polyethylenes.
To the extent this description is specific, it is solely for the purpose of illustrating preferred embodiments of the invention and should not be taken as limiting the present invention to these specific embodiments.
DEFIhTITIONS
torque - horse power/rpm motor load - amps head pressure - Kpa (psi) The Encyclopedia of Polymer Science and Technology, Vol. 8, John Wiley & Sons, (1968) pp. 573-575 indicates that for a given polymer, processed at a 2o constant melt temperature, there exists a critical shear rate in the melt fabrication process. Melt processing of the polymer below this critical shear rate will result in a smooth extrudate surface while processing the polymer above it will result in a rough extrudate surface. The observed roughness is commonly referred to as "melt fracture" but may also be described by other terms such as "sharkskin" or "orange peel". For a given polymer, the critical shear rate increases as the melt processing temperature of the polymer increases.
The extent of extrudate roughness will vary depending upon the shear rate at which the polymer is processed. At shear rates just above the critical value, the extrudate roughness normally results in a loss of surface gloss and is typically called "sharkskin". At higher shear rates, the extrudate exhibits periodic areas of roughness followed by areas of smoothness in a more or less regular pattern.
This phenomenon is normally described as "cycl.ic melt fracture". At very high shear rates, the extrudate may become grossly distorted resulting in a what is commonly called "continuous melt fracture".
In general, linear polyethylenes, particularly those with high average molecular weights and/or narrow molecular weight distributions, tend to be more prone to the formation of melt fracture than highly branched polyethyienes, such as conventional LDPE made by high pressure polymerization.
The presence of melt fracture in a fabricated article can lead to poorer optical properties and is generally aesthetically unacceptable. Attempts to to eliminate melt fracture in articles fabricated from linear polyethylenes by either reducing the processing shear rate (reduced production rate) or by increasing the processing temperature (increased melt temperature) are generally not commercially viable. In addition, changes in die design to reduce the shear rate (e.g., use of wider die gaps) can result in other problems such as excessive orientation leading to unbalanced article properties. Although fluoroelastomeric processing additives have been used to eliminate sharkskin in linear polyethylenes under certain processing conditions, their u:>e is expensive due to the high cost of the fluoroelastomer.
2o POLYETHYLENES
The polyethylenes contemplated in certain embodiments of the present invention, include ethylene alpha-olefin copolymers. By copolymers we intend combinations of ethylene and one or more. alpha-olefins. In general the alpha-olefins comonomers can be selected from those having 3 to 20 carbon atoms.
Specifically the combinations may include ethylene 1-butene; ethylene 1-pentene;
ethylene 4-methyl-I-pentene; ethylene 1-hexene; ethylene 1-octene; ethylene decene; ethylene dodecene; ethylene, 1-but.ene, 1-hexene; ethylene, 1-butene, I-pentene; ethylene, I-butene, 4-methyl-1-p~entene; ethylene, 1-butene, 1-octene;
ethylene, 1-hexene, 1-pentene; ethylene, 1-hexene, 4-methyl-1-pentene;
ethylene, 1-hexene, 1-octene; ethylene, I-hexene, decene; ethylene, I-hexene, dodecene;
ethylene, propylene, I-octene; ethylene, 1-octene, I-butene; ethylene, I-octene, 1-pentene; ethylene, 1-octene, 4-methyl-1-pentene; ethylene, 1-octene, 1-hexene;
ethylene, 1-octene, decene; ethylene, 1-octene, dodecene; combinations thereof, and the like permutations. The comonomer or comonomers will be present in the copolymers in the range of from about 0.1 to about 40 mole percent. The actual amount of comonomers will generally define the density range.
Density ranges contemplated to be useful include 0.86-0.97 g/cc and all portions and constituents of the range. Specifically included are the 0.86 -0.91 S
g/cc (plastomers) 0.916-0.925 (LLDPE), 0.926-0.940 (MDPE), and 0.941-0.970 (HDPE). Melt indices contemplated include 0.001-30, preferably 0.5 to 5.0 for to blown films, and 0.3-10 for blow molding, and all members of these ranges (melt index in dg/min or g/10 minutes).
Polyethylenes that are produced using metallocene catalysts include ionizing activators as well as alumoxanes.
Included in the embodiments contemplated are those where either m polyethylenes and Z-N polyethylenes may be blended with each other and/or with other components such as LDPE, (highly branched, high pressure free radical polymerized) and other ethylene copolymers such as ethylene vinyl acetate (EVA), ethylene n-butyl acrylate (EnBA), ethylene methyl acrylate (EMA}, ethylene ethyl acrylate (EEA), ethylene acrylic acid (EAA), ethylene methacrylic acid (EMAA), 2o and ionomers of the acids, terpolymers such as ethylene, vinyl acetate methyl acrylate; ethylene, methyl acylate, acrylic acid; ethylene, ethyl acrylate, acrylic acid;
ethylene, methyl acrylate, methacrylic acid; ethylene, methylacrylate, methacrylic acid; and the like.
The polyethylene eiastomer combinations described above, in combination with the surfactants described below, will be substantially free of propylene polymers such as polypropylene homopolymers and copolymers. By substantially free we intend that Less than 5 wt. % of the total polymer will be a propylene based polymer, preferably less than 3%, more preferably less than 1%, most preferably to totally free of propylene polymers.
3o Also contemplated are mufti-layer blown film extrusions where one or more of the layers can include a polyethylene/surfactant or 96BG34.?CT
polyethylec:elelastomersJsurfaetant combination, Such e~ctrusion may inci,rde a linear poh~ethylene layer, a heat seal layer, a barrier (gas atidlor vapor) layer, rxycle or regind layer or combinations thera~of.
So~~ne of these blend components may affect processing variables in a s po3itive n~anner, in which case the inven~rion contemplated will include some portion of the below discussed surfactants, possibly less than with an unblended material.
laic ~st polyethylenes will contain various additives well itnow~n to those of ordinary s'~:ill in the art, including, but not luruted to slip, anti-block, anti-oxidants, ~o anti-fogs, acid neutralizers, UV inhibitor.., anti-static agents, pigments, dyes, release ag~:mts, fungicides, algecides, bactericides, and the like.
As used in this application, the processing temperature of pr~lyethy~lene in the blown r~lm process wi31 generally he in the range of 300 - 450° F
(149-232° C), preferably 35G - 410° C (177-210° C), a point generally above the melting point of 1s the poly~tliylene and below its degradation ~~r decomposition temperatu:e.
This is generally the temperature of the melt exiting the die, but may be measured at any point doa nstream of the screw elements. The processing temperature will be understood.' by those of ordinary skill to ~~ary generally by the melt fabrication technique, and within a fabrication technique, processing temperature can vary by 2o the type ~:.:.f processing equipment, or by specific requirements of a particular manufactu rer.
SL'RFAC'~~.'ANTS
Tt~ a surfactants contemplated include aliphatic sulfonate salts where the canon is o~~e of. Li, Na, K Sodium salts being preferred. The surfactants may also ~5 be describ~;d as alkali metal aliphatic sulfonates where the aliphate group is a C6 to C30 alkyl group, preferably C8 to C20, more preferably C12 to C18, The alkyl group mail be chosen from the group consisting of branched or straight chain alkenyl, bwanched or straight chain hydroxyl substituted alkyl, and combinations thereof ~freferred are combinations of branched or straight chain alkenyls and 3a branched ~ rr straight chain 96H034.PCT
hydroxyl s ~bstituted alkyf alkalai metal sulfates or sulfonates, of these the scdiurrt combinarc n is most preferred.
On . class of surfactants that arc preferred in this application are a-olefin suL°onates. As stated in the Kirk-C~thmer Encyclopedia of Chemical T
achnology, 5 Vol. 2?, J~ ~hn W'iley & Sons, (1983), pg. 35:?, a-olefin sulfonates are produced by reaction o ' a-oleixn with S03 in air followed by neutralization with a base to produce t!1e corresponding salt. The sodium salts are the mast preferred.
Commerci.3 ct-olefin sulfonates are a mi~rnare of alkene suifonates and hydroxy allcane sulf mates. The position of the double bond in alkene sulfonates as well as to the hydrox v1 group in hydraxy alkane sulfonates varies along the carbon chain of the alkyl ~ oup.
Mr-e detailed description of the surfa.otants follows.
Thn surfactant includes those, of the c;eneral formulae:
I,) ~R~ SO~~vh Ml is selected from the group consisting of~
Li, Na, K, R1 is selected from the group consisting of branched or straight chain mono or dl unsaturated alkenyl, branchad or straight chain hydroxyl substituted alkyl, and combinations thereof, 9GH034.PC'r ~ ~~herein the carbon number of said R1, ranges from 6 to 30; and ~ herein said surfactant is present in mid combination in a range of up t ~ 1.0 weight percert, preferably 0,005 to 1.0 weight percent, more preferably O.OI to 0.5, most preferably 0.03 to 0 35 weight percent brsed on the total weight of the cornbination.
Or a ~~urfactant represented by one of the formulae:
IL) ~R SO~~M
M1 is selected from the group consisting of Li, Na, K, and other rations.
R1 is selected from the group consisting of:
branched or straight chain mono or dl unsaturated alkenyl;
branched or straight chain hydroxyl substituted alkyl, arid combinations thereof, ' '~' ~"~ CA 02259529 1999-O1-04 -968034.PCi' ~Nherein said surfactant is present in said combination up to 1.0 weight percent, preferably in a range of 0.005 to 1.0 weight percent. more ;preferably 0.01 to 0.5, most pre:Ferably 0.03 to 0.35 weight percent Sased on the total weight of the combination.
The surfactant or surfactants should he substantially or essentially free of halogens. By substantially or essentially free of halogens we intend that the surfactant n olecules will have preferably no h;rlogen.
The surfactants comtemplated, whether a mixture or a single surfactant should have a melting point less than 240° C. preferably 23a°
C., more preferably to 220° C., me ~~t preferably 2I0° C.
The surfactants may be present in the polyethylene combination up to 1.0 weight pere~.nt, in the range of from 0.05-1.C~ weight percent, preferably 0.01-0.5, more prefer ~~bly 0.03- 0.35 weight percent (including all elements in these ranges}
based on th~:~ total weight of the combination. The amount and type of surfactant is present will ietermine the effect on the melt processing characteristics, for instance as shown be i ow, smaller amounts at about 0. 3 5 wt% ox below preferably 0.25°~0, more prefer ably 0.10 wt%, or below, will primarily function to reduce melt fracture, whi.!e amourrts above that level, up to the indicated higher levels will begin to also redm. a head pressures, torque, motor load or combinations thereof.
While dfl greater amo~..nts than the 0.5 levels may be used, adverse extrusion effects may result such a ~ grew slippage.
Thos: of ordinary skill will appreciate ':hat at higher levels, generally above 0.1 weight percent, the surfactant or a combination of surfactants will be ei~'ective in reducing c' of only melt fracture, but motor Ioad, torque, head pressure and the 2s like by at leant 5% for one or more ef these variables. Generally at lower levels than 0.1 weight percent the reductions of these motor load, torque and head pressure parameters will be less, but the :surfactants will be effective in reducing melt fracture.
The mechanism of melt fracture reduction is believed to involve the s formation of a layer of surfactant on the internal metal surfaces of key components of the melt processing equipment. This layer effectively increases the velocity of molten polymer at the metal interface 'thereby minimizing the polymer flow distortions that occur as the molten polyn:~er exits the melt processing equipment which typically results in melt fracture. The use of a relatively high concentration to of surfactant, e.g. 0.5 weight percent, will generally result in a faster rate of metal surface coating and, therefore, a more rapid rate of reduction in melt fracture of the final fabricated article. At lower surfactant levels, the metal surface coating rate, and the corresponding melt fracture reduction rate, will be slower.
It should be noted that when discussing the weight percent of surfactant, 1s we intend that this be based on the total weight of the surfactant and polyethylene (or polyethylene blend). If other constituents are included the amount of surfactant should be then calculated on a parts per hundred parts of polyethylene basis.
Likewise if a blend constituent (with the linear m-polyethylene) assists in improving processability, then the contemplated arr~ount of surfactant will be that level 2o sufficient to achieve the intended effect, e.g. reduction of one or more of melt fracture,. motor load, torque, or head pressure.
For example, blends of one or more of the above surfactants may be used to achieve the desired results, as well as combinations of polyolefin waxes and/or fluoroelastomers and/or fluoropolymers with one or more surfactants. For instance 2s one or more of the surfactants listed above may be combined with a polyethylene wax in ratios from 10-90 and 90-10 and all elements in and between these ranges, and a similar combination with fluoroelastomers and/or fluoropolymers is also contemplated, as well as surfactant/polyethylene wax/fluoroelastomer combinations.
3o If the polyethylene composition o:r the film made therefrom contain the optional elastomer or elastomers, the thermoplastic elastomeric films of certain embodiments of the present invention comprise a blend of at least two copolymers.
One copolymer is an elastomeric block copolymer containing blocks of a monoalkenyl arene copolymer and a conjugated diene polymer. The second component is selected from a group of highly amorphous thermoplastic ethylene copolymers having the primary characteristic of low crystallinity and low density (such as m-plastomers and/or m-LLDPE). Optional ingredients which may also be included in the polymer blends of the present invention include small amounts of conventional anti-block concentrates and slip agents, as well as antioxidants and stabilizers.
1o THE ELASTOMERIC BLOCK COPOLYMER
The elastomeric block copolymers contemplated for use herein are known materials having blocks of monoalkenyl arene polymer and blocks of conjugated diene polymer. The polymer blocks have the general configuration:
A-B-A
and are arranged such that there are at least two monoalkenyl arene polymer end blocks A and at a least one elastomeric conjugated dime mid block B. These polymer blocks may optionally be hydrogenated to eliminate the unsaturation in the mid block B. The monoalkenyl arene copolymer blocks comprise from 8% to about 55% by weight of the block copolymer. The molecular weight of the block copolymer is such that its melt index is less than about 100 as determined by ASTM Method D 1238 entitled "Standard Test Method for Flow Rates of Thermoplastics by Extrusion Plastomer" Condition E.
The term "monoalkenyl arene" includes those particular compounds of the benzene series such as styrene and its analogues and homologues including o-methyl styrene and p-methyl styrene, p-tent-butyl styrene, 1,3 dimethyl styrene, p methyl styrene in other ring aikylated styrenes, particularly ring methylated styrenes, and other monoaikenyl polycyciic aromatic compounds such as vinyl naphthalene, vinyl anthrycene and the like. For the present invention, the preferred monoalkenyl arenes are monovinyl, monocyclic arenes such as styrene and p methyl styrene, styrene being particularly preferred.
It is important to embodiments of present invention that the amount of monoalkenyl scene not exceed an amount of 55%, nor comprise an amount less than 8% by weight of the copolymer. Preferred amounts of monoalkenyl scene in the block copolymer are from 25% to 35%. Optionally, the monoalkenyl scene will s , be in an amount of about 30%. If a monoalkenyl scene is used in excess of weight percent, the block copolymer is too stiff for the instant blends. The elastomeric block copolymers are optionally "oil extended" which is the addition of a hydrocarbon oil and allows for improved processability and soRer films. The oils are optionally added to the commercial elastomeric copolymers in amounts of 10 between 10% t0 40%.
The block B comprises homopoiymers of conjugated diene monomers, copolymers of two or more conjugated dienes, and copolymers of one or more of the dienes with a monoalkenyl scene as long as the blocks B are predominantly conjugated diene units. The conjugated dienes preferably used herein contain from 15 4 to 8 carbon atoms. Examples of such suitably conjugated diene monomers include: 1,3 butadiene (butadiene); 2-methyl-1,3 butadiene; isoprene; 2,3 dimethyl-1,3 butadiene; 1,3 pentadiene (piperylene); 1,3 hexadiene; combinations thereof, and the like. Hydrogenation of the unsaturated elastomer (Block B) results in a saturated tri-block copolymer (A-B-A).
2o For the instant films, the preferred monoalkenyl scene polymer is polystyrene; and the preferred conjugated diene polymers are polybutadiene and polyisoprene, especially preferred being polybutadiene. The preferred elastomeric block copolymers are commercially available as linear tri-block copolymers (A-B-A) from the Shell Chemical Company, Polymers Division, Houston, Texas, under the trade name KRATON and from Dexco Polymers of Houston, Texas, under the family trademark VECTOR. Especially preferred are the linear tri-block copolymers having polystyrene end blocks and a polybutadiene mid-block (S-B-S).
Most commercially preferred are oil extended polymers such as ICRATON D 2104 having a melt index of about 7 as determined by ASTM Method D 1238, Condition E and VECTOR 7400D, having a melt index of about 8.
The thermoplastic elastomeric films of the present invention may contain from about 20%-70% by weight of the elastomeric block copolymer; preferably from about 45%-65%; especially preferred being from about 50%-65% based on the total weight of polyethylene, and elastomer. The percentages herein are based on the total weight of the elastomeric film composition. As indicated, commercial grades of elastomeric block copolymers can be oil extended and the oil portion is not calculated as part of the percentage herein. To firrther enumerate the elastomer, linear polyethylene (m-plastomer and/or m-LLDPE) the two parts (polyethylene/elastomer) can be present in a ratio of 1:4-2:1; preferably 1:2-2:1.
1o The thermoplastic eiastomeric films of the present invention may be used in a wide variety of applications where thin, elastic material would be useful.
Such films are particularly useful as low cost elastic members for disposable wearing apparel such as diapers; training pants, feminine hygiene devices, medical gowns, gathered laminate garments, non-woven head bands, sports apparel, bandages and protective clothing.
FILM PROPERTIES
Other final product variables or parameters that are included are discussed below.
The addition of suffcient levels of surfactant to a polyethylene should 2o generally be "property neutral" that is, the surfactant addition should not substantially diminish any important finished product property such as haze, impact resistance, gloss, tear resistance, modulus, and the like.
The surfactant should have a melting point not generally greater than 30°
C, preferably 25° C, more preferably 20° C, most preferably 15° C above the processing temperature of the linear polyethylene. The surfactant is generally and preferably molten at the processing temperature of the polyethylene. The processing temperature will be well understood by those of ordinary skill in the art and will diffier by melt fabrication technique, e.g. blown film and blow molding temperatures will vary. Also the melt processing temperature can be characterized 3o by the melt temperature itself rather than the extruder zone temperatures.
EXTR.ACTABILITY
Extractability of the surfactant from the polyethylene-surfactant matrix should be no more than 7% (wt) of the total surfactant in either water (at 100° C
for 3 hrs.) or 95°/JS% ethanoUwater (at 55° C for 4 hrs.), preferably not more than 3 5% (wt.), more preferably not more than 4% (wt.), all based on not more than wt. % of surfactant in the polyethylene.
EXAMPLES
E~cam 1R a 1 An antioxidant stabilized metallocene catalyzed linear low density to polyethylene resin (m-LLDPE), Exceed''" ECD 102 of the following nominal properties (a 1 melt index, 0.917 gm/cc density, ethylene 1-hexene copolymer available from Exxon Chemical Co., Houston, TX, USA), is used in this example.
To the ganular m-LLDPE resin (Example 1 ) is added 0.25 wt% BioTerge~ AS-90B Beads (a sodium C 14-C 16 ~Pha olefin sulfonate available from Stepan Co., 15 Northfield, IL, USA). A control sample (Comparative example C 1 ) is prepared by adding 0.08 wt% Dynamar'''~ FX-9613 (a fluoroelastomeric processing aid available from 3M Co., St. Paul, MN, USA) to a separate portion of the ganular m-LLDPE resin. Both portions are compounded and pelletized on a Werner Pfleiderei twin screw extruder.
2o The two pelletized formulations are extruded into film on a 2.5 inch (6.35 cm) Egari tubular blown film extnader. The extruder has a 24/1 length/diameter ratio, Sterlex~ barrier LLDPE screw and is equipped with a 6 inch (15.25 cm) diameter annular die with a 0.030 inch (0.076 cm) die gap. The temperature profile used ranged from 325 to 410°F ( 162-210° C). Observed melt temperatures 25 ranged from 432 to 438°F (222-225° C). Extruder screw rpm is set to achieve approximately 120 lbs (54.5 kg)/hr of polymer output. Under these conditions, the estimated shear rate is approximately 430 sec' 1. The extruded film gauge was nominally 0.0015 inch (38 microns) with a layflat of approximately 24 inches (61 cm).
The extrusion sequence for each formulation is as follows. The film line is purged with an LDPE masterbatch containing approximately 4 wt% diatomaceous earth antiblock (A1 product from Exxon Chemical Co., Houston, TX, USA).
Next, a portion of the m-LLDPE resin, to which no BioTerge~ AS-90B or DynamarTM FX-9613 is added, is extruded into film. Samples of the film are inspected to ensure complete melt fracture. Finally, the test formulation is extruded into film. Periodic samples of the film are taken and the portions which display visible melt fracture, characterized by patterns of irregular flow known as sharkskin, are measured in the transverse direction of the film. The % melt fracture to is calculated based upon the total layflat width of the film.
The data in Table 1 demonstrates that 0.25 wt% BioTerge~ AS-90B used in Example 1 substantially eliminates melt fracture in the m-LLDPE film. The elapsed time for this substantial elimination of melt fracture is nearly the same amount of time needed for 0.08 wt% DynamarTM FX-9613 (Comparative example CI) to eliminate melt fracture. At the end of each run, the extruder rpm is increased until the motor load limit is reached (93 rpm) and melt fracture-free film is maintained for each formulation (680 sec-1 ). A sample with neither FX-9613 nor AS-90B never achieves melt fracture free performances.
This is as expected since extrusion shear under these conditions results in a rate above the critical shear rate for this m-LLDPE. In the absence of the surfactant or fluoroelastomer, this will cause melt fracture in the resulting film.
Table 1 Melt Fracture Elapsed Example Example 1 Time C 1 (w/ 0.25 wt%
(w/ 0.08 AS-90B
wt%
min _ 0 =__ , 5 Table 1A
Example OutputAS-90B FX-961:3Head Die Motor (lb./hr)Conc. Conc. Pressure PressureLoad wt%) (wt% si ) si am s 1 120 None None 56?0. 4340. 57.7 1 120 0.25% None 4794. 3670. 45.0 C 1 115 None None 4945. 4008. 54.2 C1 115 None 0.08% ~ 3701. 3098. 46.8 j In addition, the extruder head pressure, die pressure and motor load measured during the extrusion of Example I was reduced by approximately 15 to l0 22 % when compared to the same m-LLDPE resin without BioTerge~ AS-90B.
Comparative example C1 showed reductions in the range of 14 to 25% when compared to the same m-LLDPE resin without DynamarTM FX-9613.
Based upon this example, 0.25 wt % of the BioTerge~ AS-90B provides equivalent performance to 0.08 wt % Dynamar~ FX-9613 in reduction of melt 15 fracture, head pressure, die pressure and motor load in Exceed~ ECD102 m-LLDPE.
Example 2 The m-LLDPE resin used is the same as that of Example 1. The granular m-LLDPE resin is split into two portions. The first portion, which contained no SUEtSTITUTE SHEET (RULE 26;
processing aid previously discussed (e.g. BioTerge~ AS-90B or FX-9613) and pelletized on a Werner Pfleiderer 57 mm twin screw extruder (Comparative example C2). To the second portion of m-LLDPE is added 0.06 wt% BioTerge~
AS-90B beads followed by compounding/pelletization on the same twin screw 5 extruder (Example 2).
The two formulations are extruded into film using the same extruder as in Example 1. The temperature profile used ranged from 325 to 400°F (162-204° C).
Observed melt temperatures range from 432 to 439°F (222-226° C). Extruder screw rpm is held constant at 74 rpm to achieve approximately 140 lbs/hr of to polymer output. Under these conditions, the estimated shear rate is approximately 500 sec-l. The extrusion sequence is as follows: A1, Comparative example C2, Example 2.
The elimination of melt fracture is measured using the same method as in Example 1. In addition, extruder measurements of head pressure, die pressure and 15 motor load are taken periodically.
The data in Table 2 demonstrates that 0.06 wt% BioTerge~ AS-90B used in Example 2 reduces melt fracture in the m-LLDPE film to approximately 1%
within an hour and completely eliminates it within 1.5 hours. As expected, the rate of elimination of melt fracture is slower when a lower concentration of BioTerge~
2o AS-90B is used. By contrast, the m-LLDPE resin which contains no BioTerge~
AS-90B yielded film which was completely melt fractured. Even at this low concentration, the BioTerge~ AS-90B reduced the extruder head pressure, die pressure and motor load by 6 - 7%. At the end of the run, the extruder rpm was increased until the motor load limit was reached (96 rpm) and the Example 2 formulation maintained melt fracture-free film (630 sec-1).
Table 2 Example ElapsedAS-90B Head Die Motor Melt Time Conc. PressurePressureLoad Fracture min wt% si 'i si am s C2 94 0 5709 4520 57.4 100 2 0 0.06 5?71 4592 57.5 100 2 30 0.06 5601 4392 55.0 18 2 57 0.06 5462 4338 54.4 1 2 86 0.06 5314 4220 53.6 0 Example 3 The antioxidant stabilized plastomer used in this example was an ExaciTM
3128 (a 1.2 melt index, 0.900 gm/cc density, ethylene 1-butene copolymer available from Exxon Chemical Co., 1-louston, TX, USA). The pelletized metallocene plastomer resin was split into two portions. The first portion, which contained no processing aid, was tested directly (Comparative example C3). To the second portion of metallocene plastom~er was added 0.06 wt% BioTerge~ AS
l0 90B beads followed by compounding/pelletization on a Werner Pfleiderer 57 mm twin screw extruder (Example 3).
The two formulations were extrudc;d into film using the same extruder and test sequence as Example 2. The temperature profile used ranged from 300 to °F (149-202° C). Observed melt temperatures ranged from 413 to 417°F (212-16 214° C). Extruder screw rpm was :held constant at 52 rpm to achieve approximately 120 lbs/hr of polymer output. Under these conditions, the estimated shear rate was approximately 430 sec' 1.
The data in Table 3 demonstrates i:hat 0.06 wt% BioTerge~ AS-90B used in Example 3 completely eliminates melt fracture within 33 minutes. By contrast, 2o the metallocene plastomer resin which contained no BioTerge~ AS-90B yielded films which was completely melt fractured. The observed reductions in extruder head pressure, die pressure and motor load ranged from 10 to 14%. At the end of the run, the extruder rpm was increased until the motor load limit was reached (64 rpm) and the Example 3 formulation maintained melt fracture-free films (520 sec-t ).
Table 3 Example ElapsedAS-90B Head Die Motor Melt Time Conc. PressurePressureLoad Fracture min wt% si si am s C3 30 0 6047 4555 62.3 100 C3 56 0 6045 4543 63.0 100 3 0 0.06 5979 4521 60.7 100 3 33 0.06 5503 4131 57.4 0 3 59 0.06 5225 3920 55.9 0 ~ ~
Example 4 An antioxidant stabilized Z-N catalyzed linear low density polyethylene resin (I,LDPE), Escorene~ LL1001 (a 1.0 melt index, 0.918 gm/cc density, ethylene 1-butene copolymer available from Exxon Chemical Co., Houston, TX, to USA), is used in this example. The granular LLDPE resin is split into two portions. The first portion, which contained no processing aid, is pelletized on a Weiner Pfleider 57mm twin screw extruder and then tested directly (Comparative example C4). To the second portion of LLDPE was added 0.06 wt% BioTerge~
AS-90B beads followed by compounding / pelletization on a Werner Pfleiderer 57 mm twin screw extruder (Example 4).
The two formulations were extruded into film using the same extruder and test sequence as Example 2. The temperature profile used ranged from 233 to °F ( 112-211 ° C). Observed melt temperatures ranged from 434 to 440°F (223-227° C). Extruder screw rpm was held constant at 69 rpm to achieve 2o approximately 147 Ibs/hr of polymer output. Under these conditions, the estimated shear rate was approximately 525 sec-1 The data in Table 4 demonstrates that 0.06 wt% BioTerge~ AS-90B used in Example 4 reduced melt fracture in the LLDPE film to approximately 24%
within an hour. By contrast, the LLDPE resin which contained no BioTerge~ AS-90B yielded film which was completely melt fractured. The observed reductions in extruder head pressure, die pressure and motor load ranged from 8 to 15%. Melt fracture was completely eliminated after 155 minutes. At the end of the run, the extruder rpm was increased up to the limit of bubble stability (105 rpm) and the Example 4 formulation maintained melt fracture-free film (700 sec-1).
1e 4 Example ElapsedAS-90BB Head Die Motor Melt Time Conc. PressurePressureLoad Fracture mlil Wt% St S1 Bin S
C4 39 0 4877 3724 48.9 100 4 0 0.06 4733 3597 45.3 100 4 41 0.06 4451 3471 41.8 45 4 56 0.06 4419 3423 41.7 24 An antioxidant stabilized metallocene catalyst produced plastomer, Exact~
1o 4049 (a 4.5 melt index, 0.873 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co., Houston, Texas, USA) is used in this example. A pelletized form of the copolymer is introduced into a BrabendeT Plasti-cordec melt mixer which was heated to 193° C. Typically, 50-60 g of material is introduced at a rotation speed of 40 RPM. Upon complete melting, the torque remains essentially invariant with time and is used as the base value. Subsequently, a measured amount of sodium alpha olefin sulfonate (Bio Terge~ AS-90B beads - product of Stepan Co., Northfield, Illinois, USA) is added. The torque is again measured at 40 RPM and compared with the base torque value. In this particular example, a torque reduction (12%) is observed at 0.5 wt% of the Bio Terge~ AS-90B beads.
At higher levels of the Bio Terge~ AS-90B beads, further reductions are noted.
For example, at a 3.0 wt% addition, the torque is reduced by >35%. To insure that complete mixing has occurred, the rotation speed is increased to 100 RPM for five minutes. The material is dumped from the Brabender, cut into small pieces, and allowed to cool to room temperature.
The material is foamed in sheets via conventional compression molding techniques (PHI Co.). 2" x 2" x 0.02" pads are formed using the following conditions: 2 minute preheat at 193° C, followed by a 3 minute press cycle at 29 tons (193° C) and finally a 4 minute cooling to room temperature again at 29 tons press~ue.
The tensile properties of all materials are measured on a computer controlled Instron tensile tester (Model 5565). In most instances, little to moderate s improvement in tensile properties are measured.
The films containing Bio Terge°~ AS-90B beads are optically clear and homogeneous.
Following the mixing procedure of Example 5 using again the Exact~ 4049 to copolymer, a 3.0 wt% of a calcium alpha olefin sulfonate material (product of Stepan Co., Northfield, Illinois, USA) was introduced into the copolymer melt.
In this particular instance, the torque was not reduced. Expanding the range of the calcium-based material from 1.0 to 5.0 wt%, again showed no reduction in torque.
Compression-molded pads were produced (as in example 5). An 15 examination of the films showed that the calcium alpha olefin sulfonate was not mixed and, in fact, a large number of specks, i.e. heterogeneous regions, were observed, illustrating poor dispersion and mixing.
Example 5 is repeated using an antioxidant stabilized metallocene catalyst 2o synthesized plastomer, Exact~ 3033 (a 1.2 melt index, 0.900 g/cc density, ethylene butene hexene terpoIymer produced by Exxon Chemical Co., Houston, Texas, USA). Two concentrations (0.5 and 3.0 wt%) of the Bio Terge'~ AS-90B beads are evaluated. The lower and higher concentrations produced a torque reduction of 28 and >35%, resp~tively.
2s The compression-molded films were optically clear and homogeneous, indicating excellent dispersion and mixing.
E~c~ple 8 Example 7 is repeated substituting the sodium alpha olefin sulfonate with 3.0 wt% calcium alpha olefin sulfonate. No torque reduction is measured. The 3o compression-molded films are heterogeneous with a large number of specks randomly distributed throughout the film, illustrating poor dispersion and mixing.
Example 9 Example 5 is repeated using an antioxidant stabilized metallocene catalyst produced plastomer, Exact~ 3028 (a 1.2 melt index, 0.900 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co., Houston, Texas, USA.
5 Three concentrations (0.5, 1.0 and 3.0 wt%) of the Bio Terge~ AS-90B beads are evaluated. The data in Table 5 demonstrates that as the concentration is increased the torque is reduced.
Table 5 Sodium Alpha Olefin Sulfonate Torque Reduction (wt%) (%) 0.5 21 1.0 27 3.0 35 to Example 10 Example S is repeated using an antioxidant stabilized metaIlocene catalyst produced plastomer, Exact~ 3025 (a 1.2 melt index, 0.910 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co., Houston, Texas, USA). Two concentrations (0.5 and 3.0 wt%) of the Bio Terge AS-90B beads are evaluated.
15 The date in Table 6 demonstrates that as the concentration is increased the torque is reduced.
Table 6 Sodium Alpha Olefin Sulfonate Torque Reduction __ (wt%) (%) 0.5 25 3.0 30 Example 11 20 Example 5 is repeated using a physical mixture of antioxidant stabilized metallocene catalyst produced plastomers. In this example, the Exact~ 4049 copolymer and Exact~ 3033 terpolymer are melt mixed in a 93:8 wt ratio and subsequently, 0.5 wt% of the Bio Terge'~ AS-90B beads were added. A 12%
torque reduction is measured.
Example 5 procedure is repeated using F.xact~ 4049 and Exact~ 3033 rM
materials with a wide range of fluorocarbon-based materials (Fluorad Fluorochemical Surfactants produced by 3M, St. Paul, MN, USA). All materials s used were free of solvents) using comrentional drying procedures prior to melt mixing. The data in Table 7 describes the products used in this example as well as their chemical structures and the measured torque reductions at 193° C
at a 0.5 wt% concentration. The data demonstrates that no torque reductions are observed for both the potassium and ammonium perfluoroallcyl sulfonates. However, a Io range of torque reductions are observed which is dependent on the specific fluorocarbon structure.
Table 7 Fluorocarboq-Based Mad 3M. ProductType Description Torque Reduction-Torqnt:.
;. Nutober Euictm 4049 Reduction.-(%) - Erict~
.
"/.
'., FC-93 AnionicAmmonium 0 0 rlyuoroalkvl sulfonates FC-95 AnionicPotassium perfluoroalkyl0 0 and FC-98 sulfonates. 0 0 FC-99 AnionicAmine pertluoroallryl35 35 sulfonates FC-100 AmphoterFl~rinated alkyl6 6 is am hoteric mixture FC-I20 AnionicAmmonium 0 25 rfluoroalkvl sulfonates FC-I29 AnionicPotassium fluorinated7 7 alkyl carhoxvlates FC-135 CatiorueFluorinated alkyl17 58 quaternary ammonium iodides FC-143 AnionicAmmonium perfluoralkylI7 34 CaTbOXVlateS
FC-431 NonionicFluorinated alkyl37 30 esters FC-740 NonionicFluorinated alkyl~ 12 ~ _ esters 8 Example 5 procedure is repeated using sodium and calcium dodecylbenzene sulfonate materials. The former material is a product of the Witco Corp., Houston, Texas, USA and the latter material is a product of Stepan Co., North&eld, Illinois, USA. The data in Table 8 shows that the calcium-based material provides no reduction in the torque, while the sodium-based material provides only a relatively modest reduction (or no enhancement).
Table 8 DodecylbenzeneProduct DesignationConcentrationTorque Sulfonate (%) Reduction (%
Sodium Witconate 90 3.0 11 Sodium Witconate LX 3.0 6 Sodium Witconate SK 3.0 0 Calcium E erimental Product1.0 0 Calcium E erimental Product3.0 0 Calcium Experimental 5.0 J 0 Product ~
1o Examnles 14-18 Table 9 shows the description of samples used in these examples and summarizes the process data. Examples 14 and 17 are the comparative control samples . All materials were fabricated on a 3/4" Haake Rheocord extruder, Model E in the cast mode. The screw was a 15/5/5, 24:1 L/D with 15° tip. The polymer was extruded through a 4" tape die and wound through a stacked calendar assembly to the winder. All polymers were preblended and compounded on a 1 "
MPM single screw (24:1L/D) compounding extruder at a melt temperature of -190°C prior to film extrusion. Each example contained 25,000-30,000 ppm silica antiblock and -2000 ppm erucamide slip. All materials were cast extruded through 2o a 20 mil die gap at -190°C melt. Materials used consisted of Exact 4049 (4.5 MI;
0.873 density ethylene-butane copolymer), a metallocene plastomer produced by Exxon Chemical Co., Houston, Texas, USA; Vector 7400 D, an 8.0 MI/0.930 density SBS (31/69/ SB ratio) produced by Dexco Co., Houston, TX USA; and 3.0 wt% of a sodium alpha olefin sulfonate (Bio-Terge~ AS-90B beads produced by Stepan Co., Northfield, Illinois, USA as in example 1 ); and 3.0 wt% of calcium alpha olefin sulfonate, also produced by Stepan Co.
As can be seen, the sodium alpha olefin sulfonate drastically reduces the torque requirements when comparing samples 14 and 15 (> 2X). This same trend ~ was also evident when comparing samples 17 and 18, the Exact~ /SBS blends.
In all fow cases, the film exhibited good melt quality and homogenization. This was not the case when comparing sample 15 (calcium alpha olefin sulfonate). The film quality was very poor with numerous unmelted gels, even after raising the melt temperature from 190-240°C. It also did not compare with the sodium alpha olefin ~o sulfonate concerning torque reductions.
Table l 0 summarizes the test results for examples I4-I 8. Tensile testing was performed according to ASTM D-882 on a United Six Station tensile tester, model 7V 1. Tear results were obtained from an Elmendorf tear tester according to ASTM D-1922.
The hysteresis testing procedure used-is described as follows. This method is an Exxon variation of a procedure described by E.L, DuPont and Co. in its brochure on its polyester urethane elastic product, T-722A. In the variation used herein, 1 inch X 6 inch strips are subjected to a strain rate of 150% or 200%
with a jaw gap separation of 2" and cross head speed of ZO"/min. The hysteresis stress/-2o strain curve is plotted on a chart also traveling at 20"/minute. Both the extension and retraction cross head speeds (20"/min) were the same and performed on an Instron model 1123. The film was held for 60 seconds at maximum extension and then retracted and held for 30 seconds relaxation prior to the next cycle.
This was repeated 2 1/2 times. Key pieces of information that are extracted from these stress/strain plots are the maximum force (modulus) of each cycle, the residual set or permanent set (the degree of deformation as measured by the point of stress divided by total strain/cycle), and the unload force of contractive power as measured from the last retraction cycle at various elongations. Generally, five specimens were tested for each sample, with mean values over these samples 3o developed.
As can be seen, there are substantially no detrimental effects) to physical s properties with the addition of surfactants. In fact, there appears to be slight improvement to the elastic properties as compared to the control comparisons (example 14 and 17).
Table 9 Process Summary Exam I~ (1) ::14 .15. 16(2)I7 18 r:
Formulation Exact 4049 100 97 97 30 27 Vector 7400D 70 70 Na oc-olefin Sulfonate 03 03 Ca a-olefin Sulfonate 03 Extruder RPM ~ 32 32 32 32 32 Ext. FidPSI ~ 650 620 560 730 580 Die PSI 100 100 100 100 100 Ext. To ue -G 2600 1200 2100 2300 700 Ext. Melt C 191 193 231 191 193 Gau a mils 2.0 1.9 2.3 2.6 3.6 Line Speed (fpm) - X17- r1' r -15 12 ~
to (1) % excludes slip and AB addition via masterbatch (2) Poor extrusion, melt quality. Numerous-unmelted particles.
Table 10 1V~D Pronertv Summarv(1) >Test I4: 15 16 I7 ' I8 Formulation Exact 4049 100 97 97 30 27 Vector 70 70 Na a-olefin Sulfonate 03 03 Ca a-olefin Sulfonate 03 Tensiles Yld SI 287 287 233 165 160 Yld Elon % 11.8 11.8 11.5 6.6 6.4 Ult.Tns SI 2780 3260 2740 1900 1520 Brk Elon % 630 670 730 630 660 Tear mil 34.7 33.3 23.2 19.1 26.3 H steresis 150% ext Set 23.9 21.8 20.0 9.8 7.3 Modulus 1 560 500 460 405 510 Modulus 2 500 440 410 350 450 Unload at 50% 6 10 19 110 150 Unload at 100% (g) 140 i30 130 19~ 260 ~ ~ J
(1) MD= Machine Direction s Examples 19-26 Table 11 shows the description of samples used in these examples and summarizes the process data at both standard rates and maximum rates. Examples 19-22 are the control comparatives. Those samples describe a new grade under to development by Exxon Chemical Co., of Houston, TX, USA referred to as APT-3.
This is an advanced performance terpolymer having an MI of 2.2 and density of 0.898. Exact 4151 (2.2 MI, 0.896 density, metallocene ethylene, butene copolymer) is the precursor grade. Advanced Performance Terpolymers are characterized as having improved processability vs. their precursor counterpart in 15 the blown film process, i.e. lower motor load and torque requirements and improved bubble stability attributes. In these embodiments of the present invention, surfactant addition in the amount of 0.05, 0.1, 0.25 and 0.5 weight percents are added to APT-3 and compared to the control (APT-3) and base precursor grade (Exact 4151 ) with and without slip/antibiock addition. The slip 2o used was Kemamide E erucamide (produced by Witco, Inc., Memphis, TIC, the antiblock (AB) was ABT-2500 Talc (produced by Specialty Minerals, Los Angeles, CA) and the fluoroeiastomeric process aid (PPA) used in some of the formuiations was Viton A (produced by E.I. Dupont, Wilmington, DE). The surfactant used is a sodium alpha olefin sulfonate (Bio-Terge~ AS-90B produced by Stepan Co., Northfield, Illinois USA as in example 1). Prior to film extnision, all materials were compounded on a Werner and Pfleiderer ZSK-57 mm twin screw extruder at a melt temperature between 410-420°F (210-216° C).
The materials were then fabricated into films on a 2.5" Egan blown film line. This is a 24:1 LID
extruder powered by a 40 HP DC drive. Maximum screw RPM's is 115, thus to capable of producing a maximum torque of 0.35 HP/Rev. The barrel is liquid cooled and consists of 3 temperature zones and 5 pressure ports. The screw is a 24:1 L/D SterleX low work barrier screw having a 0.050" barrier undercut with a Maddock mixing device at the end of the screw also having a 0.050" undercut.
The die is a 6" Uniflo lower pressure bottom fed spiral mandrel die with a 60 mil die gap. The air ring is a 6" dual lip Uniflo design. Screenpack =
20/40/80/20.
Blow up Ratio (BUR) = 2.5. Temperature profile was as follows:
girl Z1 Brl Z2 B Z3 Dies/A~~ters 280° F 375° F 345° F 365° F-~
(138° C) (191° C) (174° C) (185° C) Each material was extruded at standard rates (~-7 lbs/in die/hr) and 2o maximum rates with all pertinent process data recorded on a data logger.
Each material was run until lined out as demonstrated via data logger (~1 hr/sampIe).
The maximum rate was defined as either the point of bubble instability (BS) motor load (ML) or maximum RPM's (RPM). Bubble instability criteria used was as follows:
~ bubble fluttering ~ gauged ~10%
~ edge wrinkles after adjustments to the collapsing frame.
If any of these criteria was met, the rate was backed off until a stable condition could be maintained as indicated by the data logger (steady state).
As can be seen, surfactant addition has little to no effect on process at low rates. The real effect occurs between 0.25-0.50 weight percent levels. At 0.5 weight percent level there is an ~20% reduction in motor load compared to APT-and ~30% reduction when compared to the precursor material. Effects on torque also follow this trend with an ~30 and ~40% reduction, respectively. Low level surfactant (0.05-0.1 weight %) improves rate production slightly. Between 0.25-0.5 weight %, the rate is increased substantially due to the reduced motor load and lower melt. At 0.5 weight % level, rate production was increased by >25%
compared to APT-3 w/o surfactant and >45% when compared to the precursor.
to No pumping efficiency (lbs/RPM) is lost between 0.05-0.25 weight %.
Between 0.25-0.5 weight % there is a drop off, but this is of little consequence if there is available extruder RPM.
Surfactant addition to Exxpol~ metalIocene grades and APT grades can have a substantial effect on processability especially in monolayer blown film Z5 production where motor load and torque requirements can be limiting factors.
These advantages are also seen in conventional Z-N catalyzed LLDPE production.
Table 12 summarizes physical property test results and as can be seen, no detrimental effects can be attributed to the addition of surfactant. All tests were performed according to the appropriate ASTM standard method.
2o Table 13 illustrates no adverse surface sealing effects can be attributed to the addition of surfactant. Hot tack comparisons of Exact 4151, APT-3 w/o surfactant and APT-3 w/surfactant are virtually identical as demonstrated.
In addition, organoleptic testing by a certified odor and taste facility show no adverse effects for food packaging applications.
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Claims (12)
1. A method for processing a linear polyethylene into an article comprising:
a) selecting a linear polyethylene from the group consisting of LLDPE (linear low density polyethylene), mLLDPE (metallocene LLDPE), HDPE (high density polyethylene), plastomers, MDPE (medium density polyethylene), UHMW-HDPE (ultra high molecular weight HDPE) and combinations thereof;
b) adding an elastomer from the group consisting of SIS (styrene isoprene styrene), SBS (styrene butadiene styrene), SEBS (styrene ethylene butadiene styrene), SEPS (styrene ethylene propylene styrene), and combinations thereof to the linear polyethylene of a);
c) selecting a surfactant, said surfactant is a aliphatic sulfonate salt, wherein the cation of said salt is selected from the group consisting of Na, K, and Li;
wherein said aliphatic group is a C6-C30 alkyl group, wherein said surfactant alkyl group is selected from the group consisting of branched or straight chain alkenyl, branched or straight chain hydroxyl substituted alkyl, and combinations thereof; wherein said surfactant is present in said polyethylene and elastomers up to 1.0 wt. % based on the total weight of said polyethylene, elastomer and surfactant;
d) placing an amount of said surfactant into said polyethylene and elastomer sufficient to reduce melt fracture; and e) melt processing said polyethylene, elastomer and said surfactant to form an article.
a) selecting a linear polyethylene from the group consisting of LLDPE (linear low density polyethylene), mLLDPE (metallocene LLDPE), HDPE (high density polyethylene), plastomers, MDPE (medium density polyethylene), UHMW-HDPE (ultra high molecular weight HDPE) and combinations thereof;
b) adding an elastomer from the group consisting of SIS (styrene isoprene styrene), SBS (styrene butadiene styrene), SEBS (styrene ethylene butadiene styrene), SEPS (styrene ethylene propylene styrene), and combinations thereof to the linear polyethylene of a);
c) selecting a surfactant, said surfactant is a aliphatic sulfonate salt, wherein the cation of said salt is selected from the group consisting of Na, K, and Li;
wherein said aliphatic group is a C6-C30 alkyl group, wherein said surfactant alkyl group is selected from the group consisting of branched or straight chain alkenyl, branched or straight chain hydroxyl substituted alkyl, and combinations thereof; wherein said surfactant is present in said polyethylene and elastomers up to 1.0 wt. % based on the total weight of said polyethylene, elastomer and surfactant;
d) placing an amount of said surfactant into said polyethylene and elastomer sufficient to reduce melt fracture; and e) melt processing said polyethylene, elastomer and said surfactant to form an article.
2. The method of claim 1 wherein said linear polyethylene has a M w/M n less than 3.
3. The method of claim 1 wherein said linear polyethylene is selected from the group consisting of copolymers of ethylene and at least one a-olefin selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and combinations thereof, wherein said linear polyethylene has a density in the range of from 0.86 - 0.94 g/cc.
4. The method of claim 1 or 2 wherein said surfactant is present up to 0.5 wt.
%, based on the total weight of said polyethylene, elastomer and said surfactant, wherein said elastomer is present in said polyethylene/elastomer at from 45-65 weight percent based on the total weight of said polyethylene-elastomer, wherein said article is a blown film, and wherein said linear polyethylene has a density from 0.88 - 0.930 g/cc.
%, based on the total weight of said polyethylene, elastomer and said surfactant, wherein said elastomer is present in said polyethylene/elastomer at from 45-65 weight percent based on the total weight of said polyethylene-elastomer, wherein said article is a blown film, and wherein said linear polyethylene has a density from 0.88 - 0.930 g/cc.
5. The method of any one of claims 1 to 4 wherein said linear polyethylene further comprises a polymer selected from the group consisting of LDPE (low density polyethylene), EVA (ethylene vinyl acetate), EEA (ethylene ethyl acrylate), EnBA
(ethylene n-butyl acrylate), EMAA (ethylene methacrylic acid), EMA (ethylene methyl acrylate), EAA (ethylene acrylic acid), ionomers of the acids, and combinations thereof.
(ethylene n-butyl acrylate), EMAA (ethylene methacrylic acid), EMA (ethylene methyl acrylate), EAA (ethylene acrylic acid), ionomers of the acids, and combinations thereof.
6. The method of any one of claims 1, 2, 3 or 5 wherein said article is a blown film substantially free of melt fracture, wherein said surfactant is an aliphatic sodium sulfonate, wherein said aliphatic group is a C6 C30 alkyl group, wherein said alkyl group is selected from the group consisting of branched or straight chain alkenyl, branched or straight chain hydroxyl substituted alkyl, and combinations thereof, and wherein said surfactant is present in said blown film up to about 0.5 weight percent based on the total weight of said polyethylene, elastomer, and surfactant.
7. The method of claims 4 or 6 wherein said surfactant is a sodium .alpha.-olefin sulfonate, wherein said .alpha.-olefin has 12 to 18 carbon atoms, and said surfactant is present in said blown film up to 0.35 weight percent, based on the total weight of said polyethylene, elastomer, and surfactant.
8. The method of claim 1 wherein said surfactant is represented by the general formula:
[R1SO3]M1 where M1 is selected from the group consisting of:
Li, Na, and K, R1 is selected from the group consisting of:
branched or straight chain mono or di unsaturated alkenyl, branched or straight chain hydroxyl substituted alkyl, and combinations thereof;
and wherein the carbon number of said R1 ranges from 6 to 30;
wherein said surfactant is present in said combination in a range of 0.005 -1.0 weight percent, based on the total weight of the combination.
[R1SO3]M1 where M1 is selected from the group consisting of:
Li, Na, and K, R1 is selected from the group consisting of:
branched or straight chain mono or di unsaturated alkenyl, branched or straight chain hydroxyl substituted alkyl, and combinations thereof;
and wherein the carbon number of said R1 ranges from 6 to 30;
wherein said surfactant is present in said combination in a range of 0.005 -1.0 weight percent, based on the total weight of the combination.
9. The method of claim 8 wherein M1 is sodium.
10. The method of claim 8 wherein said surfactant has at least two different moieties.
11. A method for processing a linear polyethylene into an article comprising:
a) selecting a linear polyethylene from the group consisting of LLDPE (linear low density polyethylene), mLLDPE (metallocene LLDPE), HDPE (high density polyethylene), plastomers, MDPE (medium density polyethylene), UHMW-HDPE (ultra high molecular weight HDPE) and combinations thereof;
b) adding an elastomer from the group consisting of SIS (styrene isoprene styrene), SBS (styrene butadiene styrene), SEBS (styrene ethylene butadiene styrene), SEPS (styrene ethylene propylene styrene), and combinations thereof to the linear polyethylene of a);
c) selecting a surfactant, said surfactant is a aliphatic sulfonate salt, wherein the canon of said salt is selected from the group consisting of Na, K, and Li, said surfactant being substantially free of halogens; wherein said aliphatic group is a C6-C30 alkyl group, wherein said surfactant alkyl group is selected from the group consisting of branched or straight chain alkenyl, branched or straight chain hydroxyl substituted alkyl, and combinations thereof; wherein said surfactant is present in said polyethylene and elastomers up to 1.0 wt.
% based on the total weight of said polyethylene, elastomer and surfactant;
d) placing an amount of said surfactant into said polyethylene and elastomer sufficient to reduce melt fracture; and e) melt processing said polyethylene, elastomer and said surfactant to form an article.
a) selecting a linear polyethylene from the group consisting of LLDPE (linear low density polyethylene), mLLDPE (metallocene LLDPE), HDPE (high density polyethylene), plastomers, MDPE (medium density polyethylene), UHMW-HDPE (ultra high molecular weight HDPE) and combinations thereof;
b) adding an elastomer from the group consisting of SIS (styrene isoprene styrene), SBS (styrene butadiene styrene), SEBS (styrene ethylene butadiene styrene), SEPS (styrene ethylene propylene styrene), and combinations thereof to the linear polyethylene of a);
c) selecting a surfactant, said surfactant is a aliphatic sulfonate salt, wherein the canon of said salt is selected from the group consisting of Na, K, and Li, said surfactant being substantially free of halogens; wherein said aliphatic group is a C6-C30 alkyl group, wherein said surfactant alkyl group is selected from the group consisting of branched or straight chain alkenyl, branched or straight chain hydroxyl substituted alkyl, and combinations thereof; wherein said surfactant is present in said polyethylene and elastomers up to 1.0 wt.
% based on the total weight of said polyethylene, elastomer and surfactant;
d) placing an amount of said surfactant into said polyethylene and elastomer sufficient to reduce melt fracture; and e) melt processing said polyethylene, elastomer and said surfactant to form an article.
12. The method of claim 11 wherein the linear polyethylene has a M w/M n less than 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2243296P | 1996-08-06 | 1996-08-06 | |
| US60/022,432 | 1996-08-06 | ||
| PCT/US1997/013856 WO1998005711A1 (en) | 1996-08-06 | 1997-08-06 | Method of processing polyethylene and polyethylene/elastomer blends |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2259529A1 CA2259529A1 (en) | 1998-02-12 |
| CA2259529C true CA2259529C (en) | 2006-02-14 |
Family
ID=35892355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002259529A Expired - Fee Related CA2259529C (en) | 1996-08-06 | 1997-08-06 | Method of processing polyethylene and polyethylene/elastomer blends |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2259529C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115093637B (en) * | 2022-04-08 | 2023-06-23 | 中国石油化工股份有限公司 | Resin for polyethylene bottle cap and preparation method and application thereof |
| CN115926287B (en) * | 2022-12-01 | 2023-06-16 | 江苏极易新材料有限公司 | Granulating method of compound agent with melt finger control for polyolefin |
-
1997
- 1997-08-06 CA CA002259529A patent/CA2259529C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2259529A1 (en) | 1998-02-12 |
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