CA2027003A1 - Processing aid for polymers - Google Patents

Processing aid for polymers

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Publication number
CA2027003A1
CA2027003A1 CA002027003A CA2027003A CA2027003A1 CA 2027003 A1 CA2027003 A1 CA 2027003A1 CA 002027003 A CA002027003 A CA 002027003A CA 2027003 A CA2027003 A CA 2027003A CA 2027003 A1 CA2027003 A1 CA 2027003A1
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CA
Canada
Prior art keywords
composition
copolymer
component
polymer
tetrafluoroethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002027003A
Other languages
French (fr)
Inventor
George R. Chapman, Jr.
Donnan E. Priester
Charles W. Stewart
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EIDP Inc
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Individual
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Filing date
Publication date
Priority claimed from US07/572,921 external-priority patent/US5013792A/en
Application filed by Individual filed Critical Individual
Publication of CA2027003A1 publication Critical patent/CA2027003A1/en
Abandoned legal-status Critical Current

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Abstract

TITLE
Processing Aid For Polymers ABSTRACT OF THE DISCLOSURE
Polymer blend composition having improved processibility and comprising:
(a) a major portion of a difficultly melt-processible polymer, and (b) a minor portion of:
(1) at least an effective amount, to improve processibility, of a fluorocarbon copolymer which at the melt-processing temperature of (a) is either in a melted form if crystalline, or is above its glass transition temperature if amorphous, and (2) at least an effective amount, to improve processibility, of at least one tetrafluoroethylene homopolymer or copolymer of tetrafluoroethylene and at least one monomer copolymerizable therewith, wherein the mole ratio of fluorine to hydrogen is at least 1:1, and which is solid at the melt-processing temperature of (a);
masterbatches comprised of the processing aid: and processes utilizing the processing aid.

Description

-- 2~2~03 TITLE
Processina Aid For Polvmers BACKGROUND OF ~ ;[NVENTION
Field of the Invention The present invention relates to a processing ~ aid for polymers, and to polymers having improvedf processibility, particularly improved extrusion characteristics.
~ack~round The melt extrusion of high molecular weight polymers, for example, hydrocarbon polymers, into shaped structures such as tubing, pipe, wire coating or film is accomplished by well-known procedures wherein a rotating screw pushes a heated, molten and viscous polymer melt through the extruder barrel into a die in which the polymer is shaped to the desired form and is then subsequently cooled and resolidified, by various means~ into the general shape of the die.
In order to achieve low production costs it is desirable to extrude at high rates. Although the extrusion rate is readily increased by increasing the rate of revolution of the extruder screw, there is a technical limit to these increases because of the viscoelastic properties of the polymer. At rates above this limit the polymer may be mechanically heated to t0mperatures at which thermal decomposition can occur, or extrudates with a rough surface are obtained. The latter phenomenon can qenerate an undesirable pattern on the surface of the extrudate.
One way of a~oiding this occurrence is to extrude at a higher temperature, but this adds to the processing costs and makes cooling of the extrudate more difficult. More seriously, many polymer resins are A~-5685-B 35 already extruded at temperatures near their ` -`` 2027~03 dec^mpos:tion temperatures, and further increases are not feasible.
Additional examples of poor extrusion behavior include formation of deposits of the extruding polymer resin, degraded polymer resin or resin additives around the die exit (orifice); ~urging in polymer flow and erratic pressure fluctuations that occur due to unevèn pumping of the polymer melt, which may result in erratic fluctuations of output rate; and torquing out of the extruder, that is, overloading the pressure limit of the extruder, resulting in automatic shutdown of the extruder.
It is desirable, therefore, to find highly efficient means of increasing the extrusion rate, without raising the melt temperature, while producing products with smooth surfaces. Changes in extruder and die configuration can improve melt flow but are not always practical or economically feasible.
Another approach involves the addition of conventional wax-type process aids which reduce bulk viscosity and in some cases improve processing properties. However, the efficiency is marginal and the high levels of additive required often adversely affect other properties. In Blatz, U.S. 3,125,547, it is disclosed that the use of 0.01-2.0 wt. % of a fluorocarbon polymer that is in a fluid state at process temperature, such as a fluoroelastomer, will reduce die pressure and significantly increase the extrusion rate at which melt fracture occurs for high and low density polyethylenes and other polyolefins. It is further taught in U.S. 3,125,547 that fluororesins which are solids at process temperature afford little or no improvements in extrusion characteristics of hydrocarbon polymers. By the term solid, it is meant that the fluororesin, if crystalline in nature, is not .. . . . .. . . . .. . ..
2~7~9 ) melted, or, if amorphous in nature, i8 not above the glass transition temperature.
Xamiya and Inui, in Japanese Patent Application Publication Kokoku 45-30574 (1970, examined) cite the use of crystalline fluorocarbon polymers at temperatures below their melting points to eliminate die build-up but say nothing of other extrusion improvements. Nishida, Tate and Kitani, in Japanese Patent Application Publication Kokai 62-64847, disclose injection molding compositions comprising an ethylene/alpha olefin copolymer having an MFR of 0.2-200 g/10 min., a density of 0.850-0.945 g/cm3, and a Q value of 2.5-12, and 0.001-1% by weight of a fluorinated hydrocarbon polymer having an F/C ratio of at least 1:2.
Chu, in U.S. 4,740,341, discloses blends having improved extrudahility and comprising a linear polymer of ethylene having incorporated therein 0.01-0.5 wt. %, based on the composition, of a fluorocarbon polymer having an F/C ratio of at least 1:2 and which is fluid at 120-300C, and 0.01-0.5 wt. %, based on the composition, of a polysiloxane.
Larsen, in U.S. 3,334,157, discloses polyethylene which has been modified to improve its optical properties by incorporating therein 0.015 to greater than 1.7 % by wt., based on the mixture, of finely divided polytetrafluoroethylene.
It is an object of this invention to provide resin compositions with substantially improved ; extrusion characteristics. It is another object to provide polymers which can be extruded at high rates to give extrudates of high surface quality. It is yet another object to provide polymers that can be extruded at low die pressures and at low melt temperatures. Another object is to provide a 20~7~

processing aid by means of which all the above can be achieved. A further object is to provide masterbat~hes of the processing aid. Other objects will become apparent hereinafter.
SUMMARY OF T~E I~VEN~ION
The present invention provides a processing aid composition for difficultly melt-processible polymers. The processing aid consists essentially of, with the parts totaling 100:
(a) 2-95 parts by weight of a fluorocarbon copolymer which at the melt-processing temperature of the difficultly melt-processible polymer is either in a melted form if crystalline or is above its glass transition temperature if amorphous; and I (b) 98-5 parts by weight of a I tetrafluoroethylene homopolymer or ¦ copolymer of tetrafluoroethylene and a monomer which is copolymerizable therewith, wherein the mole ratio of fluorine to hydrogen is at least 1:1, and which is solid at the melt-processing temperature of the difficultly melt-processible polymer.
The processing aid composition consists essentially of ; a minor portion of the processing aid and a major portion of a polymer, either a melt-processible or difficultly melt-processible polymer, or both, for ~ example, a hydrocarbon polymer.
j The present invention also provides apolymer blend composition having improved processibility and which comprises:

-"" 2~2'~c~

~a~ a major portion of a difficultly melt-processible polymer, the host polymer, znd (b) a minor portion of:
(1) at least an effective amount to improve processibility, preferably to about 0.5 wt. %, based on the weight of (a), more preferably 0.002 - 0.20 wt. ~, of a fluorocarbon copolymer wherein, preferably, the mole ratio of fluorine to hydrogen is at least 1:1.5, which at the melt-processing temperature of (a) is either in a melted form if crystalline, or is above its glass transition temperature if amorphous, and (2) at least an effective amount to improve processibility, preferably 0.002 - 0.20 wt. %, based on the weight of (a), of at least one tetrafluoroethylene homopolymer or copolymer of tetrafluoroethylene and at least one monomer copolymerizable therewith, wherein the mole ratio of fluorine to hydrogen is at least 1:1, and which is solid at the melt-processing temperature of (a)-For example, when the host polymer (a) is a hydrocarbon polymer, its melt-processing temperature generally will be in the range 100-250C.

2 ~ 3 Finally, the invention provides masterbatches containing the aforesaid processing aid;
it provides processes for facilitating the processing of difficultly melt-processible polymers: and it provides difficultly melt-processible polymers containing the processing aid.
Brief Description of_~he Drawina The figures which are a part of this specification are plots of die pressure (MPa) vs throughput (g/minute), showing the superior results achieved by means of this invention, as compared to those achieved by means of the prior art. Figure 1 is representative of the invention as applied to a difficultly-melt-processible polyethylene, as described in Example 1 and Comparative Examples 1, 2 and 3. Figure 2 is similarly representative for polystyrene, as described in Example 14. ~igure 3 is similarly representative for an ethylene/vinyl acetate copolymer, as described in Example 15. Figure 4 is 2 similarly representative for polyester, as described in Examp~e 16.
Detailed Description of the Invention In accordance with the present invention it has been discovered, surprisingly, that for the improvement of extrusion behavior, difficultly : melt-processible polymers which contain combinations of fluorocarbon polymers (hereinafter called type (1) fluorocarbon polymers) that are above their melting points if crystalline, or above their glass transition temperatures if amorphous, and are thus molten and ~ fluid at the polymer-processing temperatures, and crystalline or amorphous fluorocarbon polymers (herinafter called type t2) fluorocarbon polymers) that are solid at the polymer melt-processing temperatures, have significant advantage over such 20~7~3 difficultly melt-processible polymers which contain equivalent, or even greater, amount6 of extrusion-~odifying additives of the art, as in U.S.
3,125,547 (supra).
The term ~extrusion behavior~ is intended to include euch parameters as the operating melt temperatures, die pressure reached during extrusion, maintenance of a steady die pressure during extrusion, maximum extrusion rates that can be achieved, maintenance of a steady extrusion rate, dimensional stability of the melt, absence of deposits of decomposed polymer or additives at the exit of the die surface and good ~urface quality of the extruded part.
In some cases the invention may provide a means for carrying out the extrusion at a lower temperature.
Blow molding, tubing manufacture and fiber spinning represent examples of extrusion processes that may be improved by means of this invention. Thus, the compositions of this invention, compared to polymers not containing both types (1) and ~2) fluorocarbon polymers will show improved extrusion behavior, incorporating improvements in at least some of the parameters noted above.
With respect to the fluorocarbon polymer process aid of this invention, it has ~een independently discovered that there must be present an effective amount of polar functional groups selected from -COF, S02F, -S02Cl, -S03M, -OS03M, -COOR, and -COOM, wherein R i~ a Cl_3 alkyl group and M is hydrogen, a metal cation, preferably an alkali or alkaline earth metal cation, or a guaternary ammonium cation. Such functionality is usually present in the process aid: (1) as polymer chain end groups introduced during the polymerization or copolymerization, (2) by copolymerization of a 2 ~
B

fun~tional-group-containing ~onomer, or (3~ by subjecting the fluorocarbon polymer to ionizing radiation.
The fluorocarbon polymers of type (l) are those that are fluid at the melt-processing temperature of the difficultly melt-processible polymer. Thus, at processing temperature they must be above their melting points if crystalline, or above their glass transition temperatures if amorphous, preferably no more than 300-C, more preferably no more than 200-C. The poly~ers should have sufficiently high molecular weight, with number average molecular weights greater than about 10,000, such that they do not exude from the difficultly melt-processible polymer extrudate at melt-processing temperatures.
With respect to their chemical composition, it is preferred, but not essential, to employ fluorocarbon polymers having a fluorine to hydrogen ratio of at least 1:1.5. Fluorinated monomers which give rise to suitable polymers include vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene and perfluoroalkyl perfluorovinyl ethers. Specific examples of the fluorocarbon polymers of type (l) that may be employed in this invention include copolymers of vinylidene fluoride and a monomer selected from hexafluoropropylene, chlorotrifluoroethylene, l-hydropentafluoropropylene and 2-hydropentafluoropropylene; copolymers of vinylidene fluoride, tetrafluoroethylene ar~d hexafluoropropylene or 1- or 2-hydropentafluoropropylene; copolymers of tetrafluoroethylene and propylene and, optionally, vinylidene fluoride; copolymers of tetrafluoroethylene and a perfluoro(alkyl vinyl ether), preferably perfluoro(methyl vinyl ether), optionally containing a .. . . . . . .

2~27~0~

small amount (up to 2 mole %) of a third monomer; and copolymers of tetrafluoroethylene and h~xafluoropropylene, all of which are known in the art. The presence or absence of the third monomer iB
of no known consequence in this invention. In some cases these copolymers may also include a bromG-containing cure site monomer as taught in Apotheker and Krusic, U.S. 4,035,565, or terminal iodo-groups, as taught in U.S. 4,243,770. The latter patent also discloses the use of iodo group-contaîning fluoroolefin comonomers. When certain molar ratios of monomers are used in these copolymers, then the glass transition temperature is near or below O-C; many of these polymers are useful elastomers that are readily available articles of commerce.
The fluorocarbon polymers of type (2) that are solid at the melt processing temperature of the difficultly melt-processible polymer include homopolymers of tetrafluoroethylene and copolymers of tetrafluoroethylene with certain copolymerizable monomers. The selection of the fluorocarbon polymer of type ~2) is not limited to high molecular weight polymers, whether the polymer is melt-processible or not melt-processible, whether the polymer is made by dispersion polymerization or suspension polymerization, or how much comonomer is present, except as stated above. For example, if excessive amounts of comonomer are used, the polymer will not be a solid at the temperature used for melt processing the difficultly melt-processible polymer; or, if a copolymer has too low a molecular weight, the copolymer may not be a solid at the temperature used for melt processing the difficultly melt-processible polymer. Suitable tetrafluoroethylene homopolymers include those that are high molecular weight and 2 0 2 r~

fibrillate, or do not fibrillate to a substantial extent, under shearing conditions, as well as those which are low molecular weight and non-fibrillating, such as those which have been subjected to ionizing radiation. Suitable monomers copolymerizable with tetrafluoroethylene to give melt-processible copolymers are ethylene, perfluoroolefins such as hexafluoropropylene, and perfluoro(alkyl vinyl ethers) such as perfluoro(propyl vinyl ether) and perfluoro(alkyl vinyl ethers) which contain functional groups such as -S02F or -COOCH3. More than one comonomer may be used, provided all the aforesaid requirements are met.
In certain instances, when the difficultly-melt-processible polymer is processed at a high temperature, for example, a polyester or polyamide, some type (2) fluorocarbon polymers, for example, tetrafluoroethylene/hexafluoropropylene copolymers, may also serve as a type (1) fluorocarbon polymer.
The effect of the combined addition of fluorocarbon polymers types (1) and (2) in eliminating roughness of the extrudate, allowing increases in extrusion speed and reducing die pressures is significantly greater than when either type (1) or type (2~ is used alone at concentrations equal to the sum of the concentrations of (1) and (2~. In some cases it has been shown also that combining types (1) and (2), at total concentrations egual to or greater than that of the combined concentrations of additives, also produces unexpected improvements in certain extrusion parameters, for example, reduction or elimination of die pressure fluctuations, reduction of deposits at the die exit, reduction in the pressure required to operate the screw of tha extruder, 2 ~

resulting in an increase in the time an extrusion can be carried out or in an increase in the throughput of polym~r. It has been found in some instances that even when (l) and (2) are added at total i 5 concentrations as low as 0.0025 wt. %, all extrudate roughness is eliminated at extrusion shear rates well beyond 1000 sec-l (Example 2). Quantities in excess i of 1 wt. ~ are not necessary. In general, if the fluorocarbon polymers are not compatible with the difficultly melt-processible polymer, that is to say, are not soluble in ~uch polymer, the addition of higher levels serves no useful purpose, and when the incompatible fraction ~ecomes too large, it may adversely affect the optical properties of the extrudate. Such is the case, for example, when the difficultly melt-processible polymer i8 a hydrocarbon polymer. The beneficial effects of even very low ratios of types (1) to (2) or types (2) to (l) are readily evident but, in general, there will be an optimum ratio of types (1) to (2) which may be determined experimentally for any particular combination of types (1) and (2). The weight ratio of fluorocarbon polymer type (1) to fluorocarbon polymer type (2) may ~ary from 2/98 to 95/5, preferably from 10/90 to 90/10.
Difficultly-melt-processible polymers are defined as those that either require uneconomically high extrusio~ pressures or temperatures for extrusion or extrude with unacceptable melt fracture, such that the surfaces of the extrudate are blemished under ~ conditions that would be otherwise technically ; feasible or economically attractive; those that give excessive deposits of resin, decomposed resin or additives at the die exit (orifice); those that extrude under conditions such that large fluctuations . - 2~27~3 in barrel or die pressure are experienced, sometimes to the extent that the pressure limit of the extruder is reached, resulting in automatic shutdown of the extruder.
! 5 Examples of difficultly-melt-processible polymers that may be operable in connection with the compositions and processes of the invention include i the following: mono-olefin polymers, such as ethylene homopolymers and copolymers; vinyl aromatic polymers, such as polystyrene; copolymers of alpha-olefins, particularly ethylene, with vinyl ester6, such as vinyl acetate and vinyl propionate, with (meth)acrylic esters, such a6 ethyl or methyl acrylate, with acrylonitrile, and with (meth)acrylic acids and their (ionomeric) metal salt6 and the like; chlorinated polyethylene; polyvinyl chloride; polyester; and polyamide. The difficultly-melt-processible polymer I may also be a polymer blend or polymer alloy.
¦ It will be recognized by those skilled in 2 the art that for those resins that e~trude at high temperatures and, in addition, are chemically sensitive, for example, polyester or polyamide, it is important to select fluorocarbon process aids that are thermally stable at the process temperatures.
Generally speaking, such polymers are those that are very nearly perfluorinated, such as copolymers of tetrafluoroethylene and other perfluoroolefins.
Copolymers of vinylidene fluoride and hexafluoropropylene may dehydrohalogenate at j temperatures in excess of about 250-C and are of j lesser utility under these conditions.
When the difficultly melt-processible polymer is a hydrocarbon polymer that is used, for example, in blown film extrusion, it will generally havë a melt index (ASTM D-1238) at l90-C of 5 or less, - 2~2 ,'~ 3 preferably 3 or less. For a high shear operation, such as fiber extrusion or injection molding, even hiyher melt index resins, for example, having a melt index of 20 or more, may suffer extrusion difficulties.
In the case of a hydrocarbon polymer component of the composition of this invention, it may i comprise an elastomeric copoly~er of ethylene and - propylene and, optionally, a non-con~ugated diene monomer, for example, 1,4-hexadiene, or, in general, any thermoplastic hydrocarbon polymer obtained by the homopolymerization or copolymerization of a monoolefin(s) of the formula CH2=CHR, where R is H or an alkyl radical, usually of not more than eight carbon atoms. In particular, this invention is applicable to polyethylene, both of the high density type and the low density type, for example, densities within the range 0.89 to 0.97; polypropylene;
polybutene-1; poly(3-methylbutene);
poly(methylpentene3; and linear low density copolymers of ethylene and an alpha-olefin such as propylene, butene-1, octene-l, hexene-1, decene-1, octadecene, or
4-methylpentene-1. Similarly, the invention is also applicable to blends of difficultly melt-processible 25 polymers, and difficultly melt-processible polymers containing additives, such as antioxidants, light stabilizers, antiblocking agents, pigments, etc.
Difficultly-melt-processible polyesters are . condensation polymers derived from dicarboxylic acids and dialcohols and/or from hydrocarboxylic acids or ~ the corresponding lactones, such as polyethylene - terephthalate, polybutylene terephthalate and poly-1,4-dimethylolcyclohexane terephthalate.
Difficultly-melt-processible polyamides and copolyamides are derived from diamines and " 2027~

dicarboxylic acids and/or amino acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11 and polyamide 12.
Because of the different melt characteristics of the various difficultly-melt-processible polymers disclosed hereinabove, the addition of the types ~1) and (2) fluorocarbon polymers may be of greater value in ome polymers than in other6. Thust for example, hydrocarbon polymers, ~uch as polypropylene and branched polyethylene, that are not of high molecular weight have good melt flow characteristics even at low temperatures, so that surface roughness and other surface defects can be avoided by adjustment of extrusion conditions. Such hydrocarbon polymers may not reguire the use of the fluorocarbon polymer additives of this invention, or be noticeably improved I by them, except under unusual, adverse extrusion ¦ conditions. Such polymers, therefore, are considered 1 20 herein as not difficultly melt-processible polymers.
However, othPr polymers, such as high molecular weight, high density polyethylene or linear low density ethylene copolymers, particularly those with narrow molecular weight distributions, do not have this degree of freedom in the variation of extrusion conditions and it is particularly with these resins that remarkable improvements in the surface quality of the extruded product are obtained with compositions containing the described type (1) and type (2) fluorocarbon polymars.
It will also be recognized by one skilled in the art that it may not be possible to achieve, simultaneously, reduced die pressure, increased throughput, improved surface quality or reduced pressure fluctuations to the maximum extent at~given 2~2'7~0~

concentration of types (1) and (2). Thus, one might elect to attain maximum improvement in one parameter, in particular, at the expense of corresponding improvements in other parameters. For example, increased output of extrudate with high quality surface characteristics may not necessarily be accompanied by reduced die pressure. Moreover, certain difficultly-melt-processible polymers may show no melt fracture, but may require extremely high extrusion pressure in the absence of the processing aid of the invention. The best set of conditions will ; be determined by the ~pecific requirements of the extrusion.
The addition of the fluorocarbon polymer modifiers to the difficultly melt-processible polymer can be accomplished by any of the means heretofore developed for the addition of modifiers to such polymers. For example, the fluorocarbon polymers (1) ¦ and (2) may be added independently to, for example, a hydrocarbon polymer on a rubber compounding mill or in a Banbury or other internal mixer or in a mixing - extruder, in all of which the fluorocarbon polymers are uniformly distributed throughout the host polymer.
It is also feasible to dry-blend the two fluoropolymers with the host polymer in the solid state, and then effect uniform distribution of the fluoropolymers in the melt extruder employed in the fabrication by using an extruder screw with good mixing capability.
Alternatively, masterbatch dispersions ~ (mixtures) of types (1) and (2) in a diluent polymer, _ either together or separately, can be metered to the feed section of the extruder by appropriate devices.
The diluent polymer can be a difficultly melt-processible polymer, or it can be a compatible 2 0 2, ~ O ~

melt-processible polymer that does not substantially deleteriously affect the interaction of the aforesaid components (a), (b)(l) and (b)(2) in achieving the beneficial effects of the invention. For example, the diluent polymer can be a melt-processible hydrocarbon ; polymer, such as a homopolymer or copolymer of a monoolefin(s) of the formula RCHzCH2 wherein R is H or an alkyl radical, usually of not more than eight carbon atoms. In most cases such a hydrocarbon polymer will have a melt index (ASTM D-1238) at l90-C
of 20.0 or less, preferably 5.0 or less. In preparing such masterbatches the amounts of fluorocarbon polymers types (1) and (2) will usually be such that they provide 1-25 wt. %, preferably 1-10 wt. %, most preferably 1-5 wt. %, of the masterbatch. Further to the above regarding the need to avoid adversely affecting the beneficial effects of the invention, in . preparing the masterbatch, the concentrations of types (1) and (2), as well as the diluent polymer, will be selected so as to achieve good mixing of all the ingredients. Particularly, fibrillation of the fluorocarbon polymer type (2) is to be avoided. In any of the above procedures, it is also possible to employ previously prepared mixtures of fluorocarbon polymer type (1) with fluorocarbon polymer t~pe (2).
j In the practice of this invention, it will be found that the beneficial effects are not necessarily obserYed immediately on the onset of extrusion, and depending on the overall concentrations 7 30 of modifier, it may take from 10 minutes to 8 hours to reach stable extrusion rate and die pressure. Longer times are required at low concentrations of types (1) and (2). When it is desirable to operate at very low levels of modifiers and hasten the achievement of equilibrium, it may be expedient to first ncondition"

2~27~a3 the e~truder rapidly using a composition containing 0.1 to 1 wt. % of the fluorocarbon polymers types (1) and (2), and then to switch to the desired concentrations of types (1) and (2).
Just as it has been observed that the beneficial effects may not be observed immediately, it has also been observed that the beneficial effects may ! continue to be observed after addition of the fluorocarbon polymers of types (1) and (2) is discontinued. Consistent with this observation, after stable extrusion rate and die pressure are achieved, the beneficial effects of the invention may be realized by alternating a feed of difficultly melt-processible polymer and one containing the processing aid of the invention.
Except where noted, the evaluations reported below employ a C. W. Brabender Computerized Plasti-Corder equipped with a 19.1 mm (3/4 in.) diameter extruder with a 25/1 length/diameter ratio.
The screw has ten feed flights, 10 compression flights with a compression ratio of 3:1, and 5 metering flights. Operating parameters are controlled by five independent heating zones (No. 5 closest to the die), four pressure transducers and a torque-measuring drive unit with 1-120 rpm capability. The instrument is equipped with software for rheometric capillary extrusion testing. ~he capillary die, made from #416 nitrided stainless steel, has a diameter of 2 mm and a length of 4G mm, unless otherwise noted. In I operation, the required machine conditions are set and the polymer is then extruded, usually at 40 rpm, until equilibrium (constant throughput and constant die pressure) is reached. For a linear low density polyethylene with a melt index at 190-C of 1, extrusion at 40 rpm at 204-C gives a throughput of .

2~7~

about 19-20 g/min. snd a die pressure of 28 MPa (Comparative Example 1). For experiments that are run in sequence, by changing the feed composition, the initial output parameters correspond to the previous ! 5 equilibrium, and then gradually change to ~ new ! eguilibrium. When equilibrium is achieved a range of screw speeds i8 then run to produce new equilibrium values of throughput and die pressure. The relation between throughput and die pressure is determined from a plot of the data, and die pressure data at certain fixed production rates can be estimated for comparison of data between experiments. Surface quality of the extrudate is judged by visual examination.
After each run the extruder is thoroughly cleaned. The equipment is first purged with a highly filled abrasive composition, for example, the j commercially available UCC-DFD-0964. The capillary die is removed and heated with a propane torch until it is free of polymer and has reached a red glow. The extruder is disassembled and each section - screw, barrel, die assembly, and transducers - is cleaned, first with a wire brush, and then with methyl ethyl ketone solvent. After reassembly and calibration of the transducers, the unmodified hydrocarbon polymer is run first to establish equilibrium conditions, and to assure that reliable output is being obtained. For this purpose, the equilibrium value at 40 rpm, only, was sometimes used. If previously established eguilibrium values for unmodified polymer are not ~ achieved, the cleanout procedure is repeated.
j In Table 1 the various materials used in the ! examples which follow are identified.

2~7~

~XAMP~S
ComRarative Example ~
Hydrocarbon Polymer A was introduaed to the extruder with the screw operating at 40 rpm and heating zones Nos. 1, 2, 3, 4 and 5 controlling at ' nominal temperature settings of 150, 180, 200, 204, - and 204-C, respectively (No. 5 is closest ta the die).
Eguilibrium extrusion conditions, when throughput and die pressure were constant, were reached after a period of 15 min. The screw rpm was then systematically varied from 12 rpm to 60 rpm. After determining the extrusion rate at various screw speeds, the data were input to a computer program which generated a curve of die pressure vs. throughput (shown in Curve 1 of Figure 1 which is a part of this specification). Selected values taken fro~ Curve 1 are shown in Table 2. The extrudates of Hydrocarbon Polymer A had surface roughness at all extrusion rates above about 4 g/min.
Comparative Example 2 Hydrocarbon Polymer A which, as a dry blend, had intimately dispersed therein 0.1% of Fluorocarbon Polymer 2A, was added to the extruder just at the end of Comparative Example 1, at the same nominal temperature settings and at a screw speed of 40 rpm.
Steady state was achieved after 10 min. and did not change after a further 240 min. The die pressure/throughput relationship was then obtained as in Comparative Example 1 and is shown in Curve 2 of j Figure 1. Data are shown in Table 2. There was no i significant effect of Fluorocarbon Polymer 2A, alone, on the flow characteristics of Hydrocarbon Polymer A, and surface roughness appeared at all extrusion rates above about 4 g/min.

20~03 ComDarative Example 3 An extruder warm-up was carried out as in Comparative Example l with unmodified Hydrocarbon Polymer A, giving the same result6. Hydrocarbon Polymer A which, as a dry blend, had intimately dispersed therein 0.02 wt. % of Fluorocarbon Polymer lA, was then added to the extruder at the same temperature settinqs and at a screw speed of 40 rpm.
Steady state was achieved after 60 min. and did not chan~e after a further 60 min. The die pressure/throughput relationship was then obtained as in Comparative Example l and is shown as Curve 3 in Figure l. Representative data are shown in Table 2.
In this case there was an approximate 10% reduction in die pressure at a given throughput, compared to Comparative Example 1, and extrudates were smooth and glossy at extrusion rates below about 30 g/min.
Example l An extruder warm-up was carried out as in ! 20 Comparative Example 1, giving the same results.
Hydrocarbon Polymer A which, as a dry blend, had intimately dispersed therein 0.01 wt. % of Fluorocarbon Polymer lA and 0.01 wt. % of Fluorocarbon Polymer 2A was then added at the same temperature settings and a screw speed of 40 rpm. A new equilibrium was established, after 180 min., at much lower pressures than for the hydrocarbon resin alone or for the composition of Comparative Example 3. The 1 30 die pressure/throughput curve was then obtained as in Comparative Example l, and is shown as Curve 4 in ! Figure 1. Representative data are shown in Table 2.
There was an approximately 30% drop in die pressure over the entire range, compared to Hydrocarbon Polymer A, even though the combined concentrations of Fluorocarbon Polymers lA and 2A in this example is no 2~27~3 greater than the concentration of Fluorocarbon Polymer lA in Comparative Example 3. Extrudate surfaces were smooth and glossy throughout the range of extrusion rates attai~able under the condition~ of the example (up to 55 g/min., which is equivalent to a shear rate of about 1500 sec~l). When a 1.5 mm diameter die was used in order to obtain shear rates up to about 3000 sec~l, the extrudate was ~mooth and glocsy over the entire range of extrusion rates.
Exam~le 2 An extruder warm-up was carried out as in Example 1, with similar results. A dry blend of Hydrocarbon Polymer A having intimately dispersed therein 0.0005 wt. % of Fluorocarbon Polymer lA and 0.0020 wt. ~ of Fluorocarbon Polymer 2A was then added at the same temperature settings and a screw speed of 40 rpm. The new equilibrium was established after 180 minutes, at a lower die pressure than for the ' hydrocarbon resin alone or for the composition of i Comparative Example 3. The die pressure/extrusion rate cur~e was obtained as in Example 1 and representative data are shown in Table 2. There was an approximately 28% reduction in die pressure over the entire extrusion rate range compared to Hydrocarbcn Polymer A, even though the combined concentrations of Fluorocarbon Polymers lA and 2A is only 12.5% of the concentration of Fluorocarbon Polymer lA in Comparative Example 3. Extrudate surfaces were smo~th and glossy at extrusion rates below 55 g/min.
I Example 3 In this example a series of compositions was evaluated to demonstrate the effect of the relative weight ratios of Fluorocarbon Polymer lA to 2027~03 Fluorocarbon Polymer 2A, as shown in Table 3. Each composition was a dry blend of Fluorocarbon Polymers lA and 2A in Hydrocarbon Polymer A, and after extruder - warm-up as described in Example 1, each was added at the same temperature settlngs and a screw ~peed of 40 rpm. New equilibria were then established after 180 minutes, at lower die pressures than for the hydrocarbon resin alone or for the composition of Comparative Example 3. Die pressure~extrusion rate data were obtained as in Example l and are shown in Table 3. There is a significant reduction in die pressure over the entire range compared to Hydrocarbon Polymer A, even though the combined concentrations of Fluorocarbon Polymers lA and 2A is no greater than the concentration in Comparative Example 3. Extrudate surfaces were smooth and glossy at extrusion rates up to 55 g/min.
Example 4 A composition of Hydrocarbon Polymer A
containing an intimate dry powder mix of Fluorocarbon Polymers lB and 2A, 0.01 wt. % of each, based on difficultly melt-processible polymer, was extruded and evaluated as in Example 1. A control experiment in which the difficultly melt-processible polymer contained 0.04 wt. % of Fluorocarbon Polymer lB, alone, was also carried out. Data in Table 4 show that the composition of this invention extrudes at very much lower die pressures than the control and the extrudate is free of surface imperfections at much higher extrusion rates, even though it contains only half as much total modifier.
Exammle 5 A composition of Hydrocarbon Polymer A
containing an intimate dry powder mix of Fluorocarbon Polymers lC and 2A, 0.01 wt. % of each, based on 027~3 hydrocarbon polymer, was extruded and evaluated as in Example 1. A control experiment in which the hydrocarbon polymer contained 0.04 part by wt. of Fluorocarbon Polymer lC, alone, was also carried out.
! 5 Data in Table 4 show that the composition of this example extrudes at very much lower die pressures than the control and the extrudate is free of surface imperfections at much higher extrusion rates, even though it contains only half as much total modifier.
10Examples 6 and 7 For each example, Hydrocarbon Polymer A, which as a dry blend had intimately dispersed therein O.01 wt. % of Fluorocarbon Polymer lA and 0.01 wt. ~
of Fluorocarbon Polymers 2B and 2F (Examples 6 and 7, respectively), was added to the extruder and treated in the manner described in Example 1. As shown by the data in Table 5, the new equilibria were then established after 180 minutes, at lower pressures than ' for the controls represented by Comparative Examples 1 ¦ 20 and 3, Table 2. All extrudate surfaces were smooth and glossy throughout the range of extrusion rates up to 38 g/min. Compositions of Hydrocarbon Polymer A
and 0.10 wt. % of any of the Fluorocarbon Polymers 2B
and 2F showed no improvement in extrusion behavior (data not shown).
Examples 8 and 9 In these examples Hydrocarbon Polymers B and C were compared in formulations containing dry blends of Fluorocarbon Polymers lA and 2A in the amounts i shown in Table 6. Die pressure/extrusion rate data were evaluated as outlined in Example 1. For each example there is a control sample containing no additives and another showing the effect of Fluorocarbon Polymer lA alone. Data were analyzed as in Example 1 and are shown in Table 6.

-`~ 2~7a~3 Example 10 In this experiment a chrome-plated, 2.54 cm (1 in.) wide slit die having a gap of 0.76 mm (0.03 in.) and a land length of 1.27 cm (0.5 in.~ was used. A dry blend composition of Hydrocarbon Polymer A and 0.01 wt. % of each of Fluorocarbon Polymers lA
and 2A was fed at 60 rpm, giving the initial throughput and die pressure ratings indicated in Table 7. The initial extrudate had a rough dull surface.
After 3 h the extrudate was smooth and glossy and there was a 17.5% reduction in di~ pressure as well as a 3.5% increase in throughput. The extrudate surface remained excellent up to the maximum throughput achievable with the extruder (S5 q/min. at 120 rpm).
In a similarly-run control experiment with Hydrocarbon Polymer A alone, the starting and final parameters ; were as shown in Table 7, and the extrudate had a dull rough surface at all extrusion rates above about 8 g/min. In another control experiment with 0.02 wt.%
of Fluorocarbon Polymer lA, there was only a 3%
pressure drop after 3 h and nil increase in throughput. The extrudate surface was smooth and glossy at 60 rpm, but dull and rough in appearance at all higher screw speeds.
Exam~le 11 The equipment employed was a Haake Buchler Rheomix~ 19.1 mm ~3/4 in.) diameter single-screw extruder with ~ chromium plated one-stage metering screw having a 20/1 length/diameter ratio, 10 feed flights, 5 compression flights, 5 ~etering flights and a channel depth ratio of 3. Operating parameters were controlled by four independent heating zones, two pressure transducers and a torque-measuring drive with 1-200 rpm capability. The extruder was equipped with software for rheometric capillary extrusion testing.

2~270~3 The capillary die, made from #416 stainless steel, had a diameter of 1.27 D and a length of 39.1 mm and was previously unused. Prior to each use the extruder was thoroughly cleaned by first purging with Hydrocarbon Polymer A containing 20% 8ilica. ~he extruder was tben disassembled and each ~ection was cleaned with a wire brush and then methyl ethyl ketone solvent. The die holder was cleaned by heating at 600-C for 4 hrs.
~A) A commercially available extrusion grade polystyrene, Styron 685D ~Dow Chemical Co.), density 1.40 g/cc, melt flow rate 1.6 g/10 min., was fed to the extruder, equipped with a new die, with the screw operating at 5 rpm and heating zones 1, 2, 3, and 4 controlled at nominal settings of 150, 180, 200 and 240-C, respectively ~No. 4 is closest to the die).
Equilibrium extrusion conditions were achieved after ' 120 min. The screw speed was then systematically ! varied from 1 rpm to 120 rpm to generate, as I previously described, the correlation of extruder ! 20 throughput and die pressure 6hown in Curve 1 of Figure 2. Melt fracture was not observed at any screw speed tested, but die buildup (collection of polymer ; at the exit of the capillary die) was observed at screw speeds greater than 60 rpm.
~B) Without changing conditions the feed was changed to a powder blend of polystyrene containing 0.05 wt. % of Fluorocarbon Polymer 2G.
Using the procedure of Part A, a new equilibrium was established after 240 min., and the data of Curve 2 in Figure 2 was generated. Die buildup was not observed at any screw speed.
(C) Without changing conditions the extruder was thoroughly purged with Hydrocarbon -Polymer A containing 20 wt. % of silica. Then the procedure of Part A was repeated except that the o ~

extruder feed was changed to a powder blend of polystyrene containing 0.05 wt. % of Fluorocarbon Polymer ln. After a total extrusion time of 250 min., conventional capillary rheometer curves were generated and the plot of Figure 2, Curve 3 was obtained. No melt fracture or die buildup was observed.
(D) The procedure of Part C was repeated except that after purging the feed was changed to a powder blend of polystyrene containing 0.05 wt. % each of Fluorocarbon Polymers lD and 2G. After a total extrusion time of 240 min. the data shown in Figure 2, Curve 4 was obtained. No melt fracture or die buildup was observed.
Example 12 In a procedure like that of Example 11, except that the extruder heating zones Numbers 1, 2, 3 and 4 were controlled at nominal temperature ~ettings of 160, 180, 220 and 220C, respectively, the performance of an extrusion grade ethyleneJvinyl acetate copolymer Elvax~-3135 (Du Pont Co.), density 0.930 g/cc, melt index of 0.35 g/10 min., was evaluated. Curve 1 of Figure 3 shows data for extrusion of unmodified EVA copolymer. Curve 2 shows data for a blend containing 0.05 wt. ~ of Fluorocarbon Polymer 2G and Curve 3 shows data for a blend containing 0.05 wt. % of Fluorocarbon Polymer lD.
Curve 4 of the figure show the data for an EVA
containing 0.05 wt. % each of Fluorocarbon Polymers lD
and 2G.
Example 13 (A) In a procedure like that of Example 11, except that the extruder heating zones Numbers 1, 2, 3 and 4 were controlled at nominal temperature settings of 280, 310, 310 and 310~C, respectively, the 3S performance of an extrusion grade copolymer of ~ 2~27~

ethylene glycol and terephthalic acid (Goodyear PET), density 1.39 g/cc, inherent viscosity (0.05 wt. % in a 3/1 mixture of methylene chloride and trifluoroacetone) 1.65, was evaluated. Die pressure was measured at a constant screw speed of 5 rpm over a period of 120 min. The die pressure fluctuated steadily between about 3 to 10 MPa with a time period of several minutes. After 120 minutes the screw speed was varied from 1 to 30 rpm. Large die pressure fluctuations continued and at 30 rpm caused automatic shutoff of the extruder, which had a safety cutoff pressure set at 70 MPa. At 30 rpm flow rate was 19.8 g/min. Thus, the PET could not be extruded at screw speeds qreater than 30 rpm or at a flow rate greater than 19.8 g/min. In addition, an accumulation of dark decomposed polymer was observed to build up at the exit of the capillary die at all extrusion speeds.
Curve 1 of Figure 4 shows data for the extrusion of ¦ unmodified PET up to the point of automatic shutoff.
Pressure values are the averages of the high and low extremes.
(B) Without changing conditions, the feed was switched to a blend of the PET containing 0.05 wt. ~ of Fluorocarbon Polymer 2G; the blend was evaluated as in Part A. After several minutes at
5 rpm the large pressure fluctuations abruptly ceased ; and there were no pressure fluctuations at screw rates up to 60 rpm, where the flow rate was 28.2 g/min., and there was no accumulation of polymer at the die exit.
i At 90 rpm high pressure fluctuat~ons again caused automatic shutdown of the extruder. Extrusion data are shown in Curve 2 of Figure 4 and show that, at equivalent flow rates, the extrusion pressures are higher for the blend containing the process aid.

.. . . ~ . . . , . . . ~

2~ '03 (C) The extruder feed was changed to a powder blend of the PET containing 0.05 wt. % of ~luorocarbon Polymer lD; the blend was evaluated as in Part A. After several minutes at 5 rpm the large pressure fluctuations observed in Part A ceased.
After 120 ~inutes the ~crew speed was varied from 1 to 60 rpm, where the flow rate was 31.2 g/min. The pressure was steady at all speeds and there was no accumulation of decomposed polymer at the die exit.
At 90 rmp the pre~sure exceeded the 6afety cutoff pressure. Extrusion data are shown in Curve 3 of Figure 4. As in Part B, the extrusion pressures were higher for the blend than for the PET not containing process aid.
(D) The procedure of Part A was ~epeated using a powder blend of PET containing 0.05 wt. % each of Fluorocarbon Polymers lD and 2G. In this case the extrusion could be carried out at up to 90 rpm without pressure fluctuations, at which rpm a flow rate of 47.4 g/min. was achieved without die accumulation.
Moreover, using the combination of process aids the extrusion pressure was surprisingly much lower than when these fluorocarbon polymers were used singly.
Data are shown in Curve 4 of Figure 4.
Exam~le 14 The evaluations reported below employed the apparatus described in Example 11, using a capillary die made from #416 nitrided stainless steel that had a diameter of 0.38 mm and a length of 0.76 mm. The die was heated in an electric furnace for 4 hours at 450-C
prior to use.
(A) A commercially available fiber grade nylon 66 having a relative viscosity of 43, density 1.10 q/cc (T-972, Du Pont Co.) was fed into the extruder with the screw operating at 5 rpm and heating 2 ~ 0'~

zones Nos. 1, 2, 3 and 4 controlled at nominal temperature settings of 260, 270, 270 and 270-C, respectively, ~No. 4 is closest to the die). After equilibrium was achieved, screw speed was reduced to 3 rpm to achieve an extrusion rate of 2 g/min. Die pressure at this extrusion rate was 3.1 ~Pa. After a period of one hour no buildup of polymer was observed at the exit of the die. The temperatures of heating zones 3 and 4 were then both increased periodically in 5-C increments, up to a temperature of 300-C. In each case the extrusion rate was adjusted to 2 g/min. by changing the rpm, and the extrusion was continued for one hour. Whenever a die deposit was observed to collect at the die exit, at any temperature, the die was cleaned by wiping shortly after increasing to the next higher temperature and ad~ustin~ the screw speed.
Buildup of a ring of black decomposed polymer first appeared at the exit of the die, around the extruding nylon fiber, during the extrusion at 280-C.
Similarly, a ring of decomposed polymer appeared at all temperatures tested between 280- and 300-C.
(B) Starting conditions were returned to a screw speed of 5 rpm and heatinq zones Nos. 1, 2, 3 and 4 controlled at settings of 260, 270, 270 and 270-C, respectively. The extruder feed was changed to ' a powder blend of the nylon containing 0.05 wt. % of Fluorocarbon Polymer 2G. After equilibrium was achieved, screw speed was increased to 10 rpm to achieve an extrusion rate of 2 g/min. Die pressure at this extrusion rate was 3.8 MPa. After a period of ' one hour no buildup of polymer was observed at the exit of the die. The temperatures of heating zones 3 and 4 were then incrementally increased as described in Part A. Buildup of a globule of black decomposed polymer first appeared at the exit of the die, near .. .

the extruding nylon fiber, during the extrusion at 285-C. After wiping the die clean, a globule of d~composed polymer appeared at all temperatures tested between 285- and 300-C.
(C) The procedure of Part A was repeated except th~t the extruder feed was changed to a powder blend of the nylon containing 0.05 wt. % of an additive similar to Fluorocarbon Polymer 2C but having a melt viscosity of 10,300 Ns/m2 at 372-C (DSC melting point maximum at 260-C). After equilibrium was achieved at a melt temperature of 270-C and a screw speed of 5 rpm, screw speed was held constant at 5 rpm to achieve an extrusion rate of 2 g/min. Die pressure at this extrusion rate was 4.7 MPa. After a period of one hour no buildup of polymer was observed at the exit of the die. The temperatures of heating zones 3 and 4 were then both increased periodic~lly in 5-C
increments as described in Part A, and the extrusion speed was adjusted to 2 g/min. in each case. Buildup of a globule of black decomposed polymer first appeared at the exit of the die, near the extruding nylon fiber, during the extrusion at 280-C, and then at all temperatures tested between 280- and 300-C.
(D) The procedure of Part A was repeated except that the extruder feed was changed to a powder blend of the nylon containing 0.02 wt. % each of the fluorocarbon polymers described in Parts B and C.-After equilibrium was achieved at a melt temperature of 270-C and a screw speed of 5 rpm, screw speed was j held constant at 5 rpm to achieve an extrusion rate of ~ 2 g/min. pie pressure at this extrusion rate was ! 4.7 MPa. After a period of one hour no buildup of polymer was observed at the exit of the die. The temperatures of heating zones 3 and 4 were then both inc~eased periodically in 5-C increments to 300-C as 2 ~ CP

described in Part A. No buildup of either a ring or globule of decomposed polymer appeared at the exit of the die during extrusion at any temperature between ! 5 270C nd 300-C, the highest temperature tested.

2~27~3 ~ABLE 1 ~v~e (1~ Fluorocarbon Polymers:
lA: A commercially available fluoroelastomer containing polymer repeat units of 60 wt. %
vinylidene fluoridQ and 40 wt. %
- hexafluoropropylene and having a Mooney ~ viscosity of 60 at lOO-C. It was in the form of a fine powder which had been ; 10 obtained by cryogenic grinding and had a light dusting of calcium carbonate as an antiblocking agent.
; lB: A commercially available fluoroelastomer containing pol~mer repeat ~nits of 45 wt. %
vinylidene fluoride, 30 wt. %
hexafluoropropylene and 25 wt. %
tetrafluoroethylene and having a Mooney viscosity of 80 at 121-C. It was ground and i dusted as in lA.
! 20 lC: A commercially available copolymer composed of polymer repeat units of tetrafluoroethylene, propylene and vinylidene fluoride.
lD: A fluoroelastomer containing polymer repeat units of tetrafluoroethylene (55.4 wt. %), perfluoro(methyl vinyl ether) (44.2 wt. %), and vinylidene fluoride (0.4 wt. %).

Tv~e (2~ Fluorocarbon Pol~mers:
~ 2A: A commercially available free-flowing PTFE
; powder comprising loose agglomerates of ! sub-micron size particles having fibrillating characteristics that was treated with ionizing electron beam --` 2~27~Q~

TABLE 1 (Continued~

radiation until the melt viscosity was reduced to 1.1 x 104 Ns/m2.
i 5 2B: A commercially available, high molecularweight, non-melt-processible PTFE, prepared by ~uspension polymerization, having a standard specific gravity o~ 2.16 and an average particle size of 35 micrometers.
2C: A commercially available powdered copolymer of tetrafluoroethylene and 12 wt. % of hexafluoropropylene and having a melt viscosity ~f 9,500 Ns/~2 at 372-C.
2D: A commercially available powdered copolymer of tetrafluoroethylene and 3-4 wt. % of perfluoro(propyl vinyl ether~ and having a I melt viscosity of 4,700 Ns/m2 at 372-C.
I 2E: A commercially available powdered copolymer ¦ of tetrafluoroethylene and 3-4 wt. % of perfluoro(propyl vinyl ether) and having a melt viscosity of 34,000 Ns/m2 at 372-C.
2F: A commercially available powdered, essentially alternating copolymer of tetrafluoroethylene, ethylene and a small amount of a proprietary comonomer, and having a melt flow of 20 at 297-C
(ASTM-D3159).
2G: An experimental polymer sililar to 2A but - having a melt viscosity of 11.3 Ns/m2.

j Hvdrocarbon Polvmers ; A: A hi~h molecular weight, linear low density (d=0.918) copolymer of ethylene and butene-l having a melt index (ASTN D-1238, cond. E) of 1Ø

- . ~
2027~ 3 B: A high density polyethylene (d=0.945) having a melt index of 0.05.
C: A low density (d=0.925) polyethylene containing 5 wt. % of high density 1 5 polyethylene and a small ~uantity of poly(vinyl acetate), and having a melt index of 0.50.

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Claims (58)

Claims
1. Polymer blend composition having improved processibility and comprising:
(a) a major portion of a difficultly melt-processible polymer selected from the group consisting of vinyl aromatic polymers: copolymers of alpha-olefins and vinyl esters, (meth)acrylic esters, acrylonitrile, and (meth)acrylic acids and their (ionomeric) metal salts: chlorinated polyethylene;
polyvinyl chloride; polyester and polyamide, and (b) a minor portion of:
(1) at least an effective amount, to improve processibility, of a fluorocarbon copolymer which at the melt-processing temperature of (a) is either in a melted form if crystalline, or is above its glass transition temperature if amorphous, and (2) at least an effective amount, to improve processibility, of at least one tetrafluoroethylene homopolymer or copolymer of tetrafluoroethylene and at least one monomer copolymerizable therewith, wherein the mole ratio of fluorine to hydrogen is at least 1:1, and which is solid at the melt-processing temperature of (a).
2. Composition of Claim 1 wherein the polymer is polystyrene.
3. Composition of Claim 1 wherein the polymer is a copolymer of ethylene and vinyl acetate.
4. Composition of Claim 1 wherein the polymer is a polyester.
5. Composition of Claim 4 wherein the polyester is a copolymer of ethylene glycol and terephthalic acid.
6. Composition of Claim 1 wherein the polymer is a polyamide.
7. Composition of Claim 1 wherein the amount of (b)(1) is no more than 0.5 wt. %, based on the weight of (a).
8. Composition of Claim 7 wherein the amount of (b)(1) is 0.002-0.20 wt. %, based on the weight of (a).
9. Composition of Claim 7 wherein the amount of (b)(2) is 0.002-0.20 wt. %, based on the weight of (a).
10. Composition of Claim 1 wherein, in component (b)(1), the mole ratio of fluorine to hydrogen is at least 1:1.5.
11. Composition of Claim 1 wherein the melting or softening point of component (b)(1) is no more than 120-300°C.
12. Composition of Claim 11 wherein the melting or softening point of component (b)(1) is no more than 120-200°C.
13. Composition of Claim 1 wherein component (b)(1) is a fluorocarbon copolymer of vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, a perfluoro(alkyl vinyl ether), 1-hydropentafluoropropylene or 2-hydropentafluoropropylene.
14. Composition of Claim 13 wherein component (b)(1) is a copolymer of vinylidene fluoride and a monomer selected from hexafluoropropylene, chlorotrifluoroethylene, 1-hydropentafluoropropylene and 2-hydropentafluoropropylene; a copolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene or 1- or 2-hydropentafluoropropylene; a copolymer of tetrafluoroethylene and propylene; a copolymer of tetrafluoroethylene and a perfluoro(alkyl vinyl ether); or a copolymer of tetrafluoroethylene and hexafluoropropylene.
15. Composition of Claim 14 wherein the alkyl group is methyl.
16. Composition of Claim 14 wherein the copolymer includes polymer repeat units of a bromo- or iodo group-containing monomer.
17. Composition of Claim 1 wherein component (b)(2) is polytetrafluoroethylene.
18. Composition of Claim 1 wherein component (b)(2) is a copolymer of tetrafluoroethylene and one or more monomers selected from ethylene, a perfluoroolefin, a perfluoro(alkyl vinyl ether) or a perfluoro(alkyl vinyl ether) containing a functional group.
19. Composition of Claim 18 wherein the monomer is ethylene.
20. Composition of Claim 18 wherein the monomer is hexafluoropropylene.
21. Composition of Claim 18 wherein the monomer is perfluoro(propyl vinyl ether).
22. Composition of Claim 18 wherein the functional group is -SO2F or -CO2CH3.
23. Composition of Claim 1 wherein the weight ratio of component (b)(1) to component (b)(2) is within the range 2:98 to 95:5.
24. Composition of Claim 23 wherein the weight ratio of component (b)(1) to component (b)(2) is within the range 10:90 to 90:10.
25. Processing aid composition for a difficultly-melt-processible polymer selected from the group consisting of vinyl aromatic polymers:
copolymers of alpha-olefins and vinyl esters, (meth)acrylic esters, acrylonitrile, and (meth)acrylic acids and their (ionomeric) metal salts: chlorinated polyethylene: polyvinyl chloride; polyester and polyamide, said composition consisting essentially of:
(a) a major portion of a polymer that is compatible with the difficultly-melt-processible polymer, and (b) a minor portion of, with the parts totaling 100 parts:
(1) 2-95 parts by weight of a fluorocarbon copolymer which at the melt-processing temperature of the difficultly melt-processible polymer is either in a melted form if crystalline or is above its glass transition temperature if amorphous; and (2) 98-5 parts by weight of a tetrafluoroethylene homopolymer or copolymer of tetrafluoroethylene and a monomer which is copolymerizable therewith, wherein the mole ratio of fluorine to hydrogen is at least 1:1, and which is solid at the melt-processing temperature of the difficultly melt-processible polymer.
26. Composition of Claim 25 wherein the combined amounts of component (b)(1) and component (b)(2) comprise 1-10 wt. % of the composition.
27. Composition of Claim 26 wherein the combined amounts of component (b)(1) and component (b)(2) comprise 1-5 wt. % of the composition.
28. Composition of Claim 25 wherein the compatible polymer is a difficultly melt-processible polymer.
29. Composition of Claim 25 wherein the amount of component (b)(1) is 10-90 parts and the amount of component (b)(2) is 90-10 parts.
30. Composition of Claim 25 wherein the mole ratio of fluorine to hydrogen in component (b)(1) is at least 1:1.5.
31. Composition of Claim 25 wherein the melting or softening point of component (b)(1) is no more than 120-300°C.
32. Composition of Claim 31 wherein the melting or softening point of component (b)(1) is no more than 120-200°C.
33. Composition of Claim 25 wherein component (b)(1) is a fluorocarbon copolymer of vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, a perfluoro(alkyl vinyl ether), 1-hydropentafluoropropylene or 2-hydropentafluoropropylene.
34. Composition of Claim 33 wherein component (b)(1) is a copolymer of vinylidene fluoride and a monomer selected from hexafluoropropylene, chlorotrifluoroethylene, 1-hydropentafluoropropylene and 2-hydropentafluoropropylene; a copolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene or 1- or 2-hydropentafluoropropylene: a copolymer of tetrafluoroethylene and propylene; a copolymer of tetrafluoroethylene and a perfluoro(alkyl vinyl ether); or a copolymer of tetrafluoroethylene and hexafluoropropylene.
35. Composition of Claim 34 wherein the copolymer includes polymer repeat units of a bromo- or iodo group-containing monomer.
36. Composition of Claim 25 wherein component (b)(2) is polytetrafluoroethylene.
37. Composition of Claim 25 wherein component (b)(2) is a copolymer of tetrafluoroethylene and one or more monomers selected from ethylene, a perfluoroolefin, a perfluoro(alkyl vinyl ether) or a perfluoro(alkyl vinyl ether) containing a functional group.
38. Composition of Claim 37 wherein the monomer is ethylene.
39. Composition of Claim 37 wherein the monomer is hexafluoropropylene.
40. Composition of Claim 37 wherein the monomer is perfluoro(propyl vinyl ether).
41. Composition of Claim 37 wherein the functional group is -SO2F or -CO2CH3.
42. Extrusion process comprising melt extruding a difficultly melt-processible polymer selected from the group consisting of vinyl aromatic polymers; copolymers of alpha-olefins and vinyl esters, (meth)acrylic esters, acrylonitrile, and (meth)acrylic acids and their (ionomeric) metal salts:
chlorinated polyethylene: polyvinyl chloride:
polyester: and polyamide, having incorporated therein an effective amount, to improve processibility, of a processing aid consisting essentially of, with the parts totaling 100 parts:
(a) 2-95 parts by weight of a fluorocarbon copolymer which at the melt-processing temperature of the difficultly melt-processible polymer is either in a melted form if crystalline or is above its glass transition temperature if amorphous; and (b) 98-5 parts by weight of a tetrafluoroethylene homopolymer or copolymer of tetrafluoroetbylene and a monomer which is copolymerizable therewith, wherein the mole ratio of fluorine to hydrogen is at least 1:1, and which is solid at the melt-processing temperature of the difficultly melt-processible polymer.
43. Process of Claim 42 wherein the mole ratio of fluorine to hydrogen in component (a) is at least 1:1.5.
44. Process of Claim 42 wherein the melting or softening point of component (a) is no more than 120-300°C.
45. Process of Claim 44 wherein the melting or softening point of component (a) is no more than 120-200°C.
46. Process of Claim 42 wherein component (a) is a fluorocarbon copolymer of vinylidene fluoride, hexafluoropropylene, chlorotrifluoroethylene, tetrafluoroethylene, a perfluoro(alkyl vinyl ether), 1-hydropentafluoropropylene or 2-hydropentafluoropropylene.
47. Process of Claim 46 wherein component (a) is a copolymer of vinylidene fluoride and a monomer selected from hexafluoropropylene, chlorotrifluoroethylene, l-hydropentafluoropropylene and 2-hydropentafluoropropylene; a copolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene or 1- or 2-hydropentafluoropropylene: a copolymer of tetrafluoroethylene and propylene; a copolymer of tetrafluoroethylene and a perfluoro(alkyl vinyl ether); or a copolymer of tetrafluoroethylene and hexafluoropropylene.
48. Process of Claim 47 wherein the copolymer includes polymer repeat units of a bromo- or iodo group-containing monomer.
49. Process of Claim 42 wherein component (b) is polytetrafluoroethylene.
50. Process of Claim 42 wherein component (b) is a copolymer of tetrafluoroethylene and one or more monomers selected from ethylene, a perfluoroolefin, a perfluoro(alkyl vinyl ether) or a perfluoro(alkyl vinyl ether) containing a functional group.
51. Process of Claim 50 wherein the monomer is ethylene.
52. Process of Claim 50 wherein the monomer is hexafluoropropylene.
53. Process of Claim 50 wherein the monomer is perfluorotpropyl vinyl ether).
54. Process of Claim 50 wherein the functional group is -SO2F or -CO2CH3.
55. Process of Claim 42 wherein the amount of component (a) is 10-90 parts and the amount of component (b) is 90-10 parts.
56. Composition of Claim 17 wherein the polytetrafluoroethylene has been subjected to ionizing radiation.
57. Composition of Claim 36 wherein the polytetrafluoroethylene has been subjected to ionizing radiation.
58. Composition of Claim 49 wherein the polytetrafluoroethylene has been subjected to ionizing radiation.
CA002027003A 1990-01-04 1990-10-05 Processing aid for polymers Abandoned CA2027003A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US46009390A 1990-01-04 1990-01-04
US460,093 1990-01-04
US572,921 1990-08-29
US07/572,921 US5013792A (en) 1990-01-04 1990-08-29 Processing aid for polymers

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