CA1332253C - Extrudable thermoplastic hydrocarbon polymer composition - Google Patents
Extrudable thermoplastic hydrocarbon polymer compositionInfo
- Publication number
- CA1332253C CA1332253C CA000591514A CA591514A CA1332253C CA 1332253 C CA1332253 C CA 1332253C CA 000591514 A CA000591514 A CA 000591514A CA 591514 A CA591514 A CA 591514A CA 1332253 C CA1332253 C CA 1332253C
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- CA
- Canada
- Prior art keywords
- composition
- organophosphate
- organophosphite
- fluorocarbon polymer
- tris
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
Abstract
ABSTRACT
An extrudable composition comprising hydrocarbon polymer, organophosphite, organophosphate, or blend thereof and fluorocarbon polymer. The organophosphite, organophosphate or blend thereof and the fluorocarbon polymer are present in the composition in such relative proportions and concentrations as to reduce the occurrence of melt defects during the extrusion of said thermoplastic hydrocarbon polymer.
An extrudable composition comprising hydrocarbon polymer, organophosphite, organophosphate, or blend thereof and fluorocarbon polymer. The organophosphite, organophosphate or blend thereof and the fluorocarbon polymer are present in the composition in such relative proportions and concentrations as to reduce the occurrence of melt defects during the extrusion of said thermoplastic hydrocarbon polymer.
Description
13322~
EXTRUDABL~ THERMOPLASTIC HYDROCAR~ON POLYMER COMPOSITION
Thls lnventlon relates to thermoplastlc hydrocarbon polymers, ~uch a~ polyoleflns havlng improved extruslon charac-teristics. In another aspect lt relates to the use of fluoro-carbon polymers to lmprove the extru~lon characterlstlcs of such thermoplastlc hydrocarbon polymers. In stlll a further aspect lt relate~ to the use of organophosphltes or organophosphates to lmprove the extruslon characterlstlcs of such thermoplastlc hydro-carbon polymers. In a stlll further aspect lt relates to a poly-mer processlng ald composltlon.
Westover, R. F., "Melt Extruslon", Encvclo~edla of Polv-mer Sclence and Technoloqv, Vol. 8, John Wlley & ~ons, (1968) pp 573-581 states that for any polymer there ls a certaln crltlcal shear rate above whlch the ~urface of the extrudate becomes rough and below whlch the extrudate wlll be smooth. He further states that ln order to achleve the hlghest posslble flow rate from the extruder and to achleve the most unlform extrudate cross sectlon the processor must control extrudate roughness or dlstortlon.
Some of the varlous types of extrudate roughness and dlstortlon observed ln hlgh and low denslty polyethylenes are descrlbed ln Rudln, A., Worm, A.T., Blacklock J.E., "Fluorocarbon Elastomer Alds Polyolefln Extruslon," Plastlcs Enqlneerlna, March 1986, pp.
63-66. Rudln et al. state that for a glven ~et of processlng condltlons and dle geometry, a crltlcal shear stress exlsts above whlch polyoleflns llke llnear low-denslty polyethylene (LLDPE), hlgh-denslty polyethylene (HDPE), and polypropylene suffer from melt defects. At low shear rates, defects may take the form of "sharkskln", a loss \ ' ` 133223~
EXTRUDABL~ THERMOPLASTIC HYDROCAR~ON POLYMER COMPOSITION
Thls lnventlon relates to thermoplastlc hydrocarbon polymers, ~uch a~ polyoleflns havlng improved extruslon charac-teristics. In another aspect lt relates to the use of fluoro-carbon polymers to lmprove the extru~lon characterlstlcs of such thermoplastlc hydrocarbon polymers. In stlll a further aspect lt relate~ to the use of organophosphltes or organophosphates to lmprove the extruslon characterlstlcs of such thermoplastlc hydro-carbon polymers. In a stlll further aspect lt relates to a poly-mer processlng ald composltlon.
Westover, R. F., "Melt Extruslon", Encvclo~edla of Polv-mer Sclence and Technoloqv, Vol. 8, John Wlley & ~ons, (1968) pp 573-581 states that for any polymer there ls a certaln crltlcal shear rate above whlch the ~urface of the extrudate becomes rough and below whlch the extrudate wlll be smooth. He further states that ln order to achleve the hlghest posslble flow rate from the extruder and to achleve the most unlform extrudate cross sectlon the processor must control extrudate roughness or dlstortlon.
Some of the varlous types of extrudate roughness and dlstortlon observed ln hlgh and low denslty polyethylenes are descrlbed ln Rudln, A., Worm, A.T., Blacklock J.E., "Fluorocarbon Elastomer Alds Polyolefln Extruslon," Plastlcs Enqlneerlna, March 1986, pp.
63-66. Rudln et al. state that for a glven ~et of processlng condltlons and dle geometry, a crltlcal shear stress exlsts above whlch polyoleflns llke llnear low-denslty polyethylene (LLDPE), hlgh-denslty polyethylene (HDPE), and polypropylene suffer from melt defects. At low shear rates, defects may take the form of "sharkskln", a loss \ ' ` 133223~
of surface gloss, whlch ln more serlous manifestatlons, appears as rldges runnlng more or less transverse to the extruslon dlrection.
At hlgher shear rate the extrudate can undergo "contlnuous melt fracture" becomlng grossly distorted. At rates lower than those at whlch contlnuous melt fracture ls flrst observed, LLDPE and HDPE can also suffer from "cycllc melt fracture", ln whlch the extrudate surface varles from smooth to rough. The authors state that lowerlng the shear stress by ad~ustlng the processlng condltlons or changlng the dle can avold these defects to a certaln extent, but not wlthout creatlng a whole new set of problems. For example, extruslon at a hlgher temperature can result ln weaker bubble walls ln tubular fllm extruslon, and a - -~
wlder dle gap can affect fllm orlentatlon. The authors state that the use of fluorocsrbon elastomer processlng alds can permlt the operation of extruders with narrower die gaps and lower melt temperatures. Others have also descrlbed the use of fluorocarbon elastomers as processlng alds, see for example, De Smedt, C., Nam, S., "The Processlng Benefits of Fluoroelastomer Appllcation ln LLDPE," Plastlcs and Rubber Processln~ and APpllcatlons~ 8, No. 1, (1987), pp. 11-16; U.S. Pat. No's. 3,125,547 (Blat~), and 4,581,406 (Hedberg et al.).
Organophosphlte compounds have been used as antloxldants ln polyoleflns. European Pat. Appl. EP 227948 A2 (Horn et al) published July 8, 1987 disclose that a comblnatlon of a trls(alkylphenyl) phosphlte and a dlalkyl thiodlpropionate added ~
to polyolefins lmproves melt processlblllty. ~ ;
The present lnventlon provldes an extrudable composltlon comprlslng ~ -.~ .
. .
, . . ..
r ~ ~ 3 3 2 2 ~ 3 60557-3579 (A) thermoplastic olefin polymer, as the major or predominant component of the composition, (B) organophosphite, organophosphate, or blends thereof, and (C) fluorocarbon polymer where the weight ratio of said fluorocarbon polymer to said organophosphite, organo-phosphate, or blend thereof is in the range of 1/1 to 1/5, the concentration of said fluorocarbon polymer is 0.005 to 0.1 weight percent, and the concentration of said organophosphite, organophosphate, or blend thereof is 0.01 to 0.2 weight percent based on the total composition weight.
Melt defects are those defects sometimes appearing in extruded thermoplastic hydrocarbon polymers such as sharkskin, melt fracture and cyclic melt fracture.
Generally, the weight of said fluorocarbon polymer in said extrudable composition and the weight of said organo- ~;
phosphite or organophosphate present in said extrudable composition are in a ratio of 1/1 to 1/5. Where said extrudable ;
composition is a final extrudate, i.e. the final product for example a film, the concentration of said fluorocarbon polymer in said composition is 0.005 to 0.2 weight percent and the ~ ~-concentration of said organophosphite or organophosphate in said extrudable composition is 0.01 to 0.8 weight percent, where said weight percent is based on the total weight of the extrudate.
This invention also provides a processing additive composition suitable for addition to thermoplastic polymers to improve extension characteristics consisting essentally of fluorocarbon polymer and organophosphite, organophosphate, or ~ ;
:. ' '' ~' - 3a -1 3 3 2 2 ~ .~ 60557-3579 blend thereof such that the weight of said fluorocarbon polymer in said composition and the weight of said organophosphite, organophosphate, or blend thereof in said composition are in a ratio of 1/1 to 1/5, the fluorocarbon polymer and organophosphite, organophosphate or blend thereof, being the predominant component of said processing additive composition and the concentration of said fluorocarbon polymer in said composition is 14 to 50 weight percent, and the concentration of said organo-phosphite, organophosphate or blend thereof in said composition is 50 to 83 weight percent, where said weight percent is based on total additive composition weight. Optionally, said processing -:
aid composition further comprises other components such as adjuvants, e.g. antioxidants, normally added to thermoplastic hydrocarbon polymers. The concentration of said fluorocarbon polymer, organophosphite or organophosphate and any other adjuvants in said processing aid composition can vary depending upon the processorls requirement, but generally, the fluorocarbon ~ , .
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~4~ 13322~3 . .
polymer and organophosphite or organophosphate will be the major or predominant component of the composition.
The present invention is effective in reducing melt defects not ~nly by delaying the onset of melt defects in thermoplastic hydrocarbon polymers, e.g.
polyolefins, to higher extrusion shear rates than could be achieved using the same level of the fluorocarbon polymer alone, but also by permitting extruder to equilibrate and produce melt-defect-free extrudate in less time than would be required for an extrudate containing the same levEl of fluorocarbon polymer alone at the same extrusion conditions. This permits the use of l~_s fluorocarbon polymer, as well as higher extruder throughputs and shorter extruder start up times resulting in more ecffnomical thermoplastic hydro~larbon ~oIymer 4 extrusion. ~ ih ~ S
The thermoplastic hydrocarbon polymers to which the fluorocarbon polymers and organophosphite or organophosphate are added comprise polymers obtained by the homopolymerization or copolymerization of olefins, as well as copolymers of one or more olefins and up to about 30 weight percent, but preferably 20 weight percent or less, of one or more monomers which are copolymerizable with such olefins, e.q. vinyl ester compounds such as vinyl acetate. Said olefins have the general structure CH2~CHR, where R is a hydro~en or an alkyl radical, and generally, the alkyl radical contains not more than 10 carbon atoms and preferably one to four carbon atoms.
Repre~entative oleflns are ethylene, propylene and butene-1. Representative monomers which are copolymerizable with said olefins are vinyl ester monomers such a~ vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate, vinyl chloropropionate, acrylic and alpha-alkyl acrylic acid monomers, and their alkyl esters, amides, and nitriles such as acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, N,N-dimethyl acry~amide, methacrylamide, .
. . - : . , ,.. :- . ~ . , -j,t : , :. ' ' ' ' ' ;~' ' , ' ' : , , -5- 1 3 3 2 2~3 acrylonltrile, vinyl aryl monomers such as styrene, o-methoxystyrene, p-methoxystyrene, and vinyl naphthalene, vinyl and vinylidene halide monomers such as vinyl chloride, vinylidene chloride, vinylidene bromide, alkyl ester monomers of maleic and fumaric acid such as dimetilyl ~aleate, diethyl maleate, vinyl alkyl ether monomers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ethec, 2-chloroethyl vinyl ether, and vinyl pyridine monomers, N-vinyl carbazole monomers~ and N-vinyl pyrolidine monomers. The thermoplastic hydrocarbon polymers also include the metallic salts of said olefin copolymers, or blends thereof, which contain free carboxylic acid groups. Illustrative of the metals which can be used to provide the salts of said carboxylic acid polymers are the one, two and three valence metals such as sodium, lithium, potassillm, calcium, magnesium, aluminum, barium, zinc, zirconium, beryllium, iron, nickel and cobalt. The thermoplastic hydrocarbon polymers also include blends of thermoplastic hydrocarbon polymers with other thermoplastic hydrocarbon polymers or blends thereof containing conventional adjuvants such as antioxidants, light stabilizers, fillers, antiblocking agents and pigments.
Representative examples of thermoplastic hydrocarbon polymers useful in this invention are polyethylene, polypropylene, polybutene-l, poly(3-methylbutene), poly(4-methylpentene) and copolymers of ethylene with-propylene, butene-l, hexene-l, octene-l, decene-l, 4-methyl-1-pentene and octadecene-l.
Representative blends of thermoplastic hydrocarbon ! polymers useful in this invention are blends of polyethylene and polypropylene, low-denslty polyethylene and high-density polyetnylene, and polyethylene and olefin copolymers containing said copolymerizable monomers, some of which are described above, e.g., ethylene and acrylic acid copolymers; ethylene and methyl ~ 6- 13322~
acrylate copolymers, ethylene and ethyl acrylate copolymers, ethylene and vinyl acetate copolymers, ethylene, acrylic acid, and ethyl acrylate copolymers, and ethylene, acrylic acid, and vinyl acetate copolymers.
The preferred thermoplastic hydrocarbon polymers are homopolymers of ethylene and propylene and copolymers of ethylene and l-butene, l-hexene, l-octene, 4-methyl-1-pentene, propylene, vinyl acetate, and methyl acrylate.
The thermoplastic hydrocarbon polymers may be used in the form of powders, pellets, granules, or any other extrudable form. ~ ~
The fluorocarbon or fluorinated polymers useful in ~ ~ ;
this invention are generally homopolymsrs and copolymers of fluorinated olefins having a fluorine atom to carbon atom ratio of at least 1:2, preferably at least 1:1.
Homopolymers which can be used are those derived, for example, from vinylidene fluoride and vinyl fluoride. -~
Copolymers of fluorinated olefins can be those derived, _ for example, from vinylidene fluoride, and one or more addltional olefins, which can be fluorinated, e.g.
hexafluoropropylene, and non-fluorinated, e.g. propylene.
- - Preferred fluorocarbon polymers are copolymers of vinylidene fluoride with at least one terminally unsaturated fluoromonoolefin containing at least one fluorine atom on each double-bonded carbon atom, each carbon atom of said fluoromonoolefin being substitueed only with fluorine, chlorine, bromine, hydrogen or lower fluoroalkyl (e.g. perfluoroalkyl having one to four carbon atoms) or fluoroalkoxy radical, (e.g.
perfluoroalkoxy having one to four carbon atoms).
Preferred comonomers with vinylidene fluoride are perfluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, and pentafluoropropylene.
Partlcularly preferred are the fluorinated polymers produced by copolymerizing perfluoropropylene and .. . ...
`` i3322~
vlnylldene fluorlde, as descrlbed ln U.S. Pat. Nos. 3,051,677 (Rexford) and 3,318,854 lHonn et al.) and those polymers produced by copolymerlzlng perfluoropropylene, vlnylldene fluorlde and tetrafluoroethylene as descrlbed ln U.S. Pat. No. 2,968,649 (Pailthorp et al). The elastomeric copolymers of perfluoro-propylene and vlnylldene fluorlde havlng between about 15 and about 50 mole percent perfluoropropylene, optlonally wlth the addltlon of up to S to 30 mole percent tetrafluoroethylene, are partlcularly useful.
Some of the organophosphltes and organophosphates useful ln thls lnventlon can be represented by the general formula R2 ' Rl ~ O_p_(o)~ I
0 b where a ls 1 or 0, (where a ls 0 the compound depicted ls organo-phosphlte and where a 1~ 1 the compound deplcted ls organophos-phate) b ls an lnteger of 1 to 4 and equal to the valence of R~
pl ls a monovalent or polyvalent, (l.e. 2 to 4), organlc radlcal, preferably the resldue of a phenol, alcohol, dlphenol, dlol or polyol, such as ethylene glycol, 2,4-dl-tert.butylphenol, pen-taerythrltol, 4-nonylphenol, benzylalcohol, 4-chlorophenol, 1,1,1-trlmethylolpropane and the llke; the R2 groups, whlch can be the same or dlfferent, are monovalent organlc radlcals havlng from 1 to 30 carbon atoms and can be ~elected from substltuted and unsub-stltuted aryl, alkyl, or comblnatlons thereof such a3 aralkyl, and cycloalkyl groups. Rl and R2 groups can contaln heteroatoms such as 0 and N and can be ~ -8- 13322~
substituted with non-interferring substituents such as chlorine, fluorine, cyano, alkyl (branched and straight chain), alkoxy, acyl, and amidocarbonyl.
Many of organophosphites and organophosphates useful in his invention are known compounds and are, respectively, esters of phosphorous and phosphoric acids.
Synthesis can be carried out by reaction of the desired organic hydroxy compound with phosphorus trichloride (for phosphite esters), or with phosphorus oxychloride (for phosphate esters). Many examples of both organophosphites and organophosphates are available commercially, and blends of such compounds can also be used. -Representative organophosphites and organophosphates include tris(2,4-di-tert.-butylphenyl) phosphite, bis(2,4-di-tert.-butylphenyl) pentaerythritol diphosphite, tris(4-nonylphenyl) phosphite, trisl4-(1-phenylethyl)phenyl] phosphite, tetrakis~2,4-di-tert.-butylphenyl)-4,4'-bisphenylene . diphosphite, tris(4-methylphenyl) phosphite, trisl4--hlorophenyl) phosphite, decyl diphenyl phosphite, tris~2,4-di-tert.-butylphenyl) phosphate, tris(4-methylphenyl) phosphate, tris(4-nonylphenyl) phosphate, tris(4-chlorophenyl) phosphate, 2-ethylhexyl diphenyl phosphate, and blends thereof.
The addition of fluorocarbon polymer and organophosphite or organophosphate to the thermoplastic hydrocarbon polymer can be accomplished by any o~ the means conveniently employed to add adjuvants to polymers.
Thus the fluorocarbon polymer and organopho~phite or organophosphate compounds can be added to the tllermoplastic hydrocarbon polymer in a Banbury mixer, or . . , , : :
- ~ I332253 g a mixing extruder. Generally, the mixing operation is carried out at a temperature above the melting point of the polymer to provide uniform distribution of the fluorocarbon polymer and organophosphite or organophosphate throughout-the thermoplastic hydrocarbon polymer. The processing aid composition can be prepared by blending the components using any of the means conveniently employed to add adjuvants to polymers. Thus the fluorocarbon polymer, organophosphite or organophosphate and any other adjuvants can be blended usinq a Banbury mixer, a mixing extruder or can be dry blended using a mixer. Generally, the mixing operation 15 is carried out at a temperature above the meltlng point of the polymers to provide uniform distribution of components ~n said processing aid composition.
The amount of organophosphite or organophosphate and fluorocarbon polymer in said extrudable composition 20 and said processing aid composition can vary and will depend upon such factors as the particular thermoplastic hydrocarbon polymer used, the organophosphite or organophosphate used, the fluorocarbon polymer used, and the extrusion conditions. Stated functionally, the 5 amount of organophosphite or organophosphate and the amount of fluorocarbon polymer used in the extrudable composltion will be those amounts sufficient to reduce melt defects in extruded hydrocarbon polymers.
Generally, the weight of said fluorocarbon polymer 30 present ~n said extrudable composition or in said processing aid composition and the weight of said organophosphite or organophosphate present in said extrudable composition or in said processing aid composition are in a ratio of 1/1 to 1/5, and preferably `
35 in a ratio of 1/2 to 1/4. Generally said fluorocarbon -polymer will be present in said extrudable composition at ~ ~;
a concentration of 0.005 to 0.2 weight percent, and organophosphite or organophosphate will be present in the extrudable composition at a concentration of 0.01 to 0.8 û" . ~
-lo- 13322~3 weight percen~ based on the weight of the thermoplastic extrudable composition. Generally, the fluorocarbon polymer and organophosphite or organophosphate will be the_major or predominant components of said processing aid composition, and preferably said processing aid - -composition will contain 10 to 90 weight percent of organophosphite or organophosphate and 10 to 50 weight percent of fluorocarbon polymer, where said weight percent is based on total processing aid composition weight.
This invention is useful in the extrusion of thermoplastic hydrocarbon polymers, which includes for example, the extrusion of films, extrusion blow molding, injection molding, pipe, wire or cable extrusion, and - fiber production.
The following examples are offered to aid in a better understanding of the present invention and are not to be unnecessarily construed as limiting the scope thereof.
EXAMPLES 1-5 and COMP~RATIVE EXAMPLES C1 to C9 These exa~ples illustrate the use of - organophosphites and an organophosphate in conjunction with a fluorocarbon polymer in the extrusion of polyethylene.
The polyethylene used was a commercial linear low density pol~ethylene ~LLDPE) with a melt index of 1.0, containing about 2 weight percent butene-l comonomer and 0.03 weight percent of the antioxidant, octadecyl-3-(3,5-di-tert,-butyl-4-hydroxyphenyl) propionate.
The organophosphites u~ed were-tris~2,3-di-tert.-butylphenyl) phosphite ( P-l ), bis(2,4-di-tert.-butylphenyl) pentaerythritol diphosphite (P-2), tris(4-nonylphenyl) phosphite (P-3) and " ..
13322~
tris(4-methylphenyl) phosphite ~P-4). The organophosphate used wa~ trls(4-methylphenyl) phosphate ~PA-l~.
The fluorocarbon polymer used was DYNAMART~ Brand Polymer Processing Additive, FX-9163, a copolymer of vinylidene fluoride and hexafluoropropylene, Mooney viscosity of 33 ~as determined by ASTM D1646-81, ML 1~10 at 121C), containing 10 weight percent inorganic partitioning agent. FX-9613 is a free-flowing powder.
Compositions containing FX-9613 were prepared on a production scale, continuous Banbury mixing system. The initial blending of FX-9613 and the polyethylene resin was done on a ribbon blender which was fed continuously to a Mixtrument mixer. Following extrusion the material -was pelletized. Fluorine analyses performed according to the procedure described in the 3M Company brochure "Parr Bomb Analytical Method for Determining Total Organic Fluorine Concentration in Polyethylene", brochure number 98-0211-2542-6, issued 12/86) of the resin confirmed the presence of the desired level of FX-9613. The polyethylene resin used in compositions which dld not contain FX-9613 ~imilarly mixed to eliminate the effect of shear history in comparison with the FX-9613 containing blends.
Further compounding of both FX-9613 containing compositions and non-FX-9613 containing compositions w~th ~ -P-l, P-2, P-3 and P-4 organophosphites and PA-l 1 oeganophosphate was done on an HBI System 40 Torque Rheometer using a Rheomix 3000 mixer. A residence time of three minutes at 50 rpm was sufficient in each case to obtain a constant torque with a final melt temperature of 200-210C. The fully compounded resins were ground to facilitate feeding to the capillary rheometer. ~;
Rheological studies were done on an Instron Model 4202 system with a 3210 Capillary Rheometer using a 0.508 ;
mm die with length/diameter ratio of 40 and a 60 degree entrance angle. In these examples, two different 0.508 . . . , . - ,: ~ . , : -.: - .:
." . . .. . . ~ ~ ~ .
-12~ 133225~ :
mm die (nominal diameter) were used. A dwell time of 1 minutes and a temperature of 210C were used.
Equilibrium viscosities measured at a 600 sec~l shear rate were determined. The viscosities are uncorrected.
The extrudate was sampled and photomicrographs of air-cooled capillary extrudates were made. The photomicrographs were visually studied to determine the onset of melt defects.
The extrudable compostions used in the examples and the results of the rheological studies are summarized in Table 1.
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-14- ~ 3322~3 The data show that melt fracture in extruded polyethylen`e filaments occurs at higher shear rates in the presence of both fluorocarbon polymer and organophosphite or organophosphate. Also, the -equilibrium resin viscosity is significantly lower when both additives, i.e. fluorocarbon polymer and organophosphite or organophosphate are present. The phosphite or phosphate esters alone have little effect on shear rate or viscosity.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.
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At hlgher shear rate the extrudate can undergo "contlnuous melt fracture" becomlng grossly distorted. At rates lower than those at whlch contlnuous melt fracture ls flrst observed, LLDPE and HDPE can also suffer from "cycllc melt fracture", ln whlch the extrudate surface varles from smooth to rough. The authors state that lowerlng the shear stress by ad~ustlng the processlng condltlons or changlng the dle can avold these defects to a certaln extent, but not wlthout creatlng a whole new set of problems. For example, extruslon at a hlgher temperature can result ln weaker bubble walls ln tubular fllm extruslon, and a - -~
wlder dle gap can affect fllm orlentatlon. The authors state that the use of fluorocsrbon elastomer processlng alds can permlt the operation of extruders with narrower die gaps and lower melt temperatures. Others have also descrlbed the use of fluorocarbon elastomers as processlng alds, see for example, De Smedt, C., Nam, S., "The Processlng Benefits of Fluoroelastomer Appllcation ln LLDPE," Plastlcs and Rubber Processln~ and APpllcatlons~ 8, No. 1, (1987), pp. 11-16; U.S. Pat. No's. 3,125,547 (Blat~), and 4,581,406 (Hedberg et al.).
Organophosphlte compounds have been used as antloxldants ln polyoleflns. European Pat. Appl. EP 227948 A2 (Horn et al) published July 8, 1987 disclose that a comblnatlon of a trls(alkylphenyl) phosphlte and a dlalkyl thiodlpropionate added ~
to polyolefins lmproves melt processlblllty. ~ ;
The present lnventlon provldes an extrudable composltlon comprlslng ~ -.~ .
. .
, . . ..
r ~ ~ 3 3 2 2 ~ 3 60557-3579 (A) thermoplastic olefin polymer, as the major or predominant component of the composition, (B) organophosphite, organophosphate, or blends thereof, and (C) fluorocarbon polymer where the weight ratio of said fluorocarbon polymer to said organophosphite, organo-phosphate, or blend thereof is in the range of 1/1 to 1/5, the concentration of said fluorocarbon polymer is 0.005 to 0.1 weight percent, and the concentration of said organophosphite, organophosphate, or blend thereof is 0.01 to 0.2 weight percent based on the total composition weight.
Melt defects are those defects sometimes appearing in extruded thermoplastic hydrocarbon polymers such as sharkskin, melt fracture and cyclic melt fracture.
Generally, the weight of said fluorocarbon polymer in said extrudable composition and the weight of said organo- ~;
phosphite or organophosphate present in said extrudable composition are in a ratio of 1/1 to 1/5. Where said extrudable ;
composition is a final extrudate, i.e. the final product for example a film, the concentration of said fluorocarbon polymer in said composition is 0.005 to 0.2 weight percent and the ~ ~-concentration of said organophosphite or organophosphate in said extrudable composition is 0.01 to 0.8 weight percent, where said weight percent is based on the total weight of the extrudate.
This invention also provides a processing additive composition suitable for addition to thermoplastic polymers to improve extension characteristics consisting essentally of fluorocarbon polymer and organophosphite, organophosphate, or ~ ;
:. ' '' ~' - 3a -1 3 3 2 2 ~ .~ 60557-3579 blend thereof such that the weight of said fluorocarbon polymer in said composition and the weight of said organophosphite, organophosphate, or blend thereof in said composition are in a ratio of 1/1 to 1/5, the fluorocarbon polymer and organophosphite, organophosphate or blend thereof, being the predominant component of said processing additive composition and the concentration of said fluorocarbon polymer in said composition is 14 to 50 weight percent, and the concentration of said organo-phosphite, organophosphate or blend thereof in said composition is 50 to 83 weight percent, where said weight percent is based on total additive composition weight. Optionally, said processing -:
aid composition further comprises other components such as adjuvants, e.g. antioxidants, normally added to thermoplastic hydrocarbon polymers. The concentration of said fluorocarbon polymer, organophosphite or organophosphate and any other adjuvants in said processing aid composition can vary depending upon the processorls requirement, but generally, the fluorocarbon ~ , .
,~. . .
~ ,' , , " : ~ , ' . ' ' , . ' :: . :: : ' . :
'' ', , .'': ,'' " '' ' ' ' ~....... ~
~4~ 13322~3 . .
polymer and organophosphite or organophosphate will be the major or predominant component of the composition.
The present invention is effective in reducing melt defects not ~nly by delaying the onset of melt defects in thermoplastic hydrocarbon polymers, e.g.
polyolefins, to higher extrusion shear rates than could be achieved using the same level of the fluorocarbon polymer alone, but also by permitting extruder to equilibrate and produce melt-defect-free extrudate in less time than would be required for an extrudate containing the same levEl of fluorocarbon polymer alone at the same extrusion conditions. This permits the use of l~_s fluorocarbon polymer, as well as higher extruder throughputs and shorter extruder start up times resulting in more ecffnomical thermoplastic hydro~larbon ~oIymer 4 extrusion. ~ ih ~ S
The thermoplastic hydrocarbon polymers to which the fluorocarbon polymers and organophosphite or organophosphate are added comprise polymers obtained by the homopolymerization or copolymerization of olefins, as well as copolymers of one or more olefins and up to about 30 weight percent, but preferably 20 weight percent or less, of one or more monomers which are copolymerizable with such olefins, e.q. vinyl ester compounds such as vinyl acetate. Said olefins have the general structure CH2~CHR, where R is a hydro~en or an alkyl radical, and generally, the alkyl radical contains not more than 10 carbon atoms and preferably one to four carbon atoms.
Repre~entative oleflns are ethylene, propylene and butene-1. Representative monomers which are copolymerizable with said olefins are vinyl ester monomers such a~ vinyl acetate, vinyl propionate, vinyl butyrate, vinyl chloroacetate, vinyl chloropropionate, acrylic and alpha-alkyl acrylic acid monomers, and their alkyl esters, amides, and nitriles such as acrylic acid, methacrylic acid, ethacrylic acid, methyl acrylate, ethyl acrylate, N,N-dimethyl acry~amide, methacrylamide, .
. . - : . , ,.. :- . ~ . , -j,t : , :. ' ' ' ' ' ;~' ' , ' ' : , , -5- 1 3 3 2 2~3 acrylonltrile, vinyl aryl monomers such as styrene, o-methoxystyrene, p-methoxystyrene, and vinyl naphthalene, vinyl and vinylidene halide monomers such as vinyl chloride, vinylidene chloride, vinylidene bromide, alkyl ester monomers of maleic and fumaric acid such as dimetilyl ~aleate, diethyl maleate, vinyl alkyl ether monomers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ethec, 2-chloroethyl vinyl ether, and vinyl pyridine monomers, N-vinyl carbazole monomers~ and N-vinyl pyrolidine monomers. The thermoplastic hydrocarbon polymers also include the metallic salts of said olefin copolymers, or blends thereof, which contain free carboxylic acid groups. Illustrative of the metals which can be used to provide the salts of said carboxylic acid polymers are the one, two and three valence metals such as sodium, lithium, potassillm, calcium, magnesium, aluminum, barium, zinc, zirconium, beryllium, iron, nickel and cobalt. The thermoplastic hydrocarbon polymers also include blends of thermoplastic hydrocarbon polymers with other thermoplastic hydrocarbon polymers or blends thereof containing conventional adjuvants such as antioxidants, light stabilizers, fillers, antiblocking agents and pigments.
Representative examples of thermoplastic hydrocarbon polymers useful in this invention are polyethylene, polypropylene, polybutene-l, poly(3-methylbutene), poly(4-methylpentene) and copolymers of ethylene with-propylene, butene-l, hexene-l, octene-l, decene-l, 4-methyl-1-pentene and octadecene-l.
Representative blends of thermoplastic hydrocarbon ! polymers useful in this invention are blends of polyethylene and polypropylene, low-denslty polyethylene and high-density polyetnylene, and polyethylene and olefin copolymers containing said copolymerizable monomers, some of which are described above, e.g., ethylene and acrylic acid copolymers; ethylene and methyl ~ 6- 13322~
acrylate copolymers, ethylene and ethyl acrylate copolymers, ethylene and vinyl acetate copolymers, ethylene, acrylic acid, and ethyl acrylate copolymers, and ethylene, acrylic acid, and vinyl acetate copolymers.
The preferred thermoplastic hydrocarbon polymers are homopolymers of ethylene and propylene and copolymers of ethylene and l-butene, l-hexene, l-octene, 4-methyl-1-pentene, propylene, vinyl acetate, and methyl acrylate.
The thermoplastic hydrocarbon polymers may be used in the form of powders, pellets, granules, or any other extrudable form. ~ ~
The fluorocarbon or fluorinated polymers useful in ~ ~ ;
this invention are generally homopolymsrs and copolymers of fluorinated olefins having a fluorine atom to carbon atom ratio of at least 1:2, preferably at least 1:1.
Homopolymers which can be used are those derived, for example, from vinylidene fluoride and vinyl fluoride. -~
Copolymers of fluorinated olefins can be those derived, _ for example, from vinylidene fluoride, and one or more addltional olefins, which can be fluorinated, e.g.
hexafluoropropylene, and non-fluorinated, e.g. propylene.
- - Preferred fluorocarbon polymers are copolymers of vinylidene fluoride with at least one terminally unsaturated fluoromonoolefin containing at least one fluorine atom on each double-bonded carbon atom, each carbon atom of said fluoromonoolefin being substitueed only with fluorine, chlorine, bromine, hydrogen or lower fluoroalkyl (e.g. perfluoroalkyl having one to four carbon atoms) or fluoroalkoxy radical, (e.g.
perfluoroalkoxy having one to four carbon atoms).
Preferred comonomers with vinylidene fluoride are perfluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, and pentafluoropropylene.
Partlcularly preferred are the fluorinated polymers produced by copolymerizing perfluoropropylene and .. . ...
`` i3322~
vlnylldene fluorlde, as descrlbed ln U.S. Pat. Nos. 3,051,677 (Rexford) and 3,318,854 lHonn et al.) and those polymers produced by copolymerlzlng perfluoropropylene, vlnylldene fluorlde and tetrafluoroethylene as descrlbed ln U.S. Pat. No. 2,968,649 (Pailthorp et al). The elastomeric copolymers of perfluoro-propylene and vlnylldene fluorlde havlng between about 15 and about 50 mole percent perfluoropropylene, optlonally wlth the addltlon of up to S to 30 mole percent tetrafluoroethylene, are partlcularly useful.
Some of the organophosphltes and organophosphates useful ln thls lnventlon can be represented by the general formula R2 ' Rl ~ O_p_(o)~ I
0 b where a ls 1 or 0, (where a ls 0 the compound depicted ls organo-phosphlte and where a 1~ 1 the compound deplcted ls organophos-phate) b ls an lnteger of 1 to 4 and equal to the valence of R~
pl ls a monovalent or polyvalent, (l.e. 2 to 4), organlc radlcal, preferably the resldue of a phenol, alcohol, dlphenol, dlol or polyol, such as ethylene glycol, 2,4-dl-tert.butylphenol, pen-taerythrltol, 4-nonylphenol, benzylalcohol, 4-chlorophenol, 1,1,1-trlmethylolpropane and the llke; the R2 groups, whlch can be the same or dlfferent, are monovalent organlc radlcals havlng from 1 to 30 carbon atoms and can be ~elected from substltuted and unsub-stltuted aryl, alkyl, or comblnatlons thereof such a3 aralkyl, and cycloalkyl groups. Rl and R2 groups can contaln heteroatoms such as 0 and N and can be ~ -8- 13322~
substituted with non-interferring substituents such as chlorine, fluorine, cyano, alkyl (branched and straight chain), alkoxy, acyl, and amidocarbonyl.
Many of organophosphites and organophosphates useful in his invention are known compounds and are, respectively, esters of phosphorous and phosphoric acids.
Synthesis can be carried out by reaction of the desired organic hydroxy compound with phosphorus trichloride (for phosphite esters), or with phosphorus oxychloride (for phosphate esters). Many examples of both organophosphites and organophosphates are available commercially, and blends of such compounds can also be used. -Representative organophosphites and organophosphates include tris(2,4-di-tert.-butylphenyl) phosphite, bis(2,4-di-tert.-butylphenyl) pentaerythritol diphosphite, tris(4-nonylphenyl) phosphite, trisl4-(1-phenylethyl)phenyl] phosphite, tetrakis~2,4-di-tert.-butylphenyl)-4,4'-bisphenylene . diphosphite, tris(4-methylphenyl) phosphite, trisl4--hlorophenyl) phosphite, decyl diphenyl phosphite, tris~2,4-di-tert.-butylphenyl) phosphate, tris(4-methylphenyl) phosphate, tris(4-nonylphenyl) phosphate, tris(4-chlorophenyl) phosphate, 2-ethylhexyl diphenyl phosphate, and blends thereof.
The addition of fluorocarbon polymer and organophosphite or organophosphate to the thermoplastic hydrocarbon polymer can be accomplished by any o~ the means conveniently employed to add adjuvants to polymers.
Thus the fluorocarbon polymer and organopho~phite or organophosphate compounds can be added to the tllermoplastic hydrocarbon polymer in a Banbury mixer, or . . , , : :
- ~ I332253 g a mixing extruder. Generally, the mixing operation is carried out at a temperature above the melting point of the polymer to provide uniform distribution of the fluorocarbon polymer and organophosphite or organophosphate throughout-the thermoplastic hydrocarbon polymer. The processing aid composition can be prepared by blending the components using any of the means conveniently employed to add adjuvants to polymers. Thus the fluorocarbon polymer, organophosphite or organophosphate and any other adjuvants can be blended usinq a Banbury mixer, a mixing extruder or can be dry blended using a mixer. Generally, the mixing operation 15 is carried out at a temperature above the meltlng point of the polymers to provide uniform distribution of components ~n said processing aid composition.
The amount of organophosphite or organophosphate and fluorocarbon polymer in said extrudable composition 20 and said processing aid composition can vary and will depend upon such factors as the particular thermoplastic hydrocarbon polymer used, the organophosphite or organophosphate used, the fluorocarbon polymer used, and the extrusion conditions. Stated functionally, the 5 amount of organophosphite or organophosphate and the amount of fluorocarbon polymer used in the extrudable composltion will be those amounts sufficient to reduce melt defects in extruded hydrocarbon polymers.
Generally, the weight of said fluorocarbon polymer 30 present ~n said extrudable composition or in said processing aid composition and the weight of said organophosphite or organophosphate present in said extrudable composition or in said processing aid composition are in a ratio of 1/1 to 1/5, and preferably `
35 in a ratio of 1/2 to 1/4. Generally said fluorocarbon -polymer will be present in said extrudable composition at ~ ~;
a concentration of 0.005 to 0.2 weight percent, and organophosphite or organophosphate will be present in the extrudable composition at a concentration of 0.01 to 0.8 û" . ~
-lo- 13322~3 weight percen~ based on the weight of the thermoplastic extrudable composition. Generally, the fluorocarbon polymer and organophosphite or organophosphate will be the_major or predominant components of said processing aid composition, and preferably said processing aid - -composition will contain 10 to 90 weight percent of organophosphite or organophosphate and 10 to 50 weight percent of fluorocarbon polymer, where said weight percent is based on total processing aid composition weight.
This invention is useful in the extrusion of thermoplastic hydrocarbon polymers, which includes for example, the extrusion of films, extrusion blow molding, injection molding, pipe, wire or cable extrusion, and - fiber production.
The following examples are offered to aid in a better understanding of the present invention and are not to be unnecessarily construed as limiting the scope thereof.
EXAMPLES 1-5 and COMP~RATIVE EXAMPLES C1 to C9 These exa~ples illustrate the use of - organophosphites and an organophosphate in conjunction with a fluorocarbon polymer in the extrusion of polyethylene.
The polyethylene used was a commercial linear low density pol~ethylene ~LLDPE) with a melt index of 1.0, containing about 2 weight percent butene-l comonomer and 0.03 weight percent of the antioxidant, octadecyl-3-(3,5-di-tert,-butyl-4-hydroxyphenyl) propionate.
The organophosphites u~ed were-tris~2,3-di-tert.-butylphenyl) phosphite ( P-l ), bis(2,4-di-tert.-butylphenyl) pentaerythritol diphosphite (P-2), tris(4-nonylphenyl) phosphite (P-3) and " ..
13322~
tris(4-methylphenyl) phosphite ~P-4). The organophosphate used wa~ trls(4-methylphenyl) phosphate ~PA-l~.
The fluorocarbon polymer used was DYNAMART~ Brand Polymer Processing Additive, FX-9163, a copolymer of vinylidene fluoride and hexafluoropropylene, Mooney viscosity of 33 ~as determined by ASTM D1646-81, ML 1~10 at 121C), containing 10 weight percent inorganic partitioning agent. FX-9613 is a free-flowing powder.
Compositions containing FX-9613 were prepared on a production scale, continuous Banbury mixing system. The initial blending of FX-9613 and the polyethylene resin was done on a ribbon blender which was fed continuously to a Mixtrument mixer. Following extrusion the material -was pelletized. Fluorine analyses performed according to the procedure described in the 3M Company brochure "Parr Bomb Analytical Method for Determining Total Organic Fluorine Concentration in Polyethylene", brochure number 98-0211-2542-6, issued 12/86) of the resin confirmed the presence of the desired level of FX-9613. The polyethylene resin used in compositions which dld not contain FX-9613 ~imilarly mixed to eliminate the effect of shear history in comparison with the FX-9613 containing blends.
Further compounding of both FX-9613 containing compositions and non-FX-9613 containing compositions w~th ~ -P-l, P-2, P-3 and P-4 organophosphites and PA-l 1 oeganophosphate was done on an HBI System 40 Torque Rheometer using a Rheomix 3000 mixer. A residence time of three minutes at 50 rpm was sufficient in each case to obtain a constant torque with a final melt temperature of 200-210C. The fully compounded resins were ground to facilitate feeding to the capillary rheometer. ~;
Rheological studies were done on an Instron Model 4202 system with a 3210 Capillary Rheometer using a 0.508 ;
mm die with length/diameter ratio of 40 and a 60 degree entrance angle. In these examples, two different 0.508 . . . , . - ,: ~ . , : -.: - .:
." . . .. . . ~ ~ ~ .
-12~ 133225~ :
mm die (nominal diameter) were used. A dwell time of 1 minutes and a temperature of 210C were used.
Equilibrium viscosities measured at a 600 sec~l shear rate were determined. The viscosities are uncorrected.
The extrudate was sampled and photomicrographs of air-cooled capillary extrudates were made. The photomicrographs were visually studied to determine the onset of melt defects.
The extrudable compostions used in the examples and the results of the rheological studies are summarized in Table 1.
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-- u~ 00 I I p, p, p, p, p, p, I I P P~ P P~ a . .,, ~.
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-14- ~ 3322~3 The data show that melt fracture in extruded polyethylen`e filaments occurs at higher shear rates in the presence of both fluorocarbon polymer and organophosphite or organophosphate. Also, the -equilibrium resin viscosity is significantly lower when both additives, i.e. fluorocarbon polymer and organophosphite or organophosphate are present. The phosphite or phosphate esters alone have little effect on shear rate or viscosity.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention.
~
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Claims (14)
1. An extrudable composition comprising (A) thermoplastic olefin polymer, as the major or predominant component of the composition, (B) organophosphite, organophosphate, or blends thereof, and (C) fluorocarbon polymer where the weight ratio of said fluorocarbon polymer to said organophosphite, organophosphate, or blend thereof is in the range of 1/1 to 1/5, the concentration of said fluorocarbon polymer is 0.005 to 0.1 weight percent, and the concentration of said organophosphite, organophosphate, or blend thereof is 0.01 to 0.2 weight percent based on the total composition weight.
2. The extrudable composition of claim 1 wherein the concentration of said fluorocarbon polymer in said composition is 0.005 to 0.2 weight percent and the concentration of said organophosphite, organophosphate, or blend thereof in said composition is 0.01 to 0.8 weight percent, where said weight percent is based on the weight of said extrudable composition.
3. The composition of claim 1 wherein said thermoplastic hydrocarbon polymer is selected from the group consisting of homopolymers or olefin, copolymers of olefins, and copolymers of one or more olefins and up to 30 weight percent of one or more monomers which are copolymerized with such olefins, and blends thereof.
4. The composition of claim 3 wherein said thermoplastic hydrocarbon polymer is selected from the group consisting of homopolymers or ethylene, homopolymers of propylene, copolymers of ethylene and 1-butene, copolymers of ethylene and 1-hexene, copolymers of ethylene and 1-octene, copolymers of ethylene and 4-methyl-1-pentene, copolymers of ethylene and propylene, copolymers of ethylene and ethyl vinyl acetate, copolymers of ethylene and ethyl methacrylate, and blends thereof.
5. The composition of claim 1 wherein said organophosphite or organophosphate have the general formula where a is 1 or 0, b is an integer of 1 to 4 and equal to the valence of R1, R1 is a monovalent or polyvalent organic radical, the R2 groups, which can be the same or different, are monovalent organic radicals having from 1 to 30 carbon atoms and can be selected from substituted and unsubstituted aryl, alkyl, or combinations thereof and cycloalkyl groups, and R1 and R2 groups can contain heteroatoms and can be substituted with non-interferring substituents.
6. The composition of claim 5 wherein said organophosphite, organophosphate, or blend thereof is selected from the group consisting of tris(2,4-di-tert.-butylphenyl) phosphite, bis(2,4-di-tert.-butylphenyl) pentaerythritol diphosphite, tris(4-nonylphenyl) phosphite, tris[4-(1-phenylethyl)phenyl] phosphite, tetrakis(2,4-di-tert.-butylphenyl)-4,4'-bisphenylene diphosphite, tris(4-methylphenyl) phosphite, tris(4-chlorophenyl) phosphite, decyl diphenyl phosphite, tris(2,4-di-tert.-butylphenyl) phosphate, tris(4-methylphenyl) phosphate, tris(4-nonylphenyl) phosphate, tris(4-chlorophenyl) phosphate, 2-ethylhexyl diphenyl phosphate, and blends thereof.
7. The composition of claim 1 wherein said fluorocarbon polymer is selected from the group consisting of copolymers derived from fluorinated monomers and one or more additional fluorinated or non-fluorinated monomers, or homopolymers derived from fluorinated monomers.
8. The composition of claim 7 wherein said fluorocarbon polymer is a copolymer of vinylidene fluoride and hexafluoropropylene.
9. The composition of claim 7 wherein said fluorocarbon polymer is a copolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene.
10. The composition of claim 1 wherein said thermoplastic hydrocarbon polymer is a copolymer of ethylene and butene-1, said organophosphite is selected from the group consisting of tris(2,3-di-tert.-butylphenyl) phosphite, bis(2,4-di-tert.-butylphenyl) pentaerythritol diphosphite, and tris(4-nonylphenyl) phosphite, and said fluorocarbon polymer is a copolymer of vinylidene fluoride and hexafluoropropylene.
11. The composition of claim 1 wherein said thermoplastic-hydrocarbon polymer is a copolymer of ethylene and butene-1, said organophosphate is tris(4-methylphenyl) phosphate and said fluorocarbon polymer is a copolymer of vinylidene fluoride and hexafluoropropylene.
12. A processing additive composition suitable for addition to thermoplastic polymers to improve extension characteristics consisting essentially of fluorocarbon polymer and organo-phosphite, organophosphate, or blend thereof such that the weight of said fluorocarbon polymer in said composition and the weight of said organophosphite, organophosphate, or blend thereof in said composition are in a ratio of 1/1 to 1/5, the fluorocarbon polymer and organophosphite, organophosphate or blend thereof, being the predominant component of said processing additive composition and the concentration of said fluorocarbon polymer in said composition is 14 to 50 weight percent, and the concentration of said organophosphite, organophosphate or blend thereof in said composition is 50 to 83 weight percent, where said weight percent is based on total additive composition weight.
13. The composition of claim 12 further comprising other adjuvants which are added to thermoplastic hydrocarbon polymers.
14. A method of reducing melt defects in extruded hydro-carbon polymers using the additive compositions of claim 12 which comprises admixing with said thermoplastic hydrocarbon polymer said additive composition such that the concentration of said organophosphite, organophosphate, or blend thereof is 0.01 to 0.2 weight percent, and the concentration of said fluorocarbon polymer is 0.005 to 0.1 weight percent based on the total weight of the thermoplastic hydrocarbon polymer, fluorocarbon polymer and organophosphite, organophosphate, or blend thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/182,466 US4863983A (en) | 1988-04-15 | 1988-04-15 | Extrudable thermoplastic hydrocarbon polymer composition |
| US182,466 | 1988-04-15 |
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|---|---|
| CA1332253C true CA1332253C (en) | 1994-10-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000591514A Expired - Fee Related CA1332253C (en) | 1988-04-15 | 1989-02-20 | Extrudable thermoplastic hydrocarbon polymer composition |
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|---|---|
| US (1) | US4863983A (en) |
| JP (1) | JPH0243267A (en) |
| KR (1) | KR900016354A (en) |
| AU (1) | AU618336B2 (en) |
| CA (1) | CA1332253C (en) |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0447535B1 (en) * | 1989-10-06 | 1996-04-17 | E.I. Du Pont De Nemours And Company | Processing aid for polymers |
| JPH0637075B2 (en) * | 1989-10-18 | 1994-05-18 | 三菱油化株式会社 | Molding method for resin pipes |
| US5149576A (en) * | 1990-11-26 | 1992-09-22 | Kimberly-Clark Corporation | Multilayer nonwoven laminiferous structure |
| US5145727A (en) * | 1990-11-26 | 1992-09-08 | Kimberly-Clark Corporation | Multilayer nonwoven composite structure |
| US5162151A (en) * | 1991-01-23 | 1992-11-10 | Hoechst Celanese Corporation | Polyphenylene sulfide monofilaments and fabrics therefrom |
| WO1993018090A1 (en) * | 1992-03-10 | 1993-09-16 | The Dow Chemical Company | Ignition resistant polycarbonate blends |
| US5328948A (en) * | 1992-09-23 | 1994-07-12 | Ausimont, U.S.A., Inc. | Stabilization of halopolymers with ionomers |
| CA2124237C (en) | 1994-02-18 | 2004-11-02 | Bernard Cohen | Improved nonwoven barrier and method of making the same |
| US5688157A (en) * | 1994-04-05 | 1997-11-18 | Kimberly-Clark Worldwide, Inc. | Nonwoven fabric laminate with enhanced barrier properties |
| US5482765A (en) * | 1994-04-05 | 1996-01-09 | Kimberly-Clark Corporation | Nonwoven fabric laminate with enhanced barrier properties |
| CA2136576C (en) | 1994-06-27 | 2005-03-08 | Bernard Cohen | Improved nonwoven barrier and method of making the same |
| US5550193A (en) * | 1994-12-07 | 1996-08-27 | Novacor Chemicals Ltd. | Melt fracture elimination in film production |
| AU4961696A (en) | 1994-12-08 | 1996-06-26 | Kimberly-Clark Worldwide, Inc. | Method of forming a particle size gradient in an absorbent article |
| CA2153278A1 (en) | 1994-12-30 | 1996-07-01 | Bernard Cohen | Nonwoven laminate barrier material |
| US5459187A (en) * | 1995-02-13 | 1995-10-17 | Novacor Chemicals Ltd. | Polyethylene with reduced melt fracture |
| AU5747396A (en) * | 1995-05-25 | 1996-12-11 | Kimberly-Clark Worldwide, Inc. | Filter matrix |
| ZA965786B (en) | 1995-07-19 | 1997-01-27 | Kimberly Clark Co | Nonwoven barrier and method of making the same |
| US5710217A (en) * | 1995-09-15 | 1998-01-20 | Minnesota Mining And Manufacturing Company | Extrudable thermoplastic hydrocarbon compositions |
| US5834384A (en) | 1995-11-28 | 1998-11-10 | Kimberly-Clark Worldwide, Inc. | Nonwoven webs with one or more surface treatments |
| AU1198597A (en) * | 1995-12-22 | 1997-07-17 | Elf Atochem S.A. | Composition including a fluoroelastomer and a thermoplastic polyamide, and resulting film |
| DE19727981A1 (en) * | 1997-07-01 | 1999-01-07 | Buna Sow Leuna Olefinverb Gmbh | Molding compound based on ultra high molecular weight polyethylene and process for its production |
| ES2196597T3 (en) | 1997-07-18 | 2003-12-16 | Pirelli | OPTICAL FIBER CABLE WITH HIGH RESISTANCE TO DEGRADATION. |
| US6537932B1 (en) | 1997-10-31 | 2003-03-25 | Kimberly-Clark Worldwide, Inc. | Sterilization wrap, applications therefor, and method of sterilizing |
| US6013217A (en) * | 1997-12-22 | 2000-01-11 | Dow Corning Corporation | Method for extruding thermoplastic resins |
| US6365088B1 (en) | 1998-06-26 | 2002-04-02 | Kimberly-Clark Worldwide, Inc. | Electret treatment of high loft and low density nonwoven webs |
| AU1311100A (en) * | 1998-10-05 | 2000-04-26 | Bba Nonwovens Simpsonville, Inc. | Uv stabilized spunbond fabrics with enhanced trapezoidal tear |
| US6613704B1 (en) * | 1999-10-13 | 2003-09-02 | Kimberly-Clark Worldwide, Inc. | Continuous filament composite nonwoven webs |
| US6613268B2 (en) | 2000-12-21 | 2003-09-02 | Kimberly-Clark Worldwide, Inc. | Method of increasing the meltblown jet thermal core length via hot air entrainment |
| US7326751B2 (en) * | 2003-12-01 | 2008-02-05 | Kimberly-Clark Worlwide, Inc. | Method of thermally processing elastomeric compositions and elastomeric compositions with improved processability |
| US20050118435A1 (en) * | 2003-12-01 | 2005-06-02 | Kimberly-Clark Worldwide, Inc. | Films and methods of forming films having polyorganosiloxane enriched surface layers |
| US20060003154A1 (en) * | 2004-06-30 | 2006-01-05 | Snowden Hue S | Extruded thermoplastic articles with enhanced surface segregation of internal melt additive |
| US7285595B2 (en) * | 2004-06-30 | 2007-10-23 | Kimberly-Clark Worldwide, Inc. | Synergistic fluorochemical treatment blend |
| FR2899592B1 (en) * | 2006-04-05 | 2008-05-23 | Arkema Sa | EXTRUSION AID AGENT BASED ON PVDF |
| US20090053959A1 (en) | 2007-08-21 | 2009-02-26 | Sudhin Datta | Soft and Elastic Nonwoven Polypropylene Compositions |
| US20130130417A1 (en) | 2011-11-22 | 2013-05-23 | Jar-Yu WU | Manufacturing method of a light-emitting device |
| US9322114B2 (en) | 2012-12-03 | 2016-04-26 | Exxonmobil Chemical Patents Inc. | Polypropylene fibers and fabrics |
| JP2017533844A (en) * | 2014-10-27 | 2017-11-16 | ティパ コーポレイション リミティド | Biodegradable sheet |
| US10143998B2 (en) | 2016-02-05 | 2018-12-04 | Rohm And Haas Company | Activation energy reducers for catalytic oxidation of gaseous mixtures |
| EP4219617A1 (en) | 2022-01-31 | 2023-08-02 | Ingenia Polymers International S.A. | Functionalized-silicone based polyolefin processing aids |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3318854A (en) * | 1953-04-03 | 1967-05-09 | Minnesota Mining & Mfg | Fluorinated elastomeric copolymers |
| DE1078329B (en) * | 1955-04-27 | 1960-03-24 | Du Pont | Process for the production of an elastic copolymer from vinylidene fluoride and another fluoroolefin |
| US2968649A (en) * | 1958-12-04 | 1961-01-17 | Du Pont | Elastomeric terpolymers |
| NL133659C (en) * | 1960-02-05 | |||
| US3125547A (en) * | 1961-02-09 | 1964-03-17 | Extrudable composition consisting of | |
| US3245949A (en) * | 1963-01-07 | 1966-04-12 | Stanley A Murdock | Stabilized polyolefin polymer compositions |
| US3535276A (en) * | 1966-08-01 | 1970-10-20 | Argus Chem | Olefin polymers containing organic phosphate stabilizers |
| US3671487A (en) * | 1971-05-05 | 1972-06-20 | Gen Electric | Glass reinforced polyester resins containing polytetrafluoroethylene and flame retardant additives |
| IL75719A (en) * | 1984-07-18 | 1988-11-30 | Du Pont Canada | Polyolefin blends containing reactive agents |
| US4581406A (en) * | 1985-06-11 | 1986-04-08 | E. I. Du Pont De Nemours And Company | Fluoroelastomer containing polyethylene composition and process for extruding same |
| DE3523314A1 (en) * | 1985-06-29 | 1987-01-02 | Bayer Ag | THERMOPLASTIC POLYCARBONATE MOLDINGS |
| EP0227948B1 (en) * | 1985-11-29 | 1993-04-07 | Ge Specialty Chemicals, Inc. | Improved phosphite stabilizer compositions |
| JPS63110257A (en) * | 1986-10-28 | 1988-05-14 | Idemitsu Petrochem Co Ltd | Flame retardant resin composition |
-
1988
- 1988-04-15 US US07/182,466 patent/US4863983A/en not_active Expired - Fee Related
-
1989
- 1989-02-20 CA CA000591514A patent/CA1332253C/en not_active Expired - Fee Related
- 1989-03-13 JP JP1060598A patent/JPH0243267A/en active Pending
- 1989-04-04 KR KR1019890004959A patent/KR900016354A/en not_active Application Discontinuation
- 1989-04-12 AU AU32717/89A patent/AU618336B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| US4863983A (en) | 1989-09-05 |
| JPH0243267A (en) | 1990-02-13 |
| AU3271789A (en) | 1989-10-19 |
| AU618336B2 (en) | 1991-12-19 |
| KR900016354A (en) | 1990-11-13 |
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