CA2059945A1 - Electrically conductive blends of intrinsically conductive polymers and thermoplastic polymers and a process for their preparation - Google Patents
Electrically conductive blends of intrinsically conductive polymers and thermoplastic polymers and a process for their preparationInfo
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- CA2059945A1 CA2059945A1 CA002059945A CA2059945A CA2059945A1 CA 2059945 A1 CA2059945 A1 CA 2059945A1 CA 002059945 A CA002059945 A CA 002059945A CA 2059945 A CA2059945 A CA 2059945A CA 2059945 A1 CA2059945 A1 CA 2059945A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
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- 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
- C08L27/04—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 chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A conductive polymeric blend comprises an intrinsically conductive polymer, an insulating thermoplastic material and at least one additive selected from the group consisting of an impact modifier an ester-free plasticizer and an acidic surfactant. The thermoplastic material comprises a thermoplastic polymer. The conductive polymeric blend has a conductivity of greater than about 10-9 S/cm. Aprocess fro preparing conductive polymeric blends comprises the steps of forminga blend comprising an intrinsically conductive polymer an insulating thermoplastic material and at least one additive selected from the group consisting of an impact modifier an ester-free plasticizer and an acidic surfactant. The thermoplastic material comprises a thermoplastic polymer. The conductive polymeric blend has a conductivity of from of greater than yabout 10-9 S/cm.
A conductive polymeric blend comprises an intrinsically conductive polymer, an insulating thermoplastic material and at least one additive selected from the group consisting of an impact modifier an ester-free plasticizer and an acidic surfactant. The thermoplastic material comprises a thermoplastic polymer. The conductive polymeric blend has a conductivity of greater than about 10-9 S/cm. Aprocess fro preparing conductive polymeric blends comprises the steps of forminga blend comprising an intrinsically conductive polymer an insulating thermoplastic material and at least one additive selected from the group consisting of an impact modifier an ester-free plasticizer and an acidic surfactant. The thermoplastic material comprises a thermoplastic polymer. The conductive polymeric blend has a conductivity of from of greater than yabout 10-9 S/cm.
Description
2059~
- I -IILIIC'l'l~ICALL~' CONDUC'l`IVL~ l~LENl)S OF
IN'rl~INSlCALLY CONDUCT~V~ POLYMERS AND
Tl~ RMOPL~ST~C POLYMERS AND A PROCESS
FOl~rrHl~lK PREl'ARATlON
s TIICHNICAL FIELD
Tlle prescnt inventioll generally relates tu electrically conductive polymer blends. More particularly, the present invention relates to blends of intrinsically concluctive polymers an~l insula~ thermoplastic polymers, especially those 10 requiring thc use of a plasticizer. Specifically, the present invention relates to blends of polyalliline and polyvinyl chloride (PVC), including PVC plastisols, - clllorinaled polyelllylcllc, or olller thermoplastic polymer.
I~ACKGROUND ~RT
Intrinsically Conductive Polymers (ICP) have been studied since at the latest tlle 1970's. The term "ICP" refers to organic polymers which have (poly)-conjugated 7~-electron systems (e.g. double bonds, aromatic or heteroaromatic rings or triple l)on~ls). Lxamplcs of such polymers are polydiacetylene, polyacelylene(PAc), polypyrrole (PPy), polyaniline (P~NI), polytlliophene (PTh), 20 polyisolllionapl~ elle (l'l l N), polylleleroarylenvillylene (PArV), in wllicll tlle heteroarylene group can be the thiophene, furan or pyrrole, poly-p-phenylene (PpP), polyphtllalocyanine (PPhc) and the like, and their derivativcs (formed for example from monomers substiluted willl side chains or groups), their copolymers and thcir pllysical mixtures. They can exist in various states, each described by diEferent 25 cmpirical forlll-~ c, whicll can gellcrally be converted esscntially reversibly into one or the olher l)y (electro-) cllemical reactions such as oxidation, reduction, acid/alkali reaclion or comple.Ying. Tllese reac~ions are also occasionally known as "doping" or "compcnsatioll" in tlle literature, or can be regarded as "charging" ànd "discllarging"
in analogy ~vitll the electrochemical processes in batteries. At least one oE the 30 possil~le statcs is a vcry goo(l condllctor of electricity, c.g. llas a conductivily Or morc than 1 S/cm (in pure form), so one can speak of intrinsically conductive polyme;s.
20~99~5 ï l-cse rorms o~ thc ICI' are gencrally recognize(l as bcing polyraclical calionic or alliOIliC salts.
A goo(l overall revicw of Ihe intrinsically conductive polymers syntl~esize(l to cla~e wi~ll a cllcmical slructure suitablc for the present objective, is to bc foun~
in Synllle~ic Mclals, Issucs 17, 18, ancl 19 (1986), and in Synll~etic Metals, Issucs 27, 2~ an(l 29 (19S~ vllicll arc l~ercl)y incorporate(l I)y refcrcnce.
l~espite several polcntially useful properties e~lhibite~l by ICPs, tlleir use as col1cluclive maleria]s llas l~een limite(l l~ecause they ~lo possess some undesirable propertics S~ICIl as, poor processibility (no melting or glass transition temperature), poor solul)ility in tllc ~loped form and envirollmental instability. To be commercially useful, it is ncccssary to ren~ler these polymers processil~le by conventional teclmi(lues.
Severill articles llave appeare~l in the literature describing ways to overcome tl1c processil~ility prohlem. Tllese include attempts to synthesize so~uble con~l~lctive polymers or precursors and/or polymerization o~ conductive polymers in situ thereby forming conductive polyrner composites. Much of the known work on conductive composites using inlrinsically conductive polymers such as polyaniline an~l polypyrrole llas generally inclu~led electrochemical or cllemical coating of the con~luctive polymer onlo a polymeric substrate or electrocllemical polymerization OlltO a SWOIlCll pOIylllCr Usillg all .IpprOpriatC sOIVCIlt.
For exal1lple, U.S. Pat. No. 4,G17,228 (lescribes a process for making an electrically conductive composite by treating a porous substance such as fiberglass, with tlle monomer solulion, and later treating with an oxidizing agent to pro~iuce a conductive composite contailling an intrinsically conductive polymer. Similar tecl]ni~lues using a non-poro~ls substrate and/or via solution of tlle monomer llave been illustratecJ in U.S. Pat. No. 4,604,427 an~l Japanese Pat. No. JP 61,127,737.
Tllese composiles lmve failcd to yiekl lligllly con~luctive processible blen~ls, alld their preparation has proven to l)e cuml)ersome.
Blends of intrinsically conductive polymers witll convelltional, processible thcrmoplastics havc been suggestc(l to overcome processibility, such as sllown in U.S. Pat. No. 4,935,164 (polymer blends), U.S. Patent No. 4,929,388 (conductive patllways), Interllational Patent Application WO 89/02155 and Britisll Patent No.
2,214,511. These dcscribe post polymerization processes in wllicll tlle intrinsically 20~9~
- I -IILIIC'l'l~ICALL~' CONDUC'l`IVL~ l~LENl)S OF
IN'rl~INSlCALLY CONDUCT~V~ POLYMERS AND
Tl~ RMOPL~ST~C POLYMERS AND A PROCESS
FOl~rrHl~lK PREl'ARATlON
s TIICHNICAL FIELD
Tlle prescnt inventioll generally relates tu electrically conductive polymer blends. More particularly, the present invention relates to blends of intrinsically concluctive polymers an~l insula~ thermoplastic polymers, especially those 10 requiring thc use of a plasticizer. Specifically, the present invention relates to blends of polyalliline and polyvinyl chloride (PVC), including PVC plastisols, - clllorinaled polyelllylcllc, or olller thermoplastic polymer.
I~ACKGROUND ~RT
Intrinsically Conductive Polymers (ICP) have been studied since at the latest tlle 1970's. The term "ICP" refers to organic polymers which have (poly)-conjugated 7~-electron systems (e.g. double bonds, aromatic or heteroaromatic rings or triple l)on~ls). Lxamplcs of such polymers are polydiacetylene, polyacelylene(PAc), polypyrrole (PPy), polyaniline (P~NI), polytlliophene (PTh), 20 polyisolllionapl~ elle (l'l l N), polylleleroarylenvillylene (PArV), in wllicll tlle heteroarylene group can be the thiophene, furan or pyrrole, poly-p-phenylene (PpP), polyphtllalocyanine (PPhc) and the like, and their derivativcs (formed for example from monomers substiluted willl side chains or groups), their copolymers and thcir pllysical mixtures. They can exist in various states, each described by diEferent 25 cmpirical forlll-~ c, whicll can gellcrally be converted esscntially reversibly into one or the olher l)y (electro-) cllemical reactions such as oxidation, reduction, acid/alkali reaclion or comple.Ying. Tllese reac~ions are also occasionally known as "doping" or "compcnsatioll" in tlle literature, or can be regarded as "charging" ànd "discllarging"
in analogy ~vitll the electrochemical processes in batteries. At least one oE the 30 possil~le statcs is a vcry goo(l condllctor of electricity, c.g. llas a conductivily Or morc than 1 S/cm (in pure form), so one can speak of intrinsically conductive polyme;s.
20~99~5 ï l-cse rorms o~ thc ICI' are gencrally recognize(l as bcing polyraclical calionic or alliOIliC salts.
A goo(l overall revicw of Ihe intrinsically conductive polymers syntl~esize(l to cla~e wi~ll a cllcmical slructure suitablc for the present objective, is to bc foun~
in Synllle~ic Mclals, Issucs 17, 18, ancl 19 (1986), and in Synll~etic Metals, Issucs 27, 2~ an(l 29 (19S~ vllicll arc l~ercl)y incorporate(l I)y refcrcnce.
l~espite several polcntially useful properties e~lhibite~l by ICPs, tlleir use as col1cluclive maleria]s llas l~een limite(l l~ecause they ~lo possess some undesirable propertics S~ICIl as, poor processibility (no melting or glass transition temperature), poor solul)ility in tllc ~loped form and envirollmental instability. To be commercially useful, it is ncccssary to ren~ler these polymers processil~le by conventional teclmi(lues.
Severill articles llave appeare~l in the literature describing ways to overcome tl1c processil~ility prohlem. Tllese include attempts to synthesize so~uble con~l~lctive polymers or precursors and/or polymerization o~ conductive polymers in situ thereby forming conductive polyrner composites. Much of the known work on conductive composites using inlrinsically conductive polymers such as polyaniline an~l polypyrrole llas generally inclu~led electrochemical or cllemical coating of the con~luctive polymer onlo a polymeric substrate or electrocllemical polymerization OlltO a SWOIlCll pOIylllCr Usillg all .IpprOpriatC sOIVCIlt.
For exal1lple, U.S. Pat. No. 4,G17,228 (lescribes a process for making an electrically conductive composite by treating a porous substance such as fiberglass, with tlle monomer solulion, and later treating with an oxidizing agent to pro~iuce a conductive composite contailling an intrinsically conductive polymer. Similar tecl]ni~lues using a non-poro~ls substrate and/or via solution of tlle monomer llave been illustratecJ in U.S. Pat. No. 4,604,427 an~l Japanese Pat. No. JP 61,127,737.
Tllese composiles lmve failcd to yiekl lligllly con~luctive processible blen~ls, alld their preparation has proven to l)e cuml)ersome.
Blends of intrinsically conductive polymers witll convelltional, processible thcrmoplastics havc been suggestc(l to overcome processibility, such as sllown in U.S. Pat. No. 4,935,164 (polymer blends), U.S. Patent No. 4,929,388 (conductive patllways), Interllational Patent Application WO 89/02155 and Britisll Patent No.
2,214,511. These dcscribe post polymerization processes in wllicll tlle intrinsically 20~9~
collduclivc polylllers are presenl in a dispersed phase in a thermoplastic matrix, yiclclillg ~oocl proccssil)ility an(l higll conductivily above a certaill ~ritical volume concelltra~ioll of ~llc dispersed conductive polymer pllase. l hese processes present a generally uscrul proced~lre to process conduclive polymers into various forms.S As used hl lhe art and as emyloyed llerein, tlle term "polymer blend" is gCllClally UllCICrstOOd to mC-III n-acroscopically homogeneous mixtures of partly compatible or incompatible organic polymers. They always consist of two or more phases.
Nevertheless tllere is still a disadvantage resulling from the chemical na~ure of most of the conduclive polymers whicll include protonic acids as "dopants".
They react directly or indirectly Witll various functional groups prescnt in thepolymer ma~rices whicll are susceptible to reactions witll acids or bases. More specirically, for installce, tlle basic nature of various homopolymers ;Ind copolymers of polyamides (nylons) provides a basic environment wllicll leads to partial dedoping (compensation) of the conductive polymer and/or cle~radation of the polymer matrix. The same result appears to occur with several aromatic or aliphatic eslers present in the various polyester holllopolymers or copolymers (regardless of whetller they are aromatic or alipha~ic) which are used according to the above-mentioned procedures. Polymer matrices sucl~ as PVC homopolymers or copolymers, clllorinatcd polyctllylcllc allcl similar polymeric matrices are used rouîillely with plasticizers whicll have been observed to react with concluctive polymers therel~y leadin~ to compensation reactions.
Wi~h rcspect to thermoplastic vinyl compounds in genc ral, it is kno~vn in the art to employ a plasticizer as a possible major component of a vinyl compound.
The selection of the specific plasticizer is based on compatibility witll the host polymer, cost ancl yerformallce. In order for the plasticizer to l~e compatil)le, the solubili~y parame~ers Or tlle polymer matrix ancl ~he plasticizer should match.
Typically used plasticizers include phtllalate esters such as dioclyl phthalate and clibutyl phthalate, polyesters, azelates, adipates, sebacates, organic phospllates and the like.
The "solubility parameter" is the measure of polarity of a material, and is defined as the square root of cohesive energy density (CED~. Most common~y 20~99~
use~l plcls~iCiZerS~ SUCIl as es~ers llaYe a solubility parameter in ~he range of 8 to 10 (cal/clll3) 1 /2 Estcr-type plaslicizers are those plasticizers whicll are formed by thereaction of an ~cid and an alcohol or compounds that contain the following 5slructural Ulli~:
o -C-O-Typical examples of esler plaslicizers include dioctyl phlllalate, dibulyl phtllalate and tlle like. I-Iighly polar plasticizers are those wilh solubilily parameters greater than 1011(cal/cm3)1/2. Typical of this class are sulfonamides, which are generally free of ester linkagcs.
I~urthcrmore, polymers having acetate, propionate, or other ester groups, are present in various polymers of acrylates which are used in pure form or in polymer blends, as illlp;lCt modiriers in polyvinyl chloride, polystyrenes and other 15polymers, llave also been observed to react with intrinsically conducting polymers.
Thcreforc, a neecl exists for improving the presently available processing techniques of intrinsically conductive polymer blen(ls.
DISCLOSURE: OF THE INVE:NTION
20Il is lllcrerore, all objcct of tlle present invention to provide a processible, conductive polymer blen~l which inclu(les an intrinsically con(luctive polymer and an insulating tllermoplastic material.
I~ is anolher object of tlle present inven~ion to provide a conduclivc polymeric blend as ~bove, whicll possesses mechanical properties comparable to 25polyvinyl chloride.
It is a furtller object of the present invention, to provi(le blen~ls as above, of "~loped" p()lyalliline all~l polyvinyl chloride, cl-lorhl;lted polycthylellc or olher tllermoplastic polymcr wllicll exhibit high electrical conductivity.
Il is s~ill anolller object of the invention to provide a blend as above, 30havin~ a dispersion of polyaniline witllin the thermoplastic malrix containing a plasticizer.
It is an addilional object of the invention to provi~e improved blends of "doped" polyaniline and polyamides (nylons), polyeslers or polycarbonates ~hl tlle 20~9~
form of homopolymcrs vr copolymers~, copolymers of vinyl acetate, and acrylate homopolymers or copolymers.
In general, a conductive polymer blend comprises an intrinsically conductive polymer, an insulating thermoplastic material and at least one add;tive S selected from the group consistin~ of an impact mociifier1 an ester-free plasticizer and an acidic surfactant. The insulating thermoplastic rnaterial comprises a thermoplastic polymer and the blend has a conductivity of greater than about 10-9 S/cm.
A process for preparing conductive polymeric blends according to the 10 invention comprises the step of forming a blend. The blend comprises an intrinsically conductive polymer, an insulating thermoplastic material and at least one additive selected from the group consisting of an impact modifier, an ester-free plasticizer and an acidic surfactant. The thermoplastic material comprises a thermoplastic polymer and the conductive polymeric blend has a conductivity of 15 above about 10-9 S/cm.
These and other objects, together with the advantages over the known compositions and processes shall become apparent from the specification which follows and are accomplished by the invention as hereinafter described and claimed.
BRIEF I~ESCRIPTION OF THE DRAVVING
The drawing figure provides a graphic representation of conductivity test data for conductive blends of the present invention in order to demonstrate the effectiveness thereof.
PRI~FERRED EMBODIMENT FOR CARRYING OllT THE INVENTION
According to the present invention a highly conductive blend of an intrinsically conductive polymer and an insulating thermoplastic material is achieved despite the high polarity and reactivity of the intrinsically conductive polymer. The electrically conductive blend may be employed to manufacture articles where it is desirable to have electrical conductivities in the range of those possessed by doped polyaniline. For instance, the present invention has a particular application for electro-magnetic interference shielding, electrostatic dissipation and the like.
20599~
A pre~err~cl intrinsic~llly concluctive polymer according to the present invcntion is doped polyaniline. For example, polyaniline may be doped with protonic acids sucll as hydrochloric acid or an organic sulfonic acid.
The insulating thermoplastic material may be a polyvinyl chloride 5 homopolymer or a polyvinyl chloride copolymer with vinyl acetate; chlorinated polyetllylene; polyamide (nylon); polyester; polyurethane; polyvinyl acetate;
polyacetate; polyacrylate; and the like, as well as copolymers and mixtures thereof.
By "insulating" it is understood to mean non-conductive, having a volume conductivity lower than about 10-12 S/cm.
The invention prefer~bly makes use of from about 1 to about 50 parts of the intrinsically conductive polymer blended with &om about 50 to about 99 partsof the insulating thermoplastic rnaterial.
Furthermore, as will be more appreciated from the discussion to follow, the thermoplastic material can comprise 100 percent by weight of a suitable 15 thermoplastic polymer; a blend of a thermoplastic polymer and a plasticizer; a blend of a therrnoplastic polymer and an acidic surfactant; or, a blend of a thermoplastic polymer, a plasticizer and an acidic surfactant. The term "thermoplastic material"
is thus understood to include appropriate thermoplastic polymers with or w4hout the additional blend additives. Optionally, an impact modifier may be employed as also 20 discussed hereinbelow.
It is preferred that the thermoplastic polymer be plasticized with a highly polar, ester-free plasticizer. Furthermore, it is also desirable for the blend to comprise from 0 (i~ no plasticizer is employed) to about 66 parts by weight of an ester-*ee plasticizer per 100 parts by weight of the thermoplastic material. Thus, 25 if the amount of the ester-free plasticizer is varied between the preferred range, there is a corresponding change in the amount of the thermoplastic polymer in the thermoplastic material. Heretofore, studies with conventional plasticizers have not been successful in obtaining a highly conductive blends of polyaniline and polyvinyl chloride, chlorinated polyethylene or other thermoplastic materials. This is 30 attributable to the reaction of polyaniline with conventional esters, resulting in loss of conductivity.
Highly polar plasticizers, such as the sulfonamides are not compatible with polyvinyl chloride. Polyaniline is a highly polar compound. It is an unexpected 2 ~ r3 result that the blen~s accordillg lo the invention and containing sulfonamides could be prepared in a superior quality compared to blends with conventional plasticizers.
Preferred highly polar plasticizers include those having a solubility parameter of greater than about 11 (cal/cm3)1/2. Exemplary of the plasticizers which may be 5 employed are n-butyl benzene sulronamide, n-butyl and n-ethyl toluene sulfonamides and other sulfonamides.
It rnay also be useful for the blend of the present invention to comprise an acidic surfactant, and preferrably from about 0 (if no acidic surfactant is employed) to about 20 percent by weight based UpOIl the weight of the intrinsically 10 conducting polymer. It is also useful to the practice of the present invention if the acidic surfactant is present as a pre-blend with the intrinsically conductive polymer.
For purposes of the exemplary useful ranges for the acidic surfactant, it is preferred that even if present in the pre-blend, the amount of the thermoplastic polymer present in the blend is correspondingly varied as the amount of the acidic surfactant 15 is varied. Polyaniline is stable in acidic environments. However, under alkaline conditions, polyaniline loses its conductivity, owing to the dedoping or compensation reaction. The presence of an acidic surfactant, in addition to being a dispersion aid, maintains an environment for polyaniline to remain in the conductive form.
Prefe~red surfactants include those having a pH of less than about 6. For example, 20 useful acidic surfactants include organic phosphate esters such as those of nonionic surfactants of ethylene oxide-adduct type, and an acid anhydride dispersants. A
useful acid anhydride surfactant is available from Lubri~ol Corporation as OS 65238.
Other surfactants would include those with acid, anhydride or lactone groups, and if employed, the blend can include up to about 1 part of surfactant for 25 every 10 parts of intrinsically conductive polymer.
As will be appreciated by those skilled in the art, the present invention also has applicability to preparing highly conductive blends of polyaniline/nylon, polyaniline/polyesters, and the like.
As will be fully addressed herein below, blends according to the present 30 invention possess conductivities above about 10-9 S/cm and preferably in the range of 10-9 to 10 S/cm, and uniform distribution of polyaniline. The amount of polyaniline can be varied to provide the required conductivity. Furthermore, impact - 8 2~9~5 modifiers such as chlorinated polyethylenes and the acrylics, stabilizers and other processing aids may be employed, as known in the art.
As noted hereinabove, polymer blends of the present invention can also include an impact modifier. Impact modifiers when employed, are preferably 5 blended with the thermoplastic material and incl~lde polymers such as chlorinated polyethylene. It will be appreciated by one skilled in the art, that ~ertain polymers such as chlorinated polyethylene have application both as the thermoplastic polymer constituent of the thermoplastic material, and as an impact modifier. Therefore,when the thermoplastic polymer employed is a useful impact modifier, additional 10 amounts of that polymer will not necessarily need to be added to the thermoplastic material. When an impact modifier is employed, from about 1 to about 99 percent by weight of the impact modifier may be employed with from about 99 to about 1 percent by weight of the thermoplastic polymer.
Other processing aids may incll~de lubricants, such as montan ester wax, 15 long chain alcohols and certain amid waxes, as known in the art.
Experimental In order to demonstrate the effectiveness of blends according to the present invention, a number of blends were prepared employing conventional and ~0 electron donating highly polar plasticizers. The data obtained from these experiments show the highly conductive nature of blends according to the presentinvention. Conductivity data was collected via the four-point probe method, as is known in the art. The following examples are expressed in parts by weight.
Examples 1-3 show the preparation of the insulating thermoplastic material as a 25 blend of a thermoplastic polymer, a plasticizer and chlorinated polyethylene as an impact modifier.
Example 1 A polyvinyl chloride compound containing 63 parts of homopolymer 30 polyvinyl chloride, 32 parts of a phthalate plasticizer, 15 parts of an impact modifier, 2 parts of stabilizer and 3 parts of processing aid was prepared by mixing on a 2-roll mill.
20~9~
xample 2 A polyvinyl chloride compound containing 63 parts of homopolymer polyvinyl chloride, 32 parts of a sulfonami(le plasticizer, 15 parts of an impact modifier, 2 parts of stabilizer and 3 parts of processing aid was prepared by rnixing on a 2-roll mill.
Example 3 A polyvinyl chloride compound coneaining 63 parts of homopolymer polyvinyl chloride, 32 parts of a phosphate plasticizer, 15 parts of an impact modifier, 2 parts of stabilizer and 3 parts of processing aid was prepared by mixing on a 2-roll mill.
Example 4 In order to evaluate and demonstrate the change in conductivity as a function of polyaniline concentration (percolation curve) a series of compounds based on Exarnples 1-3 were prepared by va~ing the concentration of polyaniline between 50 weight percent and 5 weight percent. The starting composition for each series was 50 parts by weight of polyaniline, 45 parts by weight of polyvinyl chloride compound and 5 parts of an organic phosphate ester surfactant.
The conductivity for each was determined and the drawing figure shows a plot of the data. The results clearly indicate the highest conductivity for the polyaniline/polyvinyl chloride compound system containing the sulfonamide type plasticizer.
Example 5 A composition containing 25 parts by weight of polyaniline and 75 parts of the thermoplastic material of Example 1 was prepared and showed a bulk conductivity of 5.6 x 10-8 S/cm.
Example 6 A composition containing 25 parts by weight of polyaniline and 75 parts of the thermoplastic material of Example 2 was prepared and showed a bulk conductivity of 4.0 x 10-2 S/cm.
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Ex~mple 7 A composition containing 25 parts by weight of polyaniline, 5 parts by weight of an organic phosphate eype surfactant and 70 parts by weight of the thermoplastic maierial of Example 1 was prepared and showed a conductivity of 3.8 S x 10-4 S/cm.
Example 8 A composition containing 25 parts by weight of polyaniline, 5 parts by weight of an organic phosphate type surfactant and 70 parts by weight of the 10 thermoplastic material Example 2 was prepared and showed a conductivity of 0.35 S/cm.
Example 9 A composition containing 25 parts by weight of polyaniline and 52 parts 15 by weight of chlorinated polyethylene, 15 parts by weight of su}fonamide plasticizer and 5 parts by weight of an organic phosphate ester and 2 parts by weight of stabilizer and 1 part by weight of processing aid was prepared by mixing on a two-roll mill and was found to have a conductivity of 0.1 S/cm.
Example 10 A composition containing 39.0 parts of a nylon copolymer, 1.0 part of montan ester wax, and S parts of a sulfonamide plasticizer, 5 parts of organic phosphate ester surfactant and 50 parts of polyaniline (PANI) was prepared yielding a 50 percent polyaniline blend. This blend was subsequently diluted with a nyloncopolymer to give varying concentrations of polyaniline. The weight concentrations and the respective conductivities are listed in Table I hereinbelow.
2~99~5 TABLE I
Weight Concentration/Conductivity PANI Conductivity Weight ~ S/crn 2.7x 10-7 2.9 x 10-3 0.13 0.32 0.98 1.85 3.72 S0 5.03 Example 11 A composition containing 21.75 parts of a polyester copolymer, 1.25 parts of a first lubricant of montan ester wax, 0.4 parts of a second lubricant comprising a long chain alcohol, 0.1 parts of stabilizer and 2.5 parts of a rmixture consisting of a sulfonamide plasticizer, organic phosphate ester surfactant and surfactant of the 20 ethylene oxide nonyl phenol condensate type and 17.4 parts of polyaniline wasprepared yielding a 40 percent polyaniline blend. This blend was subsequently diluted with additional amounts of the polyester copolymer to give varying concentrations of polyaniline. The weight concentrations and the conductivities are listed in Table II hereinbelow.
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TABLE ll Weight Concentration/Conductivity PANI Conductivity Weight ~ S/cm 7 2x 10-13 8 4 x 10-8 9 5 x 10-8 1 x 10-6 11 1x10-4 12 4 x 10-4 13 2 x 10-3 1 x 10-2 0.24 1.86 3.13 Example 12 A composition containing 22.5 parts of a polycarbonate, 4.0 parts of a 20 first lubricant of montan ester wax, 0.5 parts of a second lubricant comprising a long chain alcohol, 0.2 parts of stabilizer and 2.5 parts of a mixture consisting of sulfonamide plasticizer, organic phosphate ester surfactant and surfactant of the ethylene oxide nonyl phenol condensate type and 23.5 parts of polyaniline was prepared yielding a 44 percent polyaniline blend. This blend was subsequently 25 diluted with polycarbonate to give varying concentrations of polyaniline. The weight concentrations and the conductivities are listed in Table III hereinbelow.
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- l3 -TABLE III
Weight Concentration/Conductivity PANI Conductivity Wei~ht % S/cm 12.2 2 x 10-9 13.4 1 x 10-9 16.7 1 x 10-7 23.4 2 x 10-4 28.4 9 x 10-4 33.5 5.8x 10-3 38.6 8.2 x 10-3 44 0.21 Based upon the foregoing exemplification, it can be seen that the present 15 invention provides highly electrically conductive blends of polyaniline and polyvinyl chloride and/or chlorinated polyethylene as well as a process for their preparation.
It is to be understood that the examples reported herein have been provided to present results obtainable by practice of the disclosed invention. Inasmuch as a wide variety of thermoplastic polymers such as polyvinyl chlorides, chlorinated 20 polyethylene, nylons, polyesters, polyacetates, polyacrylates, and the like, as well as plasticizers, surfactants, impact modifiers and other components have been disclosed for use in conjunction with polyaniline to form blends according to the invention, this invention is not limited to the specific examples provided herein. Furthermore, the process for preparing these conductive blends is believed to be operable with 25 components, concentrations and conditions, other than those which have been exemplified herein. Thus, it should be evident that the determination of particular components, concentrations and other conditions, can be made without departure from the spirit of the inven~ion herein disclosed and described, and the scope of the invention shall include all modifications and variations that fall within the scope of 30 the attached claims.
Nevertheless tllere is still a disadvantage resulling from the chemical na~ure of most of the conduclive polymers whicll include protonic acids as "dopants".
They react directly or indirectly Witll various functional groups prescnt in thepolymer ma~rices whicll are susceptible to reactions witll acids or bases. More specirically, for installce, tlle basic nature of various homopolymers ;Ind copolymers of polyamides (nylons) provides a basic environment wllicll leads to partial dedoping (compensation) of the conductive polymer and/or cle~radation of the polymer matrix. The same result appears to occur with several aromatic or aliphatic eslers present in the various polyester holllopolymers or copolymers (regardless of whetller they are aromatic or alipha~ic) which are used according to the above-mentioned procedures. Polymer matrices sucl~ as PVC homopolymers or copolymers, clllorinatcd polyctllylcllc allcl similar polymeric matrices are used rouîillely with plasticizers whicll have been observed to react with concluctive polymers therel~y leadin~ to compensation reactions.
Wi~h rcspect to thermoplastic vinyl compounds in genc ral, it is kno~vn in the art to employ a plasticizer as a possible major component of a vinyl compound.
The selection of the specific plasticizer is based on compatibility witll the host polymer, cost ancl yerformallce. In order for the plasticizer to l~e compatil)le, the solubili~y parame~ers Or tlle polymer matrix ancl ~he plasticizer should match.
Typically used plasticizers include phtllalate esters such as dioclyl phthalate and clibutyl phthalate, polyesters, azelates, adipates, sebacates, organic phospllates and the like.
The "solubility parameter" is the measure of polarity of a material, and is defined as the square root of cohesive energy density (CED~. Most common~y 20~99~
use~l plcls~iCiZerS~ SUCIl as es~ers llaYe a solubility parameter in ~he range of 8 to 10 (cal/clll3) 1 /2 Estcr-type plaslicizers are those plasticizers whicll are formed by thereaction of an ~cid and an alcohol or compounds that contain the following 5slructural Ulli~:
o -C-O-Typical examples of esler plaslicizers include dioctyl phlllalate, dibulyl phtllalate and tlle like. I-Iighly polar plasticizers are those wilh solubilily parameters greater than 1011(cal/cm3)1/2. Typical of this class are sulfonamides, which are generally free of ester linkagcs.
I~urthcrmore, polymers having acetate, propionate, or other ester groups, are present in various polymers of acrylates which are used in pure form or in polymer blends, as illlp;lCt modiriers in polyvinyl chloride, polystyrenes and other 15polymers, llave also been observed to react with intrinsically conducting polymers.
Thcreforc, a neecl exists for improving the presently available processing techniques of intrinsically conductive polymer blen(ls.
DISCLOSURE: OF THE INVE:NTION
20Il is lllcrerore, all objcct of tlle present invention to provide a processible, conductive polymer blen~l which inclu(les an intrinsically con(luctive polymer and an insulating tllermoplastic material.
I~ is anolher object of tlle present inven~ion to provide a conduclivc polymeric blend as ~bove, whicll possesses mechanical properties comparable to 25polyvinyl chloride.
It is a furtller object of the present invention, to provi(le blen~ls as above, of "~loped" p()lyalliline all~l polyvinyl chloride, cl-lorhl;lted polycthylellc or olher tllermoplastic polymcr wllicll exhibit high electrical conductivity.
Il is s~ill anolller object of the invention to provide a blend as above, 30havin~ a dispersion of polyaniline witllin the thermoplastic malrix containing a plasticizer.
It is an addilional object of the invention to provi~e improved blends of "doped" polyaniline and polyamides (nylons), polyeslers or polycarbonates ~hl tlle 20~9~
form of homopolymcrs vr copolymers~, copolymers of vinyl acetate, and acrylate homopolymers or copolymers.
In general, a conductive polymer blend comprises an intrinsically conductive polymer, an insulating thermoplastic material and at least one add;tive S selected from the group consistin~ of an impact mociifier1 an ester-free plasticizer and an acidic surfactant. The insulating thermoplastic rnaterial comprises a thermoplastic polymer and the blend has a conductivity of greater than about 10-9 S/cm.
A process for preparing conductive polymeric blends according to the 10 invention comprises the step of forming a blend. The blend comprises an intrinsically conductive polymer, an insulating thermoplastic material and at least one additive selected from the group consisting of an impact modifier, an ester-free plasticizer and an acidic surfactant. The thermoplastic material comprises a thermoplastic polymer and the conductive polymeric blend has a conductivity of 15 above about 10-9 S/cm.
These and other objects, together with the advantages over the known compositions and processes shall become apparent from the specification which follows and are accomplished by the invention as hereinafter described and claimed.
BRIEF I~ESCRIPTION OF THE DRAVVING
The drawing figure provides a graphic representation of conductivity test data for conductive blends of the present invention in order to demonstrate the effectiveness thereof.
PRI~FERRED EMBODIMENT FOR CARRYING OllT THE INVENTION
According to the present invention a highly conductive blend of an intrinsically conductive polymer and an insulating thermoplastic material is achieved despite the high polarity and reactivity of the intrinsically conductive polymer. The electrically conductive blend may be employed to manufacture articles where it is desirable to have electrical conductivities in the range of those possessed by doped polyaniline. For instance, the present invention has a particular application for electro-magnetic interference shielding, electrostatic dissipation and the like.
20599~
A pre~err~cl intrinsic~llly concluctive polymer according to the present invcntion is doped polyaniline. For example, polyaniline may be doped with protonic acids sucll as hydrochloric acid or an organic sulfonic acid.
The insulating thermoplastic material may be a polyvinyl chloride 5 homopolymer or a polyvinyl chloride copolymer with vinyl acetate; chlorinated polyetllylene; polyamide (nylon); polyester; polyurethane; polyvinyl acetate;
polyacetate; polyacrylate; and the like, as well as copolymers and mixtures thereof.
By "insulating" it is understood to mean non-conductive, having a volume conductivity lower than about 10-12 S/cm.
The invention prefer~bly makes use of from about 1 to about 50 parts of the intrinsically conductive polymer blended with &om about 50 to about 99 partsof the insulating thermoplastic rnaterial.
Furthermore, as will be more appreciated from the discussion to follow, the thermoplastic material can comprise 100 percent by weight of a suitable 15 thermoplastic polymer; a blend of a thermoplastic polymer and a plasticizer; a blend of a therrnoplastic polymer and an acidic surfactant; or, a blend of a thermoplastic polymer, a plasticizer and an acidic surfactant. The term "thermoplastic material"
is thus understood to include appropriate thermoplastic polymers with or w4hout the additional blend additives. Optionally, an impact modifier may be employed as also 20 discussed hereinbelow.
It is preferred that the thermoplastic polymer be plasticized with a highly polar, ester-free plasticizer. Furthermore, it is also desirable for the blend to comprise from 0 (i~ no plasticizer is employed) to about 66 parts by weight of an ester-*ee plasticizer per 100 parts by weight of the thermoplastic material. Thus, 25 if the amount of the ester-free plasticizer is varied between the preferred range, there is a corresponding change in the amount of the thermoplastic polymer in the thermoplastic material. Heretofore, studies with conventional plasticizers have not been successful in obtaining a highly conductive blends of polyaniline and polyvinyl chloride, chlorinated polyethylene or other thermoplastic materials. This is 30 attributable to the reaction of polyaniline with conventional esters, resulting in loss of conductivity.
Highly polar plasticizers, such as the sulfonamides are not compatible with polyvinyl chloride. Polyaniline is a highly polar compound. It is an unexpected 2 ~ r3 result that the blen~s accordillg lo the invention and containing sulfonamides could be prepared in a superior quality compared to blends with conventional plasticizers.
Preferred highly polar plasticizers include those having a solubility parameter of greater than about 11 (cal/cm3)1/2. Exemplary of the plasticizers which may be 5 employed are n-butyl benzene sulronamide, n-butyl and n-ethyl toluene sulfonamides and other sulfonamides.
It rnay also be useful for the blend of the present invention to comprise an acidic surfactant, and preferrably from about 0 (if no acidic surfactant is employed) to about 20 percent by weight based UpOIl the weight of the intrinsically 10 conducting polymer. It is also useful to the practice of the present invention if the acidic surfactant is present as a pre-blend with the intrinsically conductive polymer.
For purposes of the exemplary useful ranges for the acidic surfactant, it is preferred that even if present in the pre-blend, the amount of the thermoplastic polymer present in the blend is correspondingly varied as the amount of the acidic surfactant 15 is varied. Polyaniline is stable in acidic environments. However, under alkaline conditions, polyaniline loses its conductivity, owing to the dedoping or compensation reaction. The presence of an acidic surfactant, in addition to being a dispersion aid, maintains an environment for polyaniline to remain in the conductive form.
Prefe~red surfactants include those having a pH of less than about 6. For example, 20 useful acidic surfactants include organic phosphate esters such as those of nonionic surfactants of ethylene oxide-adduct type, and an acid anhydride dispersants. A
useful acid anhydride surfactant is available from Lubri~ol Corporation as OS 65238.
Other surfactants would include those with acid, anhydride or lactone groups, and if employed, the blend can include up to about 1 part of surfactant for 25 every 10 parts of intrinsically conductive polymer.
As will be appreciated by those skilled in the art, the present invention also has applicability to preparing highly conductive blends of polyaniline/nylon, polyaniline/polyesters, and the like.
As will be fully addressed herein below, blends according to the present 30 invention possess conductivities above about 10-9 S/cm and preferably in the range of 10-9 to 10 S/cm, and uniform distribution of polyaniline. The amount of polyaniline can be varied to provide the required conductivity. Furthermore, impact - 8 2~9~5 modifiers such as chlorinated polyethylenes and the acrylics, stabilizers and other processing aids may be employed, as known in the art.
As noted hereinabove, polymer blends of the present invention can also include an impact modifier. Impact modifiers when employed, are preferably 5 blended with the thermoplastic material and incl~lde polymers such as chlorinated polyethylene. It will be appreciated by one skilled in the art, that ~ertain polymers such as chlorinated polyethylene have application both as the thermoplastic polymer constituent of the thermoplastic material, and as an impact modifier. Therefore,when the thermoplastic polymer employed is a useful impact modifier, additional 10 amounts of that polymer will not necessarily need to be added to the thermoplastic material. When an impact modifier is employed, from about 1 to about 99 percent by weight of the impact modifier may be employed with from about 99 to about 1 percent by weight of the thermoplastic polymer.
Other processing aids may incll~de lubricants, such as montan ester wax, 15 long chain alcohols and certain amid waxes, as known in the art.
Experimental In order to demonstrate the effectiveness of blends according to the present invention, a number of blends were prepared employing conventional and ~0 electron donating highly polar plasticizers. The data obtained from these experiments show the highly conductive nature of blends according to the presentinvention. Conductivity data was collected via the four-point probe method, as is known in the art. The following examples are expressed in parts by weight.
Examples 1-3 show the preparation of the insulating thermoplastic material as a 25 blend of a thermoplastic polymer, a plasticizer and chlorinated polyethylene as an impact modifier.
Example 1 A polyvinyl chloride compound containing 63 parts of homopolymer 30 polyvinyl chloride, 32 parts of a phthalate plasticizer, 15 parts of an impact modifier, 2 parts of stabilizer and 3 parts of processing aid was prepared by mixing on a 2-roll mill.
20~9~
xample 2 A polyvinyl chloride compound containing 63 parts of homopolymer polyvinyl chloride, 32 parts of a sulfonami(le plasticizer, 15 parts of an impact modifier, 2 parts of stabilizer and 3 parts of processing aid was prepared by rnixing on a 2-roll mill.
Example 3 A polyvinyl chloride compound coneaining 63 parts of homopolymer polyvinyl chloride, 32 parts of a phosphate plasticizer, 15 parts of an impact modifier, 2 parts of stabilizer and 3 parts of processing aid was prepared by mixing on a 2-roll mill.
Example 4 In order to evaluate and demonstrate the change in conductivity as a function of polyaniline concentration (percolation curve) a series of compounds based on Exarnples 1-3 were prepared by va~ing the concentration of polyaniline between 50 weight percent and 5 weight percent. The starting composition for each series was 50 parts by weight of polyaniline, 45 parts by weight of polyvinyl chloride compound and 5 parts of an organic phosphate ester surfactant.
The conductivity for each was determined and the drawing figure shows a plot of the data. The results clearly indicate the highest conductivity for the polyaniline/polyvinyl chloride compound system containing the sulfonamide type plasticizer.
Example 5 A composition containing 25 parts by weight of polyaniline and 75 parts of the thermoplastic material of Example 1 was prepared and showed a bulk conductivity of 5.6 x 10-8 S/cm.
Example 6 A composition containing 25 parts by weight of polyaniline and 75 parts of the thermoplastic material of Example 2 was prepared and showed a bulk conductivity of 4.0 x 10-2 S/cm.
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Ex~mple 7 A composition containing 25 parts by weight of polyaniline, 5 parts by weight of an organic phosphate eype surfactant and 70 parts by weight of the thermoplastic maierial of Example 1 was prepared and showed a conductivity of 3.8 S x 10-4 S/cm.
Example 8 A composition containing 25 parts by weight of polyaniline, 5 parts by weight of an organic phosphate type surfactant and 70 parts by weight of the 10 thermoplastic material Example 2 was prepared and showed a conductivity of 0.35 S/cm.
Example 9 A composition containing 25 parts by weight of polyaniline and 52 parts 15 by weight of chlorinated polyethylene, 15 parts by weight of su}fonamide plasticizer and 5 parts by weight of an organic phosphate ester and 2 parts by weight of stabilizer and 1 part by weight of processing aid was prepared by mixing on a two-roll mill and was found to have a conductivity of 0.1 S/cm.
Example 10 A composition containing 39.0 parts of a nylon copolymer, 1.0 part of montan ester wax, and S parts of a sulfonamide plasticizer, 5 parts of organic phosphate ester surfactant and 50 parts of polyaniline (PANI) was prepared yielding a 50 percent polyaniline blend. This blend was subsequently diluted with a nyloncopolymer to give varying concentrations of polyaniline. The weight concentrations and the respective conductivities are listed in Table I hereinbelow.
2~99~5 TABLE I
Weight Concentration/Conductivity PANI Conductivity Weight ~ S/crn 2.7x 10-7 2.9 x 10-3 0.13 0.32 0.98 1.85 3.72 S0 5.03 Example 11 A composition containing 21.75 parts of a polyester copolymer, 1.25 parts of a first lubricant of montan ester wax, 0.4 parts of a second lubricant comprising a long chain alcohol, 0.1 parts of stabilizer and 2.5 parts of a rmixture consisting of a sulfonamide plasticizer, organic phosphate ester surfactant and surfactant of the 20 ethylene oxide nonyl phenol condensate type and 17.4 parts of polyaniline wasprepared yielding a 40 percent polyaniline blend. This blend was subsequently diluted with additional amounts of the polyester copolymer to give varying concentrations of polyaniline. The weight concentrations and the conductivities are listed in Table II hereinbelow.
2~99~
TABLE ll Weight Concentration/Conductivity PANI Conductivity Weight ~ S/cm 7 2x 10-13 8 4 x 10-8 9 5 x 10-8 1 x 10-6 11 1x10-4 12 4 x 10-4 13 2 x 10-3 1 x 10-2 0.24 1.86 3.13 Example 12 A composition containing 22.5 parts of a polycarbonate, 4.0 parts of a 20 first lubricant of montan ester wax, 0.5 parts of a second lubricant comprising a long chain alcohol, 0.2 parts of stabilizer and 2.5 parts of a mixture consisting of sulfonamide plasticizer, organic phosphate ester surfactant and surfactant of the ethylene oxide nonyl phenol condensate type and 23.5 parts of polyaniline was prepared yielding a 44 percent polyaniline blend. This blend was subsequently 25 diluted with polycarbonate to give varying concentrations of polyaniline. The weight concentrations and the conductivities are listed in Table III hereinbelow.
2059~
- l3 -TABLE III
Weight Concentration/Conductivity PANI Conductivity Wei~ht % S/cm 12.2 2 x 10-9 13.4 1 x 10-9 16.7 1 x 10-7 23.4 2 x 10-4 28.4 9 x 10-4 33.5 5.8x 10-3 38.6 8.2 x 10-3 44 0.21 Based upon the foregoing exemplification, it can be seen that the present 15 invention provides highly electrically conductive blends of polyaniline and polyvinyl chloride and/or chlorinated polyethylene as well as a process for their preparation.
It is to be understood that the examples reported herein have been provided to present results obtainable by practice of the disclosed invention. Inasmuch as a wide variety of thermoplastic polymers such as polyvinyl chlorides, chlorinated 20 polyethylene, nylons, polyesters, polyacetates, polyacrylates, and the like, as well as plasticizers, surfactants, impact modifiers and other components have been disclosed for use in conjunction with polyaniline to form blends according to the invention, this invention is not limited to the specific examples provided herein. Furthermore, the process for preparing these conductive blends is believed to be operable with 25 components, concentrations and conditions, other than those which have been exemplified herein. Thus, it should be evident that the determination of particular components, concentrations and other conditions, can be made without departure from the spirit of the inven~ion herein disclosed and described, and the scope of the invention shall include all modifications and variations that fall within the scope of 30 the attached claims.
Claims (33)
1. A conductive polymer blend comprising:
an intrinsically conductive polymer;
an insulating thermoplastic material comprising a thermoplastic polymer;
and, at least one additive selected from the group consisting of an impact modifier, an ester-free plasticizer and an acidic surfactant;
the blend having a conductivity of greater than about 10-9 S/cm.
an intrinsically conductive polymer;
an insulating thermoplastic material comprising a thermoplastic polymer;
and, at least one additive selected from the group consisting of an impact modifier, an ester-free plasticizer and an acidic surfactant;
the blend having a conductivity of greater than about 10-9 S/cm.
2. A conductive polymeric blend as in claim 1, wherein said intrinsically conductive polymer is selected from the group consisting of polyanilines.
3. A conductive polymeric blend as in claim 2, wherein said polyaniline is doped.
4. A conductive polymeric blend as in claim 3, wherein said polyaniline is doped with hydrochloric acid or organic sulfonic acids.
5. A conductive polymeric blend as in Claim 1, wherein said thermoplastic polymer is selected from the group consisting of polyvinyl chloride, copolymers of polyvinyl chloride with vinyl acetate, chlorinated polyethylene, polyamides, polyesters, polyacetates, polyvinyl acetates, polyacrylates, polyurethanes, and copolymers and mixtures thereof.
6. A conductive polymeric blend as in claim 1, wherein said ester-free plasticizer is a sulfonamide.
7. A conductive polymeric blend as in claim 6, wherein said sulfonamide plasticizer is selected from the group consisting of N-butyl benzene sulfonamide, N-butyl toluene sulfonamide and N-ethyl toluene sulfonamide.
8. A conductive polymeric blend as in claim 1, wherein said plasticizer has a solubility parameter of greater than about 11 (cal/cm3)1/2.
9. A conductive polymeric blend as in claim 1, wherein said acidic surfactant has a pH of less than about 6.
10. A conductive polymeric blend as in claim 9, wherein said acidic surfactant selected from the group consisting of acid anhydrides, lactones and organic phosphate esters.
11. A conductive polymeric blend as in claim 10, wherein said organic phosphate ester is a nonionic ethylene oxide adduct type.
12. A conductive polymeric blend as in claim 1, wherein said impact modifier is chlorinated polyethylene.
13. A conductive polymeric blend as in claim 1, wherein the blend comprises from about 1 to about 50 parts by weight of said intrinsically conductive polymer and from about 99 to about 50 parts by weight of said thermoplastic material.
14. A conductive polymeric blend as in claim 13, wherein said thermoplastic material comprises from about 99 to 1 percent by weight of said thermoplastic polymer and from 1 to about 99 percent by weight of said impact modifier.
15. A conductive polymeric blend as in claim 13, wherein said thermoplastic material further comprises from about 0 to about 66 parts by weight of said ester-free plasticizer with an attendant decrease in the amount of said thermoplastic polymer present in said thermoplastic material.
16. A conductive polymeric blend as in claim 15, wherein said thermoplastic material further comprises from about 0 to about 20 percent by weight of said acidic surfactant based upon the amount of said intrinsically conductive polymer, with an attendant decrease in the amount of said thermoplastic polymer.
17. A process preparing conductive polymeric blends comprising the step of:
forming a blend comprising an intrinsically conductive polymer, an insulating thermoplastic material and at least one additive selected from the group consisting of an impact modifier, an ester-free plasticizer and an acidic surfactant;
said thermoplastic material comprising a thermoplastic polymer;
such that the conductive polymeric blend has a conductivity above about 10-9 S/cm.
forming a blend comprising an intrinsically conductive polymer, an insulating thermoplastic material and at least one additive selected from the group consisting of an impact modifier, an ester-free plasticizer and an acidic surfactant;
said thermoplastic material comprising a thermoplastic polymer;
such that the conductive polymeric blend has a conductivity above about 10-9 S/cm.
18. A process as in claim 17, wherein said intrinsically conductive polymer is selected from the group consisting of polyanilines.
19. A process as in claim 18, wherein said polyaniline is doped.
20. A process as in claim 19, wherein said polyaniline is doped with hydrochloric acid or organic sulfonic acids.
21. A process as in Claim 17, wherein said thermoplastic polymer is selected from the group consisting of polyvinyl chloride, copolymers of polyvinyl chloride with vinyl acetate, chlorinated polyethylene, polyamides, polyesters, polyacetates, polyvinyl acetates, polyacrylates, polyurethanes, and copolymers and mixtures thereof.
22. A process as in claim 17, wherein said ester free plasticizer is a sulfonamide,
23. A process as in claim 17, wherein said sulfonamide plasticizer is selected from the group consisting of N-butyl benzene sulfonamide, N-butyl toluene sulfonamide and N-ethyl toluene sulfonamide.
24. A process as in claim 17, wherein said plasticizer has a solubility parameter of greater than about 11 (cal/cm3)1/2.
25. A process as in claim 17, wherein said acidic surfactant has a pH of less than about 6.
26. A process as in claim 25, wherein said acidic surfactant is selected from the group consisting of acid anhydrides, lactones and organic phosphate esters.
27. A process as in claim 26, wherein said organic phosphate ester is a nonionic ethylene oxide adduct type.
28. A process as in claim 17, wherein said impact modifier is chlorinated polyethylene.
29. A process as in claim 17, wherein the blend comprises from about 1 to about 50 parts by weight of said intrinsically conductive polymer and from about 99 to about 50 parts by weight of said thermoplastic material.
30. A process as in claim 29, wherein said thermoplastic material comprises fromabout 99 to 1 percent by weight of said thermoplastic polymer and from 1 to about 99 percent by weight of said impact modifier.
31. A process as in claim 29, wherein said thermoplastic material further comprises from about 0 to about 66 parts by weight of said ester-free plasticizer with an attendant decrease in the amount of said thermoplastic polymer present in said thermoplastic material.
32. A process as in claim 31, wherein said thermoplastic material further comprises from about 0 to about 20 percent by weight of said acidic surfactant based upon the amount of said intrinsically conductive polymer, with all attendant decrease in the amount of said thermoplastic polymer present in said thermoplastic material.
33. A process as in claim 32, comprising the initial steps of forming a pre-blend of said intrinsically conductive polymer and said acidic surfactant, and blending said pre-blend with said thermoplastic material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/648,734 US5217649A (en) | 1991-01-31 | 1991-01-31 | Electrically conductive blends of intrinsically conductive polymers and thermoplastic polymers containing sulfonamide plasticizer and acidic surfactant |
| US648,734 | 1991-01-31 |
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| Publication Number | Publication Date |
|---|---|
| CA2059945A1 true CA2059945A1 (en) | 1992-08-01 |
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| CA002059945A Abandoned CA2059945A1 (en) | 1991-01-31 | 1992-01-23 | Electrically conductive blends of intrinsically conductive polymers and thermoplastic polymers and a process for their preparation |
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| Country | Link |
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| US (1) | US5217649A (en) |
| EP (1) | EP0497514B1 (en) |
| JP (1) | JPH04318069A (en) |
| AT (1) | ATE150577T1 (en) |
| CA (1) | CA2059945A1 (en) |
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| JPH0826231B2 (en) * | 1991-08-16 | 1996-03-13 | インターナショナル・ビジネス・マシーンズ・コーポレイション | Conductive polymer material and its use |
| JP3056001B2 (en) * | 1992-02-18 | 2000-06-26 | 日本ゼオン株式会社 | Conductive plastisol molded product |
| US5494609A (en) * | 1992-04-15 | 1996-02-27 | Kulkarni; Vaman G. | Electrically conductive coating compositions and method for the preparation thereof |
| USH1523H (en) * | 1993-03-08 | 1996-04-02 | The United States Of America As Represented By The Secretary Of The Army | Method of making a polymer film having a conductivity gradient along its thickness and polymer film so made |
| DE4317010A1 (en) * | 1993-05-17 | 1994-11-24 | Zipperling Kessler & Co | Dispersible intrinsically conductive polymer and process for its manufacture |
| US5532025A (en) * | 1993-07-23 | 1996-07-02 | Kinlen; Patrick J. | Corrosion inhibiting compositions |
| US5783111A (en) * | 1993-09-03 | 1998-07-21 | Uniax Corporation | Electrically conducting compositions |
| US5382491A (en) * | 1993-12-21 | 1995-01-17 | International Business Machines Corporation | Toner composition |
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| EP3183290A4 (en) * | 2014-08-21 | 2018-09-05 | Yen, William Winchin | Microporous sheet product and methods for making and using the same |
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| GB1399467A (en) * | 1971-10-26 | 1975-07-02 | Ici Ltd | Textile articles |
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| USH944H (en) * | 1989-11-03 | 1991-08-06 | The United States Of America As Represented By The Secretary Of The Army | Heterogeneous composite and method of making |
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-
1991
- 1991-01-31 US US07/648,734 patent/US5217649A/en not_active Expired - Lifetime
-
1992
- 1992-01-23 CA CA002059945A patent/CA2059945A1/en not_active Abandoned
- 1992-01-24 AT AT92300622T patent/ATE150577T1/en active
- 1992-01-24 DE DE69218274T patent/DE69218274T2/en not_active Expired - Fee Related
- 1992-01-24 EP EP92300622A patent/EP0497514B1/en not_active Expired - Lifetime
- 1992-01-30 JP JP4038331A patent/JPH04318069A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE150577T1 (en) | 1997-04-15 |
| EP0497514A1 (en) | 1992-08-05 |
| DE69218274D1 (en) | 1997-04-24 |
| DE69218274T2 (en) | 1997-08-28 |
| EP0497514B1 (en) | 1997-03-19 |
| US5217649A (en) | 1993-06-08 |
| JPH04318069A (en) | 1992-11-09 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |