USH1601H - Compatibilized polyketone polymer blend - Google Patents
Compatibilized polyketone polymer blend Download PDFInfo
- Publication number
- USH1601H USH1601H US08/396,809 US39680995A USH1601H US H1601 H USH1601 H US H1601H US 39680995 A US39680995 A US 39680995A US H1601 H USH1601 H US H1601H
- Authority
- US
- United States
- Prior art keywords
- blend
- polycarbonate
- polymer
- polyketone
- polymers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920001470 polyketone Polymers 0.000 title claims abstract description 33
- 229920002959 polymer blend Polymers 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 42
- 239000004417 polycarbonate Substances 0.000 claims abstract description 42
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- -1 nitro-substituted phenylene Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 3
- 229920001897 terpolymer Polymers 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920006126 semicrystalline polymer Polymers 0.000 description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- 229920004142 LEXAN™ Polymers 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
-
- 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
Definitions
- This invention is related to polyketone polymers. More particularly, the invention relates to compatibilized polyketone polymers blends.
- Polymers of carbon monoxide and ethylenically unsaturated hydrocarbons have been known and available for some time.
- High molecular weight linear alternating polyketones are of considerable interest because they exhibit good physical properties.
- These polymers can be represented by units of the repeating formula ##STR1## wherein A is the moiety obtained by the polymerization of an ethylenically unsaturated hydrocarbon through the ethylenic unsaturation.
- This class of polymers is disclosed in numerous U.S. patents assigned to Shell Oil Company and is exemplified by U.S. Pat. Nos. 4,880,865 and 4,818,811 which are incorporated herein by reference.
- polymers are relatively high molecular weight materials having established utility as premium thermoplastics in the production of shaped articles such as containers for food and drink and parts for the automotive industry. These articles and applications can be produced by processing the polyketone polymer according to well known methods.
- Semi-crystalline polymers tend to have good chemical resistance but have dimensional stability and toughness characteristics that are not optimal for certain applications.
- Amorphous polymers tend to have better dimensional stability than semi-crystalline polymers (less mold shrinkage, and lower coefficient of thermal expansion in useful temperature ranges) and in some instances exhibit better toughness.
- amorphous polymers invariably exhibit chemical resistance characteristics that are inferior to those of semi-crystalline polymers. Indeed, they can be completely insuffuicient for certain applications.
- polymer blends possess an average of the properties found in the components. U.S. Pat. No. 4,880,908 to Lutz and Gergen is drawn to a blend of polyketone (which is semi-crystalline) and polycarbonate (which is amorphous). Thus, one might consider a blend of the two types of polymers. Unfortunately, it is has been found that when such blends have been produced the overall properties have not been adequate for certain applications because the two types of polymers have limited compatibility.
- polymer blends can be classified as either miscible (single-phase) or immiscible (multi-phase). Most combinations of polymers are immiscible.
- the formation of a dispersed phased in a continuous phase and phase separation (e.g., upon changing temperatures) are common occurrences.
- Blend morphology can thus be a dynamic phenomenon especially during processing.
- the introduction of compatibilizers is one method of stablizing and improving the internal structure, or morphology of the blend.
- Such substances can alter the interfacial tension of blend phases or work via mechanisms such as the formation of an interpenetrating polymer network (IPN) to improve adhesion between phases.
- IPN interpenetrating polymer network
- blend compatibility is a utilitarian one. It is used as an overall description of the properties of the blend relative to the expected weighted average properties of the pure constituents. The properties in question are those most relevant to the application of the blend. As such, determining whether a given blend is compatible may be specific to the requirements of the planned application. Nevertheless, it is has been found that among multiphase blends, compatibility generally increases as the strength of the blend interface increases. Thus, most efforts directed toward improving the compatibility of a polymer blend are concerned with strengthening this interfacial region.
- the present invention is a compatibilized polymeric blend comprising polyketone polymer, polycarbonate polymer, and a minor amount of a reactive graft compatibilizer.
- the compatibilizer is a blend of polycarbonate in polyamide which comprises polycarbonate/polyamide graft copolymer.
- a blend comprising between about 70 and 30% wt polyketone, between about 30 and 70% wt polycarbonate, and between about 1 and 20% wt of a reactive graft compatibilizer (weight percents are based on the total weight of the blend).
- the materials useful in the practice of this invention include a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon (sometimes simply referred to as a polyketone polymer), polycarbonate polymer, and a graft copolymer of polycarbonate and polyamide.
- compositions may also be included in the blend.
- fillers, extenders, lubricants, pigments, plasticizers, and other polymeric materials can be added to the compositions to improve or otherwise alter the properties of the composition.
- the practice of this invention involves suitably contacting sufficient quantities of the useful material to form the inventive blend.
- the polyketone polymers which are employed as the major component of the inventive polymer blend are of a linear alternating structure and contain substantially one molecule of carbon monoxide for each molecule of ethylenically unsaturated hydrocarbon.
- the preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon of at least 3 carbon atoms, particularly an ⁇ -olefin such as propylene.
- the preferred polyketone terpolymers When the preferred polyketone terpolymers are employed as the major polymeric component of the blends of the invention, there will be within the terpolymer at least about 2 units incorporating a moiety of ethylene for each unit incorporating a moiety of the second hydrocarbon. Preferably, there will be from about 10 units to about 100 units incorporating a moiety of the second hydrocarbon.
- the polymer chain of the preferred polyketone polymers is therefore represented by the repeating formula ##STR2## where G is the moiety of ethylenically unsaturated hydrocarbon of at least three carbon atoms polymerized through the ethylenic unsaturation and the ratio of y:x is no more than about 0.5.
- polyketone polymers of number average molecular weight from about 1000 to about 200,000, particularly those of number average molecular weight from about 20,000 to about 90,000 as determined by gel permeation chromatography.
- the physical properties of the polymer will depend in part upon the molecular weight, whether the polymer is a copolymer of a terpolymer, and in the case of terpolymers the nature of the proportion of the second hydrocarbon present.
- Typical melting points for the polymers are from about 175° C. to about 300° C., more typically from about 210° C. to about 270° C.
- the polymers have a limiting viscosity number (LVN), measured in m-cresol at 60° C. in a standard capillary viscosity measuring device, of from about 0.5 dl/g to about 10 dl/g, more frequently of from about 0.8 dl/g to about 4 dl/g.
- LPN limiting viscosity number
- U.S. Pat. No. 4,808,699 teaches the production of linear alternating polymers by contacting ethylene and carbon monoxide in the presence of a catalyst comprising a Group VII metal compound, an anion of a nonhydrohalgenic acid with a pKa less than 6 and a bidentate phosphorous, arsenic or antimony ligand.
- U.S. Pat. No. 4,868,282 teaches the production of linear random terpolymers by contacting carbon monoxide and ethylene in the presence of one or more hydrocarbons having an olefinically unsaturated group with a similar catalyst.
- the polycarbonates employed in the blends of the invention are polyesters of carbonic acid having a structure illustratively formed by an ester exchange between a dihydroxy compound and carbonate diester.
- the method by which the polycarbonates are produced is not material and polycarbonates produced by a variety of methods are useful in the blends of the invention. It is conventional to prepare polycarbonates either by reacting a carbonate precursor, such as phosgene, and a dihydroxy compound, such as bisphenol A, or by ester exchange between a dihydroxy compound and a carbonate diester, such as a diphenyl carbonate.
- a carbonate precursor such as phosgene
- a dihydroxy compound such as bisphenol A
- ester exchange between a dihydroxy compound and a carbonate diester such as a diphenyl carbonate.
- the preferred polycarbonates used in the blends of the invention are linear aromatic polycarbonates of the general formula ##STR3## wherein Ar is selected from the group consisting of phenylene and alkyl, aryl, alkoxy, aryloxy, halogen and nitro-substituted phenylene; Z is a divalent hydrocarbon radical containing 1-15 carbon atoms, m is an integer of 0 or 1, and p is an integer of at least 2. The exact value of p is not critical but for commercial applications p is typically chosen to give a number average molecular weight of no more than about 60,000.
- the preferred linear aromatic polycarbonate for use in this invention is obtained when Ar in the formulae immediately above is p-phenylene and Z is isopropylidene.
- This aromatic polycarbonate is prepared by reacting bisphenol A with phosgene and is sold by General Electric Company under the trademark LEXAN®.
- Commercial polycarbonate typically has a molecular weight of at least 18,000 and a melt processing temperature of at least 235° C.
- the compatibilizers usable herein are reactive graft compatibilizers which are generally polymer mixtures which comprise one component identical to, or reactive with, the polyketone component of the blend, and another component identical to, or reactive with, the polycarbonate component of the blend.
- the compatibilizer also comprises grafted copolymer of the components of the mixture of the compatibilizer.
- a mixture of polycarbonate and polyamide which mixture also comprises graft copolymer of polycarbonate and polyamide is one example of such a compatibilizer.
- the polycarbonate component is identical with the polycarbonate component of the blend while the polyamide component is reactive with the polyketone component of the blend.
- the mixture commercially available as "DEXCARB" (a product of the Dexter Plastics Company comprising 60% wt polycarbonate and 40% wt polycaprolaction (Nylon 6)) is the most preferred compatibilizer.
- compositions of the invention may be modified by one or more conventional additives such as stabilizers and inhibitors of oxidative, thermal, and ultraviolet light degradation; lubricants and mold release agents, fire resistant materials, colorants including dyes and pigments, and other substances to modify the polymer.
- additives can be incorporated into the composition at any stage in the preparation of the thermoplastic composition.
- the stabilizers are included early to preclude the initiation of degradation before the composition can be protected.
- the method of producing the inventive polymer blend is not material so long as a relatively uniform distribution of the components is obtained.
- any conventional or known method for producing blends is considered suitable. It is preferred for the blend to have intimate mixing of the polymers. That is, microscopic distribution of the consitituents having the size of the dispersed phase of no more than about 10 microns, preferably about 1 micron is desired.
- the inventive blend can be processed by conventional methods such as extrusion and injection molding into various articles of manufacture such as automobile parts, household or outdoor appliance parts, machine housings or other molded articles.
- a terpolymer of carbon monoxide, ethylene, and propylene was produced in the presence of a catalyst composition formed from palladium acetate, the anion of triflouroacetatic acid and 1,3-bis(diphenylphosphino)-propane.
- the melting point of the linear terpolymer was 220° C. and it had a limiting viscosity number (LVN) of 1.8 measured at 60° C. in m-cresol.
- Blends were prepared of the terpolymer of Example 1, "LEXAN 141-112" (a polycarbonate polymer commercially available from General Electric Plastics), and “DEXCARB 507W” (a 60% wt polycarbonate/40% wt nylon graft copolymer commercially available from Dexter Plastics Company).
- the blends were prepared as shown in Table 1 and compounded on a 30 mm Haake co-rotating, intermeshing twin screw extruder operating at a melt processing temperature of between about 275° and 285° C. The speed of the screws was about 250 RPM.
- Blend A a blend of polyketone polymer and polycarbonate polymer without reactive graft compatibilizer, was a white opaque melt with poor melt strength and some die swelling.
- Blends B-E displayed improved melt strength and reduced die swelling which are indicative of improved compatibility when melt compounding polymer blends.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A blend of polyketone and polycarbonate polymers is presented. The polymer blend is produced by blending polyketone polymer, polycarbonate polymer, and a reactive graft compatibilizer. The a reactive graft compatibilizer compatibilizes the blend.
Description
This invention is related to polyketone polymers. More particularly, the invention relates to compatibilized polyketone polymers blends.
Polymers of carbon monoxide and ethylenically unsaturated hydrocarbons, commonly called polyketones, have been known and available for some time. High molecular weight linear alternating polyketones are of considerable interest because they exhibit good physical properties. These polymers can be represented by units of the repeating formula ##STR1## wherein A is the moiety obtained by the polymerization of an ethylenically unsaturated hydrocarbon through the ethylenic unsaturation. This class of polymers is disclosed in numerous U.S. patents assigned to Shell Oil Company and is exemplified by U.S. Pat. Nos. 4,880,865 and 4,818,811 which are incorporated herein by reference.
These polymers are relatively high molecular weight materials having established utility as premium thermoplastics in the production of shaped articles such as containers for food and drink and parts for the automotive industry. These articles and applications can be produced by processing the polyketone polymer according to well known methods.
Semi-crystalline polymers tend to have good chemical resistance but have dimensional stability and toughness characteristics that are not optimal for certain applications. Amorphous polymers, on the other hand, tend to have better dimensional stability than semi-crystalline polymers (less mold shrinkage, and lower coefficient of thermal expansion in useful temperature ranges) and in some instances exhibit better toughness. However, amorphous polymers invariably exhibit chemical resistance characteristics that are inferior to those of semi-crystalline polymers. Indeed, they can be completely insuffuicient for certain applications. Generally, polymer blends possess an average of the properties found in the components. U.S. Pat. No. 4,880,908 to Lutz and Gergen is drawn to a blend of polyketone (which is semi-crystalline) and polycarbonate (which is amorphous). Thus, one might consider a blend of the two types of polymers. Unfortunately, it is has been found that when such blends have been produced the overall properties have not been adequate for certain applications because the two types of polymers have limited compatibility.
In the case of polyketone polymers, it would be advantageous to retain the more desirable properties of the polyketone polymers and yet improve other properties. Finding the correct types and proportions of polymers that will comprise such a blend and determining whether such blends are workable can be complex.
Generally, polymer blends can be classified as either miscible (single-phase) or immiscible (multi-phase). Most combinations of polymers are immiscible. The formation of a dispersed phased in a continuous phase and phase separation (e.g., upon changing temperatures) are common occurrences. Blend morphology can thus be a dynamic phenomenon especially during processing. The introduction of compatibilizers is one method of stablizing and improving the internal structure, or morphology of the blend. Such substances can alter the interfacial tension of blend phases or work via mechanisms such as the formation of an interpenetrating polymer network (IPN) to improve adhesion between phases. Employing theoretical considerations to such problems is not an entirely reliable approach. For example, it has often been found that model compounds that may suggest one or the other such formulations are amenable to a particular mechanism proves to be inaccurate when the polymeric analogues of those models are employed.
Futhermore, the term "blend compatibility" is a utilitarian one. It is used as an overall description of the properties of the blend relative to the expected weighted average properties of the pure constituents. The properties in question are those most relevant to the application of the blend. As such, determining whether a given blend is compatible may be specific to the requirements of the planned application. Nevertheless, it is has been found that among multiphase blends, compatibility generally increases as the strength of the blend interface increases. Thus, most efforts directed toward improving the compatibility of a polymer blend are concerned with strengthening this interfacial region.
Compatibilized polyketone/polycarbonate blends which present properties that are better than those of the binary blends would enhance the range of applications of such blends.
The present invention is a compatibilized polymeric blend comprising polyketone polymer, polycarbonate polymer, and a minor amount of a reactive graft compatibilizer.
In one aspect of the invention the compatibilizer is a blend of polycarbonate in polyamide which comprises polycarbonate/polyamide graft copolymer.
In another aspect of the invention, a blend is presented comprising between about 70 and 30% wt polyketone, between about 30 and 70% wt polycarbonate, and between about 1 and 20% wt of a reactive graft compatibilizer (weight percents are based on the total weight of the blend).
It has been found that a blend of polyketone polymer and polycarbonate polymer compatibilzed with a reactive graft compatibilizer results in a polymeric blend having excellent physical properties. Generally speaking,the materials useful in the practice of this invention include a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon (sometimes simply referred to as a polyketone polymer), polycarbonate polymer, and a graft copolymer of polycarbonate and polyamide.
Other common polymers additives may also be included in the blend. For instance, fillers, extenders, lubricants, pigments, plasticizers, and other polymeric materials can be added to the compositions to improve or otherwise alter the properties of the composition. In general, the practice of this invention involves suitably contacting sufficient quantities of the useful material to form the inventive blend.
The polyketone polymers which are employed as the major component of the inventive polymer blend are of a linear alternating structure and contain substantially one molecule of carbon monoxide for each molecule of ethylenically unsaturated hydrocarbon. The preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon of at least 3 carbon atoms, particularly an α-olefin such as propylene.
When the preferred polyketone terpolymers are employed as the major polymeric component of the blends of the invention, there will be within the terpolymer at least about 2 units incorporating a moiety of ethylene for each unit incorporating a moiety of the second hydrocarbon. Preferably, there will be from about 10 units to about 100 units incorporating a moiety of the second hydrocarbon. The polymer chain of the preferred polyketone polymers is therefore represented by the repeating formula ##STR2## where G is the moiety of ethylenically unsaturated hydrocarbon of at least three carbon atoms polymerized through the ethylenic unsaturation and the ratio of y:x is no more than about 0.5. When copolymer of carbon monoxide and ethylene arc employed in the compositions of the invention, there will be no second hydrocarbon present and the copolymer are represented by the above formula wherein y is zero. When y is other than zero, i.e. terpolymers are employed, the .brket open-st.CO.paren open-st.CH2 --CH2 .paren close-st. units and the --CO.paren open-st.G.paren close-st. units are found randomly throughout the polymer chain, and preferred ratios of y:x are from about 0.01 to about 0.1. The precise nature of the end groups does not appear to influence the properties of the polymer to any considerable extent so that the polymers are fairly represented by the formula for the polymer chains as depicted above.
Of particular interest are the polyketone polymers of number average molecular weight from about 1000 to about 200,000, particularly those of number average molecular weight from about 20,000 to about 90,000 as determined by gel permeation chromatography. The physical properties of the polymer will depend in part upon the molecular weight, whether the polymer is a copolymer of a terpolymer, and in the case of terpolymers the nature of the proportion of the second hydrocarbon present. Typical melting points for the polymers are from about 175° C. to about 300° C., more typically from about 210° C. to about 270° C. The polymers have a limiting viscosity number (LVN), measured in m-cresol at 60° C. in a standard capillary viscosity measuring device, of from about 0.5 dl/g to about 10 dl/g, more frequently of from about 0.8 dl/g to about 4 dl/g.
Preferred methods for the production of the polyketone polymers are illustrated by U.S. Pat. Nos. 4,808,699 and 4,868,282 to Van Broekhoven, et. al. which issued on Feb. 28, 1989 and Sep. 19, 1989 respectively and are incorporated herein by reference. U.S. Pat. No. 4,808,699 teaches the production of linear alternating polymers by contacting ethylene and carbon monoxide in the presence of a catalyst comprising a Group VII metal compound, an anion of a nonhydrohalgenic acid with a pKa less than 6 and a bidentate phosphorous, arsenic or antimony ligand. U.S. Pat. No. 4,868,282 teaches the production of linear random terpolymers by contacting carbon monoxide and ethylene in the presence of one or more hydrocarbons having an olefinically unsaturated group with a similar catalyst.
The polycarbonates employed in the blends of the invention are polyesters of carbonic acid having a structure illustratively formed by an ester exchange between a dihydroxy compound and carbonate diester. The method by which the polycarbonates are produced is not material and polycarbonates produced by a variety of methods are useful in the blends of the invention. It is conventional to prepare polycarbonates either by reacting a carbonate precursor, such as phosgene, and a dihydroxy compound, such as bisphenol A, or by ester exchange between a dihydroxy compound and a carbonate diester, such as a diphenyl carbonate. U.S. Pat. Nos. 3,028,365 and 4,291,15 1 describe preparatory procedures for the production of polycarbonates useful in this invention and are incorporated herein by reference.
The preferred polycarbonates used in the blends of the invention are linear aromatic polycarbonates of the general formula ##STR3## wherein Ar is selected from the group consisting of phenylene and alkyl, aryl, alkoxy, aryloxy, halogen and nitro-substituted phenylene; Z is a divalent hydrocarbon radical containing 1-15 carbon atoms, m is an integer of 0 or 1, and p is an integer of at least 2. The exact value of p is not critical but for commercial applications p is typically chosen to give a number average molecular weight of no more than about 60,000.
The preferred linear aromatic polycarbonate for use in this invention is obtained when Ar in the formulae immediately above is p-phenylene and Z is isopropylidene. This aromatic polycarbonate is prepared by reacting bisphenol A with phosgene and is sold by General Electric Company under the trademark LEXAN®. Commercial polycarbonate typically has a molecular weight of at least 18,000 and a melt processing temperature of at least 235° C.
The compatibilizers usable herein are reactive graft compatibilizers which are generally polymer mixtures which comprise one component identical to, or reactive with, the polyketone component of the blend, and another component identical to, or reactive with, the polycarbonate component of the blend. However, both components of the reactive graft compatibilizer need not be identical with both components of the blend to be compatibilized. The compatibilizer also comprises grafted copolymer of the components of the mixture of the compatibilizer. A mixture of polycarbonate and polyamide which mixture also comprises graft copolymer of polycarbonate and polyamide is one example of such a compatibilizer. The polycarbonate component is identical with the polycarbonate component of the blend while the polyamide component is reactive with the polyketone component of the blend. The mixture commercially available as "DEXCARB" (a product of the Dexter Plastics Company comprising 60% wt polycarbonate and 40% wt polycaprolaction (Nylon 6)) is the most preferred compatibilizer.
It has been found that when a mixture of comparable quantities (by weight) of a polyketone polymer ( especially a copolymer or terpolymer) and polycarbonate polymer are blended together with a minor amount of a reactive graft compatibiler in the relative proportions between about 1:3 Polycarbonate to Polyketone and 3:1 Polycarbonate to Polyketone with between about 1 and 20% wt compatibiler (based on total weight of blend), a novel and useful blend is produced. Preferred proportions of Polycarbonate to Polyketones are between about 1:2 and 2:1 with the addition of between about 1 and 20% wt compatabilizer (based on total weight of the blend).
The compositions of the invention may be modified by one or more conventional additives such as stabilizers and inhibitors of oxidative, thermal, and ultraviolet light degradation; lubricants and mold release agents, fire resistant materials, colorants including dyes and pigments, and other substances to modify the polymer. The additives can be incorporated into the composition at any stage in the preparation of the thermoplastic composition. Preferably the stabilizers are included early to preclude the initiation of degradation before the composition can be protected.
The method of producing the inventive polymer blend is not material so long as a relatively uniform distribution of the components is obtained. Generally speaking, any conventional or known method for producing blends is considered suitable. It is preferred for the blend to have intimate mixing of the polymers. That is, microscopic distribution of the consitituents having the size of the dispersed phase of no more than about 10 microns, preferably about 1 micron is desired.
The inventive blend can be processed by conventional methods such as extrusion and injection molding into various articles of manufacture such as automobile parts, household or outdoor appliance parts, machine housings or other molded articles.
The invention is further illustrated by the following non-limiting examples.
A terpolymer of carbon monoxide, ethylene, and propylene was produced in the presence of a catalyst composition formed from palladium acetate, the anion of triflouroacetatic acid and 1,3-bis(diphenylphosphino)-propane. The melting point of the linear terpolymer was 220° C. and it had a limiting viscosity number (LVN) of 1.8 measured at 60° C. in m-cresol.
Blends were prepared of the terpolymer of Example 1, "LEXAN 141-112" (a polycarbonate polymer commercially available from General Electric Plastics), and "DEXCARB 507W" (a 60% wt polycarbonate/40% wt nylon graft copolymer commercially available from Dexter Plastics Company). The blends were prepared as shown in Table 1 and compounded on a 30 mm Haake co-rotating, intermeshing twin screw extruder operating at a melt processing temperature of between about 275° and 285° C. The speed of the screws was about 250 RPM.
Blend A, a blend of polyketone polymer and polycarbonate polymer without reactive graft compatibilizer, was a white opaque melt with poor melt strength and some die swelling.
______________________________________
POLY- POLY-
KETONE CARBONATE COMPATIBILIZER
SAMPLE (wt %) (wt %) (wt %)
______________________________________
A 50 50 0
B 49 49 2
C 47.5 47.5 5
D 45 45 10
E 40 40 20
______________________________________
Blends B-E displayed improved melt strength and reduced die swelling which are indicative of improved compatibility when melt compounding polymer blends.
Subsequent to blending, specimens of the blends of Example 2 were injection molded at 280° C. into standard test specimens using an Arburg Allrounder injection molding machine. Tensile and impact testing were conducted according to ASTM D638 and ASTM D256 respectively. Results are shown in Table 2.
______________________________________
TENSILE TENSILE IZOD
STRENGTH ELONGATION STRENGTH
SAMPLE (psi) (%) (22 C, ft-lb/in)
______________________________________
A 8710 217 1.8
B 8870 225 1.9
C 9260 230 1.9
D 10550 295 3.0
E 10310 296 6.9
Neat 9120 256 4.7
Polyketone
Neat Poly-
8820 198 15.4
carbonate
______________________________________
The increase in tensile strength and tensile elongation exhibited by samples B-E over that of sample A shows the improvement in compatibility achieved through the introduction of compatibilizer. Notched impact strength increases as the amount of reactive compatabilizer in the blend increases. This is indicative of good blend compatibility since weak interfaces in the blend would have been manifested as a site for crack initiation and lesser impact strength.
Claims (7)
1. A compatibilized polymer blend comprising a linear alternating polymer of carbon monoxide and one or more ethylenically unsaturated hydrocarbons, a polycarbonate polymer, and a minor amount of a compatibilizer comprising about 60% wt polycarbonate and about 40% wt nylon 6.
2. The blend of claim 1 wherein the ratio of polyketone to polycarbonate is between about 3:1 and 1:3 (based upon total weight of said blend).
3. The blend of claim 1 comprising about 40 wt % of polyketone, about 40 wt % of polycarbonate, and about 20 wt % reactive graft compatibilizer.
4. The blend of claim 1 wherein said polycarbonate polymer is selected from the group consisting of ##STR4## wherein Ar is selected from the group consisting of phenylene and alkyl, aryl, alkoxy, aryloxy, halogen and nitro-substituted phenylene; Z is a divalent hydrocarbon radical containing 1-15 carbon atoms, m is an integer of 0 or 1, and p is an integer of at least 2.
5. The blend of claim 1 wherein said polycarbonate polymer is a polycarbonate of bisphenol A.
6. The blend of claim 1 wherein said reactive graft compatibilizer comprsies nylon 6 and a polycarbonate of bisphenol A.
7. An article of manufacture made from the blend of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/396,809 USH1601H (en) | 1995-03-02 | 1995-03-02 | Compatibilized polyketone polymer blend |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/396,809 USH1601H (en) | 1995-03-02 | 1995-03-02 | Compatibilized polyketone polymer blend |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH1601H true USH1601H (en) | 1996-10-01 |
Family
ID=23568691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US08/396,809 Abandoned USH1601H (en) | 1995-03-02 | 1995-03-02 | Compatibilized polyketone polymer blend |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USH1601H (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336637A (en) * | 2016-08-26 | 2017-01-18 | 青岛海尔新材料研发有限公司 | PC/PK alloy material and preparation method thereof |
| CN106589882A (en) * | 2016-11-29 | 2017-04-26 | 中广核俊尔新材料有限公司 | Polycarbonate and polyketone alloy and preparation method thereof |
| CN106751654A (en) * | 2016-11-29 | 2017-05-31 | 中广核俊尔新材料有限公司 | A kind of wear-resisting regeneration PC/POK alloy materials and its preparation method and application |
| CN108603006A (en) * | 2015-10-02 | 2018-09-28 | 三星电子株式会社 | Polymer composition, method for producing polymer composition, electronic device and method for producing electronic device |
| US20200010676A1 (en) * | 2016-12-27 | 2020-01-09 | Lg Chem, Ltd. | Polyketone resin composition and polyketone resin molded article |
| CN111171506A (en) * | 2018-11-12 | 2020-05-19 | 万华化学集团股份有限公司 | A kind of low internal stress polycarbonate material and preparation method thereof |
| US10941291B2 (en) * | 2016-12-27 | 2021-03-09 | Lg Chem, Ltd. | Polyalkylene carbonate resin composition and polyalkylene carbonate resin molded article |
| CN112724642A (en) * | 2020-12-31 | 2021-04-30 | 广东乔艺塑胶有限公司 | POK (polyester pre-oriented Ketone) environment-friendly material composition and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4880908A (en) * | 1988-04-11 | 1989-11-14 | Shell Oil Company | Polymer blend of carbon monoxide/olefin copolymer and polycarbonate |
| US5079316A (en) * | 1990-02-22 | 1992-01-07 | The Dow Chemical Company | Graft copolymers of polymerizable monomers and olefin/carbon monoxide copolymers |
| US5124402A (en) * | 1990-08-21 | 1992-06-23 | The Dow Chemical Company | Thermoplastic molding compositions with improved solvent resistance and impact strength, and methods for preparation thereof |
| US5210137A (en) * | 1990-11-19 | 1993-05-11 | Shell Oil Company | Polyketone polymer blends |
-
1995
- 1995-03-02 US US08/396,809 patent/USH1601H/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4880908A (en) * | 1988-04-11 | 1989-11-14 | Shell Oil Company | Polymer blend of carbon monoxide/olefin copolymer and polycarbonate |
| US5079316A (en) * | 1990-02-22 | 1992-01-07 | The Dow Chemical Company | Graft copolymers of polymerizable monomers and olefin/carbon monoxide copolymers |
| US5124402A (en) * | 1990-08-21 | 1992-06-23 | The Dow Chemical Company | Thermoplastic molding compositions with improved solvent resistance and impact strength, and methods for preparation thereof |
| US5210137A (en) * | 1990-11-19 | 1993-05-11 | Shell Oil Company | Polyketone polymer blends |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603006A (en) * | 2015-10-02 | 2018-09-28 | 三星电子株式会社 | Polymer composition, method for producing polymer composition, electronic device and method for producing electronic device |
| US10851238B2 (en) | 2015-10-02 | 2020-12-01 | Samsung Electronics Co., Ltd. | Polymeric composition, method for producing polymeric composition, electronic apparatus, and method for manufacturing electronic apparatus |
| CN108603006B (en) * | 2015-10-02 | 2021-02-02 | 三星电子株式会社 | Polymer composition, method for manufacturing polymer composition, electronic device, and method for manufacturing electronic device |
| CN106336637A (en) * | 2016-08-26 | 2017-01-18 | 青岛海尔新材料研发有限公司 | PC/PK alloy material and preparation method thereof |
| CN106589882A (en) * | 2016-11-29 | 2017-04-26 | 中广核俊尔新材料有限公司 | Polycarbonate and polyketone alloy and preparation method thereof |
| CN106751654A (en) * | 2016-11-29 | 2017-05-31 | 中广核俊尔新材料有限公司 | A kind of wear-resisting regeneration PC/POK alloy materials and its preparation method and application |
| US20200010676A1 (en) * | 2016-12-27 | 2020-01-09 | Lg Chem, Ltd. | Polyketone resin composition and polyketone resin molded article |
| US10844220B2 (en) * | 2016-12-27 | 2020-11-24 | Lg Chem, Ltd. | Polyketone resin composition and polyketone resin molded article |
| US10941291B2 (en) * | 2016-12-27 | 2021-03-09 | Lg Chem, Ltd. | Polyalkylene carbonate resin composition and polyalkylene carbonate resin molded article |
| CN111171506A (en) * | 2018-11-12 | 2020-05-19 | 万华化学集团股份有限公司 | A kind of low internal stress polycarbonate material and preparation method thereof |
| CN111171506B (en) * | 2018-11-12 | 2023-03-03 | 万华化学集团股份有限公司 | Low-internal-stress polycarbonate material and preparation method thereof |
| CN112724642A (en) * | 2020-12-31 | 2021-04-30 | 广东乔艺塑胶有限公司 | POK (polyester pre-oriented Ketone) environment-friendly material composition and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4528335A (en) | Polymer blends | |
| US4415706A (en) | Compatible blends of polyglutarimides and polyamides | |
| AU701035B2 (en) | Flame retardant polyketone polymer blend | |
| US4874819A (en) | Polymer blend | |
| USH1601H (en) | Compatibilized polyketone polymer blend | |
| EP0339745B1 (en) | Polyketone polymer composition | |
| US4900789A (en) | Polymer blend of carbon monoxide/olefin copolymer and conjugated alkadiene | |
| US4851470A (en) | Mineral filled polyketone blend | |
| US4880908A (en) | Polymer blend of carbon monoxide/olefin copolymer and polycarbonate | |
| US5162432A (en) | Polyketone polymer blends | |
| CA1327663C (en) | Thermoplastic polyamide-polyarylate compositions | |
| US4960838A (en) | Blend of polyketone polymer with an amorphous polyamide polymer | |
| CA1135436A (en) | Polyarylene ester compositions | |
| JPS62146952A (en) | Thermoplastic polycarbonate molding material | |
| US6001955A (en) | High modulus polyketones | |
| US4891405A (en) | Moldable styrene-maleic anhydride/polybutylene terephthalate composition | |
| US4866124A (en) | Blends based on vinyl-aromatic polymers endowed with improved characteristics of chemical resistance | |
| USH917H (en) | Polymer blend | |
| US4826926A (en) | Polymer blend of carbon monoxide/olefin copolymer and a poly(2-oxazoline) polymer | |
| EP0517157B1 (en) | Polyarylate/polyester thermoplastic resin composition having high impact resistance and low melt viscosity | |
| US5219954A (en) | Miscible polyketone phenolic novolac blends | |
| KR0123043B1 (en) | Thermoplastic resin composition | |
| US5227437A (en) | Isomorphic polyketone polymer blend | |
| JPH02305850A (en) | Thermoplastic resin composition | |
| USH1187H (en) | Polymer blends |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |