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Patent US5081184 - Containing polystyrene - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsImpact- and solvent-resistant resin blends are prepared from a polyphenylene ether or blend thereof with a polystyrene, a linear polyester such as a poly(alkylene dicarboxylate), at least one polymer containing a substantial proportion of aromatic polycarbonate units as a compatibilizing agent, and,...http://www.google.com/patents/US5081184?utm_source=gb-gplus-sharePatent US5081184 - Containing polystyreneAdvanced Patent SearchPublication numberUS5081184 APublication typeGrantApplication numberUS 07/354,607Publication dateJan 14, 1992Filing dateMay 22, 1989Priority dateAug 2, 1985Fee statusLapsedPublication number07354607, 354607, US 5081184 A, US 5081184A, US-A-5081184, US5081184 A, US5081184AInventorsSterling B. Brown, Dennis J. McFay, John B. Yates, III, Gim F. LeeOriginal AssigneeGeneral Electric CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (17), Referenced by (9), Classifications (26), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetContaining polystyreneUS 5081184 AAbstract Impact- and solvent-resistant resin blends are prepared from a polyphenylene ether or blend thereof with a polystyrene, a linear polyester such as a poly(alkylene dicarboxylate), at least one polymer containing a substantial proportion of aromatic polycarbonate units as a compatibilizing agent, and, preferably, at least one elastomeric polyphenylene ether-compatible impact modifier. There may also be present a minor amount of at least one epoxide and/or masked isocyanate such as triglycidyl isocyanurate or a glycidyl methacrylate polymer. The polyphenylene ether preferably has a low proportion of unneutralized amino nitrogen, if any.
What is claimed is: 1. A resinous composition comprising:(A) about 15-50% of at least one polyphenylene ether, or a blend thereof with at least one polystyrene, said polyphenylene ether comprising structural units having the formula ##STR9## wherein in each of said units independently, each Q1 is independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms, and each Q2 is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined or grafted or coupled derivatives thereof; (B) about 20-80% of at least one poly(alkylene dicarboxylate), the weight ratio of component A to component B being at most 1.2:1; and (C) from 3% to about 50% of at least one polymer containing a substantial proportion of aromatic polycarbonate units and having a weight average molecular weight of at least about 40,000 as determined by gel permeation chromatography relative to polystyrene, or a blend thereof with a styrene homopolymer; all percentages being by weight and based on total components A, B and C. 2. A composition according to claim 1 wherein component A is a blend of a poly(2,6-dimethyl-1,4-phenylene ether) with said polystyrene.
3. A composition according to claim 2 wherein the polystyrene in component A is a homopolymer.
4. A composition according to claim 2 wherein the polystyrene in component A is a rubber-modified polystyrene.
5. A composition according to claim 1 wherein component A is a poly(2,6-dimethyl-1,4-phenylene ether).
6. A composition according to claim 5 wherein component B is a poly(ethylene terephthalate) or a poly(butylene terephthalate) and the polycarbonate units in component C are bisphenol A polycarbonate units.
8. A composition according to claim 7 wherein component C is a polycarbonate homopolymer having a weight average molecular weight inthe range of about 40,000-80,000.
9. A composition according to claim 6 wherein the polyphenylene ether contains no more than 800 ppm. of unneutralized amino nitrogen and has an intrinsic viscosity of at least 0.25 dl/g/ as measured in chloroform at 25� C.
10. A composition according to claim 9 wherein the polyphenylene ether has been prepared by oxidative coupling of at least one monohydroxyaromatic compound in the presence of a catalyst comprising a combination of cuprous or cupric ions, halide and at least one amine.
11. A composition according to claim 9 wherein component C is a polycarbonate homopolymer having a weight average molecular weight in the range of about 71,000-200,000.
Ser. No. 154,751, filed Feb. 9, 1988, now U.S. Pat. No. 4,866,130;
Ser. No. 220,396, filed July 1, 1988, now abandoned;
Ser. No. 232,413, filed Aug. 15, 1988, now U.S. Pat. No. 4,978,715. Said Ser. Nos. 154,751 and 232,413 are continuations-in-part of Ser. No. 891,457, filed July 29, 1986, which is a continuation-in-part of Ser. No. 761,712, filed Aug. 2, 1985, and Ser. No. 828,410, filed Feb. 11, 1986, all now abandoned. Said Ser. No. 220,396 is a continuation of Ser. No. 10,867, filed Feb. 4, 1987, now abandoned.
This invention relates to resinous compositions having a combination of such advantageous properties as solvent resistance, high impact strength, favorable tensile properties and thermal stability. More particularly, it relates to improved polyphenylene ether compositions.
An increasing trend in recent years is the employment of resinous compositions as a replacement for metal in such areas as parts for motor vehicles. For such use, it is naturally required that the compositions have a high degree of solvent resistance, particularly to petroleum liquids such as gasoline. If exterior body parts are to be constructed of resinous compositions, they must also have very high impact strength. Other properties such as hydrolytic stability, dimensional stability, toughness, heat resistance and dielectric properties are also important in these and other areas of use.
Many of these properties are possessed by polyphenylene ethers; however, solvent resistance is not one. Therefore, it would be desirable to blend the polyphenylene ethers with resins which have a high degree of crystallinity and thus are highly resistant to solvents. Illustrative of such resins are the linear polyesters including poly(alkylene dicarboxylates), especially the poly(alkylene terephthalates). However, such blends frequently undergo phase separation and delamination. They typically contain large, incompletely dispersed polyphenylene ether particles and no phase interaction between the two resin phases. Molded parts made from such blends are typically characterized by extremely low impact strength.
The present invention provides polymer blends having a high degree of solvent resistance and other favorable properties, which may include high impact and/or tensile strength. It also provides highly compatible polymer blends containing polyphenylene ethers and poly(alkylene dicarboxylates), and resinous molding compositions suitable for use in the fabrication of automotive parts and the like.
The invention is based on the discovery of a new genus of compatible blends containing polyphenylene ethers and poly(alkylene dicarboxylates) in weight ratios as high as 1:1, or even higher under certain circumstances. According to the invention, there is also incorporated in the resinous composition a polymer containing a substantial proportion of aromatic polycarbonate structural units. Said polymer, in combination with the poly(alkylene dicarboxylate), achieves a unique and unexpected compatibilization mechanism with respect to the polyphenylene ether.
In one of its aspects, therefore, the invention is directed to resinous compositions comprising:
(A) about 15-50% of at least one polyphenylene ether, or a blend thereof with at least one polystyrene;
(B) about 20-80% of at least one poly(alkylene dicarboxylate), the weight ratio of component A to component B being at most 1.2:1; and
(C) from 3% to about 50% of at least one polymer containing a substantial proportion of aromatic polycarbonate units and having a weight average molecular weight of at least about 40,000 as determined by gel permeation chromatography relative to polystyrene, or a blend thereof with a styrene homopolymer;
all percentages being by weight and based on total components A, B and C.
The polyphenylene ethers (also known as polyphenylene oxides) used as all or part of component A in the present invention are a well known class of polymers. They are widely used in industry, especially as engineering plastics in applications requiring toughness and heat resistance. Since their discovery, they have given rise to numerous variations and modifications all of which are applicable to the present invention, including but not limited to those described hereinafter.
The polyphenylene ether generally has a number average molecular weight within the range of about 3000-40,000 and a weight average molecular weight within the range of about 20,000-80,000, as determined by gel permeation chromatography. Its intrinsic viscosity is most often in the range of about 0.15-0.6 and preferably at least 0.25 dl./g., as measured in chloroform at 25� C.
The polyphenylene ethers are typically prepared by the oxidative coupling of at least one corresponding monohydroxyaromatic compound. Particularly useful and readily available monohydroxyaromatic compounds are 2,6-xylenol (wherein each Q1 is methyl and each Q2 is hydrogen), whereupon the polymer may be characterized as a poly(2,6-dimethyl-1,4-phenylene ether), and 2,3,6-trimethylpherol (wherein each Q1 and one Q2 is methyl and the other Q2 is hydrogen).
In many polyphenylene ethers obtained under the above-described conditions, a substantial proportion of the polymer molecules, typically constituting as much as about by wight of the polymer, contain end groups having one or frequently both of formulas II and III. It should be understood, however, that other end groups may be present and that the invention in its broadest sense may not be dependent on the molecular structures of the polyphenylene ether end groups.
The use of polyphenylene ethers containing substantial amounts of unneutralized amino nitrogen may, under certain conditions, afford compositions with undesirably low impact and/or tensile strengths. The possible reasons for this are explained hereinafter. The amino compounds include, in addition to the aminoalkyl end groups, traces of amine (particularly secondary amine) in the catalyst used to form the polyphenylene ether.
It has further been found that the properties of the composition can often be improved in several respects, particularly impact strength, by removing or inactivating a substantial proportion of the amino compounds in the polyphenylene ether. Polymers so treated are sometimes referred to hereinafter as "inactivated polyphenylene ethers". They preferably contain unneutralized amino nitrogen, if any, in amounts no greater than 800 ppm. and more preferably in the range of about 200-800 ppm., as determined by the Kjeldahl method. Various means for inactivation have been developed and any one or more thereof may be used.
One such method is to precompound the polyphenylene ether with at least one non-volatile compound containing a carboxylic acid, acid anhydride or ester group, which is capable of neutralizing the amine compourds. This method is of particular interest in the preparation of compositions of this invention having high resistance to heat distortion. Illustrative acids, anhydrides and esters are citric acid, malic acid, agaricic acid, succinic acid, succinic anhydride, maleic acid, maleic anhyhdride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, fumaric acid, diethyl maleate and methyl fumarate. Because of their relatively high reactivity with amino compounds, the free carboxylic acids and especially fumaric acid are generally most useful.
EXAMPLE 1 A mixture of 1.43 parts of maleic anhydride and 100 parts of a poly-(2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight (as determined by gel permeation chromatography) of about 20,000 and an intrinsic viscosity in chloroform at 25� C. of 0.46 dl./g. was tumble-mixed for 15-30 minutes and then extruded on a 20-mm. twin screw extruder at 400 rpm. over a temperature range of about 10�-325� C. The feed rate of the mixture was about 524 grams per 10 minutes. The extruder was vacuum vented with a vacuum pump to a pressure less than 20 torr during the extrusion. The product was the desired inactivated polyphenylene ether.
Component B is at least one linear polyester. The linear polyesters include thermoplastic poly(alkylene dicarboxylates) and alicyclic analogs thereof. They typically comprise structural units of the formula ##STR6## wherein R4 is a saturated divalent aliphatic or alicyclic hydrocarbon radical containing about 2-10 and usually about 2-6 carbon atoms and A1 is a divalent aromatic radical containing about 6-20 carbon atoms. They are ordinarily prepared by the reaction of at least one diol such as ethylene glycol, 1,4-butanediol or 1,4-cyclohexanedimethanol with at least one aromatic dicarboxylic acid such as isophthalic or terephthalic acid, or lower alkyl ester thereof. The poly(alkylene terephthalates), particularly poly(ethylene terephthalate) and poly(butylene terephthalate) and especially the latter, are preferred. Such polyesters are known in the art as illustrated by the following patents:
______________________________________2,465,319            3,047,5392,720,502            3,671,4872,727,881            3,953,3942,822,348            4,128,526.______________________________________
The polyesters generally have number average molecular weights in the range of about 20,000-70,000, as determined by intrinsic viscosity (IV) at 30� C. in a mixture of 60% (by weight) phenol and 40% 1,1,2,2-tetrachloroethane. When high impact strength is an important factor the polyester molecular weight should be relatively high, typically above about 40,000.
The A2 radicals preferably have the formulas
wherein each of A3 and A4 is a monocyclic divalent aromatic radical and Y is a bridging radical in which one or two atoms separate A3 from A4. The free valence bcnds in formula IX are usually in the meta or para positions of A3 and A4 in relation to Y. Such A2 values may be considered as being derived from bisphenols of the formula HO-A3 -Y-A40 H. Frequent reference to bisphenols will be made hereinafter, but it should be understood that A2 values derived from suitable compounds other than bisphenols may be employed as appropriate.
In formula IX, the A3 and A4 values may be unsubstituted phenylene or substituted derivatives thereof, illustrative substituents (one or more) being alkyl, alkenyl (e.g., crosslinkable-graftable moieties such as vinyl and allyl), halo (especially chloro and/or bromo), nitro, alkoxy and the like. Unsubstituted phenylene radicals are preferred. Both A3 and A4 are preferably p-phenylene, although both may be o- or m-phenylene or one o- or m-phenylene and the other p-phenylene.
The bridging radical, Y, is one in which one or two atoms, preferably one, separate A3 from A4. It is most often a hydrocarbon radical and particularly a saturated radical such as methylene, cyclohexylmethylene, 2-[2.2.1]-bicycloheptylmethylene, ethylene, 2,2-propylene, 1,1-(2,2-dimethylpropylene), 1,1-cyclohexylene, 1,1-cyclopentadecylene, 1,1-cyclododecylene or 2,2-adamantylene, especially a gem-alkylene radical. Also included, however, are unsaturated radicals and radicals which are entirely or partially composed of atoms other than carbon and hydrogen. Examples of such radicals are 2,2-dichloroethylene, carbonyl, thio and sulfone. For reasons of availability and particular suitability for the purposes of this invention, the preferred radical of formula VIII is the 2,2-bis(4-phenylene)propane radical, which is derived from bisphenol A and in which Y is isopropylidene and A3 and A4 are each p-phenylene.
Various methods of preparing polycarbonate homopolymers are known, and any of them may be used for preparing component C. They include interfacial and other methods in which phosgene is reacted with bisphenols, transesterification methods in which bisphenols are reacted with diaryl carbonates, and methods involving conversion of cyclic polycarbonate oligomers to linear polycarbonates. The latter method is disclosed in U.S. Pat. Nos. 4,605,731 and 4,644,053.
Copolycarbonates are also useful as component C. Examples thereof are the copolyestercarbonates of the type obtained by the reaction of at least one dihydroxyaromatic compound with a mixture of phosgene and at least one dicarboxylic acid chloride, especially isophthaloyl chloride, terephthaloyl chloride or both. Such copolyestercarbonates contain structural units of formula VIII combined with units of the formula ##STR8## wherein A5 is an aromatic and usually a p- or m-phenylene radical. Other examples are the siloxane-carbonate block copolymers disclosed, for example, in U.S. Pat. Nos. 3,189,662 and 3,419,634, and the polyphenylene ether-polycarbonate block copolymers of U.S. Pat. Nos. 4,374,223 and 4,436,876, which frequently provide compositions with substantially higher heat distortion temperatures than those containing homopolycarbonates. The disclosures of the patents and applications listed above relating to polycarbonates and copolycarbonates are also incorporated by reference herein.
The weight average molecular weight of the homo- or copolycarbonate should be at least about 40,000 (as determined by gel permeation chromatography relative to polystyrene). It is most often in the range of about 40,000-80,000 and especially about 50,000-80,000. However, compositions in which component C has a molecular weight in the range of about 80,000-200,000 often have favorable properties.
In most instances, component C consists of the polycarbonate or copolycarbonate; that is, said polymer is the entire component except for impurities. It is within the scope of the invention, however, to use as component C a blend of polycarbonate or copolyestercarbonate with a styrene homopolymer, typically having a number average molecular weight of about 50,000-250,000. Such blends generally contain at least 50% of the polycarbonate or copolyestercarbonate.
It is often highly preferred, according to the present invention, for the composition also to contain (D) at least one polyphenylene ether-compatible impact modifier. This is particularly true when the area of use is one which demands extremely high impact strength, such as for body parts for motor vehicles. On the other hand, impact modifiers are not necessary when impact strength is not critical but such factors as tensile properties are important; e.g., for under-hood automotive components such as electrical connectors and for internal computer parts.
Suitable impact modifiers include various elastomeric copolymers, of which examples are ethylenepropylene-diene polymers (EPDM's), both unfunctionalized and functionalized with (for example) sulfonate or phosphonate groups; ethylene-propylene rubbers, both unfunctionalized and functionalized (e.g., carboxylated); and block copolymers of alkenylaromatic compounds such as styrene with polymerizable olefins or dienes, including butadiene, isoprene, chloroprene, ethylene, propylene and butylene. Also suitable are core-shell polymers containing, for example, a poly(alkyl acrylate) core attached to a polystyrene shell via an interpenetrating network. Such core-shell polymers are more fully disclosed in U.S. Pat. No. 4,681,915.
It is also appropriate to define compositions containing component D in percentage terms based on total resinous components. In those terms, the particularly preferred compositions according to this invention comprise the following, all percentage proportions being by weight of total resinous components: about 10-45% of component A; about 10-46% of component B; from 3% to about 40% of component C and about 8-25% of component D.
It will be noted that various polystyrenes may be used in the invention as all or part of components A, C and D. However, the specific polystyrenes used are different in various respects. The polystyrene in component A is a homopolymer, random copolymer or rubber-modified polystyrene; homopolymers are used in component C; and component D may be a block or core-shell copolymer. Moreover, polystyrenes are ordinarily present in only one of components A and C, if in either.
It is also within the scope of the invention to employ a polyester-aromatic polycarbonate blend as a source of part or all of components B and C. As explained hereinafter, the use of such a blend may provide somewhat more flexibility in component proportions.
Particularly in compositions containing inactivated polyphenylene ethers and relatively small amounts of polycarbonate, it is frequently found that impact strength and/or resistance to heat distortion are improved if there is also blended into the composition (E) at least one compound selected from those containing at least one cyanurate or isocyanurate moiety and those containing a plurality of epoxide moieties. Illustrative cyanurates and isocyanurates are cyanuric chloride, triethyl cyanurate, triallyl cyanurate, triallyl isocyanurate and triphenyl cyanurate. Epoxide compounds include homopolymers of such compounds as glycidyl acrylate and glycidyl methacrylate, as well as copolymers thereof, preferred comonomers being lower alkyl acrylates, methyl methacrylate, acrylonitrile and styrene. Also useful are epoxy-substituted cyanurates and isocyanurates such as triglycidyl cyanurate and triglycidyl isocyanurate.
In various respects, the proportions of ingredients in the compositions of this invention are an important consideration. It is generally contemplated that components A and B will be present in the compositions described hereinabove in the amounts of about 15-50% and 20-80% respectively, based on total components A, B and C. The preferred proportions of components A and B are in the ranges of about 20-45% and about 20-75%, respectively. Moreover, the weight ratio of component A to component B should be at most 1.2:1, since if component A is present in greater amounts the impact strength of the composition may decrease sharply. Said weight ratio is preferably about 0.7-1.0:1. When employed, the impact modifier (component D) is present in amounts up to about 35% and preferably in the range of about 10-25%, based on the total of components A, B and C. In terms of total resinous components, it is generally contemplated to employ about 10-45% and preferably about 15-45% of each of components A and B, and about 8-25% and preferably about 10-20% of component D.
With respect to the proportion (based on components A, B and C) of component C, the compatibilizing polymer, the invention includes three major embodiments although species outside these embodiments are also contemplated. The first embodiment includes compositions containing about 15-45% of component C. In such compositions, component A is typically a polyphenylene ether which has not been inactivated. Levels of components A, B and C of about 20-40%, 30-45% and 25-45% (respectively), based on the total of components A, B and C, are usually preferred in such compositions for maximum ductility. More preferably, compositions of the first embodiment comprise the following, percentages being based on total resinous components: about 15-35% of polyphenylene ether as component A, about 10-35% of component B, about 10-40% and most often about 20-40% of component C and from 8% to about 25% of component D.
When component A is not inactivated and components B and C are supplied in full or in part by a polyester-aromatic polycarbonate blend, it is frequently possible to attain the desired high impact strengths by using proportions of certain components outside of those previously described. This is true in at least two respects: the possibility of using a lower proportion of component B with respect to component A, and of employing more than 40% of component C. Thus, another aspect of the present invention is compositions comprising (based on total resinous components) about 15-35% of polyphenylene ether as component A, about 10-35% of component B, from 12% to about 50% of at least one aromatic polycarbonate as component C and about 10-25% of component D; with the provisos that all of component B and at least about 60% of component C are supplied as a poly(alkylene dicarboxylate)-aromatic polycarbonate blend, and that the weight ratio of component A to component B is at most about 1.8:1 and preferably about 0.7-1.8:1.
In the second embodiment, component A is an inactivated polyphenylene ether and the proportions of components A and B are each about 35-55%, based on the total of components A, B and C. The proportion of component C is about 5-15%, and the blend may also include component D and component E, the latter in the amount of about 0.15-3.5 and preferably at least about 0.4 part per 100 parts of total components A, B and C). Most preferably according to this embodiment, the compositions contain about 30-45% each of components A and B and about 3-10% of component C, all based on total resinous components, and component E in the amount of about 0.1-3.0 and most desirably at least about 0.25 part per 100 parts of components A, B, C and D taken together. This embodiment is often characterized by relatively high heat distortion temperatures.
The chemical roles of the inactivated polyphenylene ether and of component E in the compositions of this invention are not fully understood, and any reliance on chemical theory as a basis for the invention is specifically disclaimed. It is believed, however, that the presence of more than a certain minimum proportion of amino compounds in the polyphenylene ether can cause degradation in the molecular weight of the polycarbonate and/or polyester. Such amino compounds include, in addition to the aminoalkyl end groups, traces of amines (particularly secondary amine) in the catalyst used to form the polyphenylene ether. If this is true, the removal or neutralization of the greater part of such amino compounds produces an environment in which high molecular weight is maintained in the polycarbonate, thus maximizing its effect as a compatibilizing agent, and/or in the polyester.
The compositions of this invention have been shown by scanning electron microscopy to consist essentially of particles of polyphenylene ether (component A) dispersed in a continuous polyester-containing phase. The size and shape of said particles varies with such factors as the proportion of polyphenylene ether in the composition. The elastomeric impact modifier (component D), when present, is substantially entirely in the disperse phase. Component C is present in the continuous phase and improves the ductility thereof; it also forms a "coating" around the dispersed polyphenylene ether particles and provides good adhesion of said particles to the continuous phase. By reason of the size and shape of the disperse phase particles and/or their degree of adhesion to the continuous phase as a result of the action of component C, the compositions are highly resistant to delamination and similar types of failure under stress.
It is within the scope of the invention for the composition to contain other conventional ingredients such as fillers, flame retardants, pigments, dyes, stabilizers, antistatic agents, mold release agents and the like. The presence of other resinous components is also contemplated. These include impact modifiers compatible with component B, such as various graft and core-shell copolymers of such monomers as butadiene, styrene, butyl acrylate and methyl methacrylate. It is frequently preferred to preextrude such impact modifiers with component B, optionally in admixture with component C, prior to its utilization in the invention. By this method, compositions having improved ductility at low temperatures may be prepared.
The preparation of the compositions of this invention is normally achieved by merely blending the ingredients thereof under conditions adapted for the formation of an intimate blend. Such conditions often include extrusion, which may be conveniently effected in a screw-type or similar extruder which applies a substantial shearing force to the composition, thereby decreasing the particle size thereof. The extrusion temperature is generally in the range of about 100�-325� C. over the length of the extruder.
In another embodiment, a single extruder is employed which has at least two ports for introduction of ingredients, one such port being downstream from the other. Component A or any reactants for preparation thereof and at least a portion of component D are introduced through the first port and extruded, preferably at a temperature in the range of about 300�-350� C. This portion of the extruder is preferably vacuum vented.
The remaining ingredients are introduced through the downstream port and extrusion is continued, preferably at a lower temperature to minimize degradation of components B and D. For further minimization of degradation, it may be advantageous to introduce a portion of component D at this point. Typical extrusion temperatures at this stage are in the range of about 260�-320� C.
PPE--a poly(2,6-dimethyl-1,4-phenylene ether) having a number average molecular weight of about 20,000 and an intrinsic viscosity in chloroform at 25� C. of 0.46 dl./g; it was found to contain about 1000 ppm. nitrogen.
Example 2 (etc )-NVV--a product similar to that of Example 2 (etc.) but prepared with atmospheric rather than vacuum venting.
HIPS--American Hoecht 1897 rubber-modified polystyrene.
PBT(50,000) and PBT(25,000)--poly(butylene terephthalates) having number average molecular weights, as determined by gel permeation chromatography, of about 50,000 and 25,000, respectively.
PC(43,000), PC(50,000), PC(71,000), PC(192,000)--bisphenol A homopolycarbonates prepared interfacially and having weight average molecular weights of about 43,000, 50,000, 71,000 and 192,000, respectively.
SB(H)--a styrene butadiene diblock copolymer having weight average molecular weight of about 164,00 and a butadiene-styrene weight ratio of about 2:1, in which the butadiene block has been hydrogenated.
GMA-M--a commercially available copolymer of glycidyl methacrylate (50% by weight) and styrene, having a weight average molecular weight of about 11,000.
All proportions in the examples are by weight. Impact and tensile values were determined in British units and have been converted to metric units. Heat distortion temperatures were determined by ASTM procedure D648, at 0.455 MPa. unless otherwise indicated.
EXAMPLES 7-13 A series of compositions according to the invention was prepared by tumble mixing the ingredients in a jar mill for 1/2 hour and extruding at 120�-287� C. on a twin screw extruder at a screw speed of 400 rpm. The extrudates were quenched in water and pelletized. The pellets were then injection molded into test bars which were evaluated for notched Izod impact strength according to ASTM procedure D256. (An impact strength greater than about 105 joules/m. is generally an indication of suitability as a molding composition, and a value above about 550 is exceptional.) The fracture surfaces of the Izod test bars were inspected for delamination and none was detected.
TABLE I______________________________________     Example     7    8      9      10   11   12   13______________________________________Component A: PPE,       21     27     25   25   21   21   21partsComponent B, parts:PBT(50,000) 29     27     25   25   --   --   29PET(28,000) --     --     --   --   29   --   --PET(45,000) --     --     --   --   --   29   --Component C:       36     33     31   31   36   36   36PC(50,000), partsComponent D,parts:SEBS        14     13     19   --   14   14   --SI(H)       --     --     --   19   --   --   --SBS         --     --     --   --   --   --   14Izod impact 603    160    609  550  198  278  598strength, joules/m.______________________________________
EXAMPLES 15-20 The procedure of Example 7 was repeated, using other resins as components B and C. The relevant parameters and results are given in Table II. No delamination of any specimen was observed.
TABLE II______________________________________        Example        15   16     17     18   19   20______________________________________Component A: PPE, parts          28     28     31   31   34   34Component B: PBT-ES,          28     28     31   31   34   34partsComponent C, parts:PC(50,000)     25     --     19   --   12   --PC(71,000)     --     25     --   19   --   12Component D: SEBS,          19     19     19   19   19   19partsIzod impact strength,          625    801    694  790  139  112joules/m.Heat distortion temp., �C.          111    --     --   --   127  --______________________________________
TABLE III__________________________________________________________________________         Example          21 22 23 24 25 26 27 28__________________________________________________________________________Component A: PPE, parts          21 21 21 28 21 34 31 28Component B: PBT-ES, parts          29 29 29 28 29 34 31 28Component C, parts:PC(43,000)     36 -- -- -- -- -- -- --SH-PC          -- 36 18 -- -- -- -- --PE-PC          -- -- -- -- 36 -- -- --PPE-PC         -- -- -- -- -- 12 25 25PC-SIL         -- -- -- 25 -- -- -- --PS             -- -- 18 -- -- -- -- --Component D: SEBS, parts          14 14 14 19 14 19 13 19Izod impact strength,          176             278                182                   449                      251                         117                            764                               732joules/m.Heat distortion temp., �C.          -- -- -- -- 97 150                            157                               149__________________________________________________________________________
EXAMPLES 29-31 Following the procedure of Example 7, blends were prepared in which component B was provided entirely and component C entirely or partially by a polyester-polycarbonate blend containing 39% PBT-ES, 49% PC(50,000), 8.5% of a commercial butadiene-styrene-methyl methacrylate graft copolymer and 3.5% of various fillers and stabilizers.
TABLE IV______________________________________              Example              29    30      31______________________________________Polyester-polycarbonate blend, parts                64      32      50Polycarbonate, parts --      32      14Component A, parts   21.7    21.5    21.6Component B, parts   25.8    12.7    20.0Component C, parts   32.4    48.7    39.6Component D, parts   14.5    14.3    14.4Graft copolymer, parts                5.6     2.8     4.4Izod impact strength, joules/m.                481     529     534______________________________________
EXAMPLES 32-34 Compositions were prepared according to the procedure of Example 7, except that the extrusion temperature range was 120�-260� C. In these compositions, component A was the product of Example 1 and the other components were as listed in Table V. TGIC was also present in Examples 33 and 34.
TABLE V______________________________________             Example             32    33       34______________________________________Component A: Example 1, parts               40      41.4     40Component B: PBT(50,000), parts               40      41.4     40Component C: PC(50,000), parts               8       8.1      8Component D: SEBS, parts               12      9.1      12Component E: TGIC, parts               --      0.5      0.8Izod impact strength, joules/m.               107     166      267Heat distortion temp., �C.               --      166      156Tensile strength at yield, MPa.               44.9    --       46.0Tensile elongation, %               45      --       58______________________________________
TABLE VI__________________________________________________________________________          Example          36  37  38  39  40  41  42  43__________________________________________________________________________Component A, parts:Example 3      40  40  40  40  42  40  40  --Example 3-NVV  --  --  --  --  --  --  --  40Component B, parts:PBT(50,000)    40  40  40  40  42  --  40  40PBT(25,000)    --  --  --  --  --  40  --  --Component C, parts:PC(50,000)     8   8   8   --  --  --  8   8PC(71,000)     --  --  --  8   4   8   --  --Component D, parts:SEBS           12  12  12  12  12  12  --  12SB(H)          --  --  --  --  --  --  12  --Component E: TGIC, parts          0.8 0.32                  0.5 0.8 0.8 0.8 0.8 0.8Izod impact strength,          790 673 828 806 395 192 219 155joules/m.Heat distortion temp., �C.          177 148 175 158 --  156 172 --Tensile strength at yield,          46.9              47.9                  50.1                      46.9                          --  45.5                                  47.6                                      --MPa.Tensile elongation, %          96  54  106 69  --  48  40  --__________________________________________________________________________
TABLE VII______________________________________             Example             45   46     47      48______________________________________Component A, parts:Example 6           40     --     --    --PPE-VV              --     40     40    40Component B: PBT(50,000), parts               40     40     40    40Component C, parts:PC(50,000)          8      8      --    8PC(192,000)         --     --     8     --Component D, parts:SEBS                12     12     12    --CS                  --     --     --    12Component E: TGIC, parts               0.8    0.5    --    0.5Izod impact strength, joules/m.               785    769    764   486Heat distortion temperature, �C.               --     167    --    --______________________________________
EXAMPLES 49-51 Following the procedure of Example 32, compositions were prepared using as components B and C the following preextruded blend:
PBT(50,000): 69.55%
PC(50,000): 15%
PBT impact modifier: 15%
Stabilizers, exchange suppressor: 0.45%.
TABLE VIII______________________________________           Example           49     50       51______________________________________Component A, parts:Example 3         36.6     --       --PPE-VV            --       36.6     36.6Component B, parts             36.4     36.4     36.4Component C, parts             7.9      7.9      7.9Component D: SEBS, parts             11.2     11.2     11.2Component E: TGIC, parts             0.4      0.4      --KM-330, parts     7.9      7.9      7.9Izod impact strength, joules/m.             721      192      198______________________________________
TABLE IX______________________________________            Example            53   54      55     56______________________________________Component A, parts:PPE-VV             40     --      --   --Example 2          --     40      40   40Component B: PBT(50,000), parts              40     40      40   40Component C, parts:PC-Trans           8      8       8    --Allyl-PC           --     --      --   8Component D: SEBS, parts              12     12      12   12Component E: TGIC, parts              --     --      0.5  --Izod impact strength, joules/m.              182    256     828  278______________________________________
EXAMPLES 56-67 Following the procedure of Example 32, compositions were prepared containing 40 parts of the inactivated polyphenylene ether of Example 3, 40 parts of PBT(50,000), 12 parts of SEBS, 8 parts of PC(50,000) and, as component E, various materials. The identity of these materials and the test results are given in Table X.
TABLE X______________________________________                       Tensile              Izod     strength TensileComponent E        impact   at       elong-Ex-                Amt.,   strength                             break  ation,ample Identity     parts   joules/m.                             MPa.   %______________________________________57      --         --      219    38.8   4558    TGIC         0.8     673    42.7   7859    GMA          1.0     764    42.8   7160    GMA-AA(15)   1.0     657    41.7   5061    GMA-AA(30)   1.0     678    43.8   6662    GMA-S-M      1.0     609    47.9   7963    GMA-S        1.0     710    46.5   9864    GMA-M        1.0     587    48.2   8665    GMA-S-A(10A) 1.0     657    41.4   5366    GMA-S-A(10B) 1.0     684    40.2   4967    GMA-S-A(20)  1.0     646    43.2   65______________________________________
TABLE XI______________________________________Component E          Izod impactExample Identity   Amt., parts                        strength, joules/m.______________________________________68      --         --        29469      GMA        1.0       68070      GMA-M      1.0       660______________________________________
EXAMPLES 71-75 These examples show the effect on polyester melt viscosity of premixing the polyester with component E, the proportions of the latter being percentages by weight of polyester. Premixing was effected by dry blending followed by melt extrusion. The melt viscosities, or, in some cases, melt flow rates (which are inversely proportional to melt viscosities) were compared with those of controls which had been similarly extruded without the addition of component E. The melt viscosity of the polyester before extrusion was about 7,500 poises.
TABLE XII______________________________________                 Melt     MeltComponent E           viscosity,                          flow rate,Example Identity    Amt., %   poises g./10 min.______________________________________Controls     --        --          5,900                                38.771      TGIC        0.5         41,000                                --72      TGIC        1.0       &gt;135,000                                --73      GMA         1.0       --     5.074      GMA-M       1.0       --     3.475      GMA-S-A(20) 1.0       --     4.5______________________________________
EXAMPLES 76-79 Following the procedure of Example 32, compositions were prepared containing 40 parts of the inactivated polyphenylene ether of Example 2, 40 parts of poly(butylene terephthalate) which had been premixed with TGIC as described in Examples 71-75, 12 parts of SEBS and 8 parts of PC(50,000). They were compared with Controls I and II prepared from untreated poly(butylene terephthalates), and Control III, wherein the TGIC was dry blended with all of the other components. The relative parameters and test results are given in Table XIII.
TABLE XIII__________________________________________________________________________   Example                     Control   76     77     78     79     I      II     III__________________________________________________________________________Component B,   25,000 25,000 25,000 50,000 25,000 50,000 25,000mol. wt.Component E(TGIC):% based on   0.5    1.0    2.0    0.5     0      0     --polyesterAmt. in blend,   0.2    0.4    0.8    0.2    --     --     0.8partsIzod impact   224    256    570    500    80     220    192strength,joules/m__________________________________________________________________________
EXAMPLE 80 This example demonstrates the effect on impact strength of nitrogen content and molecular weight of the polyphenylene ether. Blends similar to that of Example 32 were prepared by the procedure described therein, using as component C two different bisphenol A polycarbonates prepared interfacially and as component A a number of polyphenylene ethers prepared by procedures which did not include functionalization or vacuum venting. Components B and D were PBT(50,000) and SEBS, respectively. The results are given in Table XIV.
TABLE XIV______________________________________                            IzodPolyphenylene ether     Polycar- impactIV,                     bonate   strength,dl./g.  Nitrogen, ppm.  mol. wt. joules/m.______________________________________0.46    1020            50,000   200.40    1115            "        200.29    497             "        780.18    353             "        220.53    576             "        570.46    1020            71,000   260.40    1115            "        260.29    497             "        1150.18    353             "        220.53    576             "        265______________________________________
EXAMPLE 81 This example shows the effect of fumaric acid level in the inactivated polyphenylene ether on the impact strengths of the compositions. The procedure of Example 32 was employed to prepare compositions from 40 parts of various fumaric acid-inactivated polyphenylene ethers, 40 parts of PBT(50,000), 12 parts of SEBS, 8 parts of PC(50,000) and, in certain cases, 0.32 part of TGIC. The impact strengths of the compositions are given in Table XV.
TABLE XV______________________________________        Fumaric            Impact strength,Polyphenylene ether        acid level*                  TGIC     joules/m.______________________________________Ex. 2        0.7       No       155Ex. 4        1.0       No       198Ex. 5        1.4       No       294Ex. 2        0.7       Yes      700Ex. 4        1.0       Yes      774Ex. 5        1.4       Yes      726______________________________________ *Parts per 100 parts of polyphenylene ether.
The extrudates were quenched in water and pelletized. The pellets were then injection molded into test specimens which were evaluated for heat distortion temperature, flow channel, Dynatup impact, notched Izod impact and tensile yield and elongation. Test results are given in Table XVI.
TABLE XVI______________________________________Examples            82       83     84______________________________________Component A, parts:PPE                 31.3     28.3   28.3Polystyrene homopolymer               --       9.4    --HIPS                --       --     9.4Component B: PBT(50,000), parts               47.9     43.4   43.4Component C: PC(71,000), parts               8.3      7.6    7.6Component D: SEBS, parts               12.5     11.3   11.3Heat distortion temperature, �C.               147      154    150Flow channel, cm.   39.4     53.3   48.3Dynatup impact, joulesRoom temperature    44.7     51.5   52.9-29� C.      47.5     50.2   56.9Izod impact strength, joules/m.               828      662    651Tensile strength at yield, MPa.               41.4     47.6   50.3Tensile elongation, %               43       29     29______________________________________
EXAMPLES 85-88 In this series of examples, blends were prepared in the same manner as described above for Examples 82-84. The weight ratio of the polyphenylene ether to polystyrene was varied. In this series, component B was PBT(50,000), (45 parts), component C was PC(71,000) (8 parts) and component D was SEBS (12 parts). Table XVII indicates the manner in which the polyphenylene ether and the polystyrene were varied and reports the results of the physical property tests. It is evident that the proportions of polyphenylene ether and polystyrene can be widely varied and still provide a variety of useful thermoplastic products.
TABLE XVII______________________________________Example       85      86     87    88   Control______________________________________Component A, parts:PPE           35      30     25    20   0HIPS          0       5      10    15   35Heat distortion         162     158    150   138  103temperature, �C.Flow channel, cm.         41.9    44.5   44.5  54.6 83.8Dynatup impact, joulesRoom temperature         50.2    47.5   54.2  50.2 17.6-29� C.         62.4    66.4   54.2  47.5 --Izod impact strength,         694     721    716   342  69.4joules/m.Flex. modulus, GPa.         1.85    1.90   1.91  1.85 1.70Flex. strength, MPa.         68.3    68.9   68.9  64.8 49.6Tensile strength at yield,         46.2    49.0   45.5  48.3 29.6MPa.Tensile elongation, parts         33      30     43    36   8______________________________________
EXAMPLES 89-96 A series of compositions not containing impact modifiers was prepared by tumble mixing the ingredients in a jar mill and extruding at 265� C. on a twin screw extruder with a screw speed of 400 rpm. The extrudate was quenched in water and pelletized, and the pellets were injection molded into test bars.
The relevant parameters are given in Table XVIII.
TABLE XVIII______________________________________Example     89    90    91   92   93   94   95  96______________________________________Component A, parts:PPE         40    45    25   --   --   --   --  --PPE-VV      --    --    --   19.8 19.8 47.5 45  42.5Component; B, parts:PBT         40    45    --   66.8 66.8 47.5 45  42.5PBT-ES      --    --    33.3 --   --   --   --  --Component C, parts:PC(50,000)  20    10    41.7 13.4 --   --   --  --PC(71,000)  --    --    --   --   --   5.0  10  15.0PPE-PC      --    --    --   --   13.4 --   --  --______________________________________
EXAMPLES 97-106 The procedure of Examples 89-96 was repeated, using various other combinations of ingredients. In Examples 101-104, conventional antioxidants were also present in effective amounts.
The relevant parameters and test results are given in Table XIX, in comparison with a control containing no polycarbonate.
TABLE XIX__________________________________________________________________________Example       97 98 99 100                     101                        102                           103                              104 105                                     106                                        Control__________________________________________________________________________Component A, partsPPE           -- -- -- -- -- -- -- --  21.4                                     21.4                                        --PPE-VV        -- -- -- -- 34.9                        44 34.9                              20  -- -- 60.5Example 2     45.5            19.8               19.8                  -- -- -- -- --  -- -- --Example 5     -- -- -- 45.8                     -- -- -- --  -- -- --HIPS          -- -- -- -- -- -- -- --  14.3                                     14.3                                        --Component B, partsPBI           45.5            66.8               66.8                  45.8                     53.5                        46 53.5                              71  28.6                                     -- 39.5PBI-ES        -- -- -- -- -- -- -- --  -- 28.6                                        --Component C, partsPC(50,000)     9.0            13.4               --  8.4                     -- -- -- --  35.7                                     35.7                                        --PC(71,000)    -- -- -- -- 11.6                        10 11.6                              9   -- -- --PC(192,000)   -- -- 13.4                  -- -- -- -- --  -- -- --Component E: TGIC, parts         -- -- --  0.5                     -- -- -- --Tensile strength, MPa.:At yield      -- -- -- -- -- -- 56.6                              52.7                                  -- --  4.1At break      -- -- -- -- -- -- 40.3                              35.4                                  -- -- 26.9Tensile elongation, %         -- -- -- -- -- -- 50 185 -- -- 5__________________________________________________________________________
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