CA1134531A - Ultrasonically bondable polyphenylene ether compositions - Google Patents
Ultrasonically bondable polyphenylene ether compositionsInfo
- Publication number
- CA1134531A CA1134531A CA000292811A CA292811A CA1134531A CA 1134531 A CA1134531 A CA 1134531A CA 000292811 A CA000292811 A CA 000292811A CA 292811 A CA292811 A CA 292811A CA 1134531 A CA1134531 A CA 1134531A
- Authority
- CA
- Canada
- Prior art keywords
- styrene
- composition
- resin
- polyphenylene ether
- polymeric material
- 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.)
- Expired
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- 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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Thermoplastic polyphenylene ether molding compositions are provided which, after molding, are ultrasonically bondable to acrylic or to polycarbonate poly-mers with improved bond strength, the compositions comprising an admixture of a polyphenylene ether resin, a styrene resin and at least 40 parts by weight of a polymeric material which is polar in relation to the styrene resin, based on 100 parts by weight of said polyphenylene ether resin and said styrene resin. Especially suitable for such polymeric materials are copolymers of styrene and maleic anhydride; copolymers of styrene and methyl methacrylate and terpolymers of styrene, maleic anhydride and a diene. Optionally, an A-B-A block copolymer, e. g., a styrene-butadiene-styrene resin, can also be included in the compositions.
Thermoplastic polyphenylene ether molding compositions are provided which, after molding, are ultrasonically bondable to acrylic or to polycarbonate poly-mers with improved bond strength, the compositions comprising an admixture of a polyphenylene ether resin, a styrene resin and at least 40 parts by weight of a polymeric material which is polar in relation to the styrene resin, based on 100 parts by weight of said polyphenylene ether resin and said styrene resin. Especially suitable for such polymeric materials are copolymers of styrene and maleic anhydride; copolymers of styrene and methyl methacrylate and terpolymers of styrene, maleic anhydride and a diene. Optionally, an A-B-A block copolymer, e. g., a styrene-butadiene-styrene resin, can also be included in the compositions.
Description
This invention relates to thermoplastic molding compositi.ons which, when ultrasonically bonded or welded in the molded state to acrylic or polycarbonate polymers, possess improved bond strength in the ultrasonically formed bond. More particularly the present compositions comprise, in admixture, a polyphenylene ether resin, a styrene resin, preferably a rubber modi~ied high impact polystyrene, a polymeric material which is polar in rela-tion to the polystyrene component and, optionally, an A-B-A block copolymer. In order to confer the desired polyphenylene ether/polystyrene to acrylic bond strengths, the polar polymeric material should be present in at least 40 parts by weight per 100 parts by weight of said ~ :
polyphenylene ether resin and said styrene resin.
I The polyphenylene ether resins are known and described in numerous publications, including Hay, U.S.3,306,874 dated February 28, 1967 and 3,306,875 dated February 28; 1967 : and stamatoff, U.S. 3,257,357 dated June 21, 1966 and 3,257,358 dated June 21, 1966. In Cizek, U.S. 3,383,435 ; dated ~ay 14, 1968 , it is disclosed that polyphenylene ethers and polystyrene resins, including many modified polystyrenes, : are combinable in all proportions to provide compositions having many properties impro~ed over those of either the polyphenylene ether resin or the polystyrene resin alone.
Compositions of polyphenylene ether and polystyrene are useful for many commercial applications and because they are thermoplastic, they can be shaped into various articles by compression molding, extrusion, or the like. The shaped articles can then, in turn, be joined with other parts in plastics welding operations.
Ultrasonic methods o~ assembly provide an especially use~ul means for welding or bonding plastics to plastics. In general, ultrasonic vibrations above the audible range are used *~
~ 3.~ 8 CH ~335 to generate localized heat by vibrating one plastic surface against the other. Sufficient frictional heat is released, usually within a fraction of a second, to cause most thermoplastic materials to melt~ flow and fuse. Ultrasonic methods of assembly are cleaner, faster, and more economical than conventional bonding methods, and they avoid the need or applied heat, solvents, adhesives, curing times, and the like.
The ultrasonic bonding o~ thermoplastic materials is described in further detail in the "Encyclopedia o Polymer lQ Science and Technolo~y", ~olume 1~, John Wiley & Sons, Inc., 1971, pages 116-124.
Although ultrasonic bonding provides numerous advan~
tagesl as mentioned above, when molded parts made of polyphenylene ether/polystyrene compositions have heretofore been joined or welded to acrylic or to polvcarbonate polymers using ultrasonic techni~ues, it has been possible to form only relatively weak bonds. For most practical applications, a bond strength of about -3QO lbs. or greater is required. ~owever, when prior art poly~
phenylene ether/polystyrene compositions are ultrasonically -~
2Q bonded to acrylic or to polycarbonate polymers, bond strengths of far less than 300 lbs. are typically obtained.
It has now been surprisingly discovexed that if at least a portion of the polystyrene component in polyphenylene ; ether/polystyrene compositions is replaced by a component which is polar in relation to the polystyrene compon~nt, the resulting thermoplastic compositions can be ultrasonically bonded to acrylic or to polycarbonate polymers with unexpectedly improved bond strengths in the ultrasonically formed bond.
Accordingly, the present invention, in its broadest aspects, provides thermoplastic molding compositions which are ultrasonically bondable or weldable in the molded state, i.e., after being compression molded, ~xtruded, or the li3~e, to acrylic or to polycarbonate polymers with improved bond 8 C~l 2335 strength in the ultrasonically formed bond, the compositions comprising an admixture of:
(a) a polyphenylene ether resin;
(b) a styrene resin; and (c~ a polymeric material which is polar in relation to styrene resin (b) The polyphenylene ether resins of this invention are described in detail in the above-mentibned Hay and Stamatoff ~i patents. In general, the polyphenylene ether resin (a~ is a self-condensation product of monohydric, monocyclic phenols which can be produced, for example, by reacting the phenols with oxygen in the presence of complex copper catalysts. The molecular weight can be controlled by reaction time, longer times providing a higher average number of repeating units.
A preferred family of polyphenylene ethers will have repeating structural units of the formula:
20 ~ Q ~n ~I~
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent sub-stituent selected from the group consisting of hydro~en, halo- -gen, hydrocarbon radlcals;free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least -~wo carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy xadicals and halohydrocarbonoxy radicals having at least t~o carbon atoms between the halogen atom and the phenyl nucleus.
~ For purposes of the present lnvention an especially .~ , ~3~3 ~ 8 CH 2335 preferred family of polyphenylene ethers include those having alkyl substitution in the two positions ortho to the oxygen e-ther atom, i.e., those of the above formula wherein each Q
is alkyl, most preferably having from 1 to 4 carbon atoms.
Examples include poly (2,6-dimethyl-1,4-phenylene)ether, poly (2,6-diethyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4-phenylene)ether, poly(2 methyl-6-propyl-1, 4-phenylene)ether, poly(2,6-dipropyl-1,4-phenylene)ether, and poly(2-ethyl-6-propyl-1,4-phenylene~ether. Especially preferred is poly ;
(2,6-dimethyl-1,4-phenylene)ether.
The styrene resin (b), in general, will be selected from those having at least 25% by weight of the polymer units -~
- derived from a vinyl aromatic monomer, e.g., one having the ..
formula: --RC=jH
(II) wherein R is hydrogen, (lower) alkyl, e.g., of from 1 to 4 carbon atoms or halogen; Z is hydrogen, vinyl, halogen or (lower) alkyl; and p is 0 or a whole number of from 1 to 5. Illustrative polystyrene resins include homopolymers of polystyrene, poly-chlorostyrene, poly-2 methylstyrene, and the like; styrene-containing copolymers, such as styrene-acrylonitrile copolymers, copolymers of ethylvinylbenzene and divinylbenzene, styrene-acrylonitrile-a-methylstyrene terpolymers, and the like.
Preferred polystyrene resins of this class are i~
rubber-modified, high impact styrene resins, i.e., polystyrene which has been modified with natural or synthetic ma~erials ~whic~ a~e el~s~tomers~ at room tem~erature~ e g~ 20 to 25 C.
The term "rubber" therefore includes polybutadiene, polyiso-. ~ .
~ 3 !~ 8 CH 2335 prene, rubbery copolymers of dienes with other comonomers, such as styrene, acrylonitrile, acrylic esters and the li~e, including block sopolymers of the A-B-A and A-B type wherein A is a vinyl aromatic, such as styrene, and B is a diene such as butadiene, as well as EPDM rubber and the like. Most preferably, the polystyrene is modified with a butadiene rubber.
Component (c) is a polymeric ma~terial which is characteristically polar in relation to polystyrene resin (b).
The presence of polar component (c) is essential for the achieve-ment of improved bond strengths in the ultrasonic bonding ofpolyphenylene ether/ polystyrene blends with acrylics or polycarbon-ates. The nature of polar component (c) can vary, provided the requisite property of polariky relative to polystyrene component (b) is always present. Especially preerred polar materials in-clude copolymers of a vinyl aromatic compound ànd an ~ un-saturated cyclic anhydride, e.g., styrene-maleic anhydride co-polymers; copolymers of a vinyl aromatic compound and an acrylic ester, e.g., styrene-methyl methacrylate copolymers; and terpoly-~ers of a vinyl aromatic compound, an acrylic ester and a diene, e.g., styrene-methylmethacrylate-butadiene.
As is described in Cizek, U.S. 3,383,435 dated May 14, 1968, polyphenylene ethers and polystyrene resins are combinable with each other in all proportions. Thus, the present compositions can comprise from 1 to 99% by weight `~
polyphenylene ether resin and from 99 to 1% by weight polystyrene resin, on a rubber-free basis, and these are included within the scope o~ the invention.
Polar component (c) is present in amounts of at leas-t 40 and up to about 150 parts by weight, based on 100 parts by weight of components (a) and (b). Such amounts are necessary in order to achieye u~able bon~ stren~ths in ~ltrasonically ~orm~
ed bonds with acrylic polymers~ ~mounts o~ polar compone~t ~c) ~3~ 8 CH 2335 of ~rom about 40 to 120 parts by weight per 100 parts by weight of (a~ and (b) are especially preferred. Higher amounts may be employed but impact strength may be adversely afected. ;~
In general, if more cyclic anhydride or acrylate is present in the copolymer or terpolymer component (c), less of component (c) need be combined with (a) and (b) to produce the desired degree of bondability.
Other ingredients, such ~s plasticizexs, pigments, flame retardants, reinforcing agents, stabilizers, and the like, can be added for their conventionally employed purposes. In such cases, all concentrations and ratios of the resinous ingredients disclosed herein, and the like, will be adjusted accordingly to `~
. .
reflect the presence of such additives.
The method of forming the compositions of the invention is not critical and ~arious conventional means can be employed. The preferred method is one in which the ingredients are admixed to form a preblend, the preblend is processed through an extruder and the extrudate is molded to any desired shape such as by extrusion, hot molding or the like.
The invention is further illustrated by the following examples, which are not to be construed as limiting.
Unless otherwise indicated, all compositions are prepared by blending, then passing the blend through a variable pitch, twin screw extruder with extrusion temperature maintained between 500 and 600F. The emerging strands are cooled, chopped into pellets and molded into test bars using a Newbury injection molding machine. The test bars are tested ~ox physical properties according to ASTM test methods. All parts o the compositions shown in the examples are by welght.
3a Examples 1-7 The following composi-tions were prepared, molded into test bars and tested for physical properties.
~34~3 L
(Parts by Examples Components We'i~ht~ 1 2* 3 4* 5 6 7 Polyphenylene ether resina 25 25 40 35 30 20 30 Rubber modified, high-impact poly-styrene resin -- 65 -- 40 -- -- --Styrene-butadiene-styrene resinC 15 -- 20 -- 20 20 20 Styrene-methyl-methacrylate co-polymer (60:40)d 60 -- -- -- -- -- --Styrene-maleic anhydride co-polymere -- -- 40 25 50 60 50 Triphenyl phosphate -- -- 4 -- -- -- 4 Acryflic copoly-mer -- 10 -- -- -- -- --* Control Experiments a Poly(2,6-dimethyl-1,4-phenylene)ether, intrinsic viscosity about 0.45 dl/g in CHC13 at 30C., PPO, General Electric Co., b Foster Grant Co., Leominster, Mass., FG 834 c Shell Chemical Co., Houston, Texas, Kraton 1101 d The Richardson Co., Des Plaines, Ill., NAS 8L ' e ARCO Polymers, Inc., Pittsburgh, Pa., Dylark 232 f Rohm & Haas Co., Philadelphia, Pa., Acryloid KM 611 Properties 1 2 3 4 5 6 Heat DOeflection temp.( F.) 203 220 237 247 245 234 225 Izod impact (in.
lbs~/in.n.) 1.6 4.0 4.6 2.0 2.5 2.6 2.7 M.V. (poise~ 2050 1950 1900 1400 1700 Test pieces molded from the compositions of Examples 1-7 were ultrasonically welded to molded ~est pieces of a polyphenylene ether resin high impact polystyrene resin and test pieces of an acrylic resin, respectively. The welded pieces were tested for bond strengths at failure under tensile type loading conditions, using an Instron testing machine. The ~3~;i3~
bond strengths at break, in units of pounds, are shown in Table I (for comparison purposes, an acrylic-to-acrylic ultrasonic bond strength is 425 lbs.):
ULTRASONICALLY WELDED BOND STRENGTHS
Bonded to polyphenylene ether/polystyrene Bonded to Acrylic Example No~ ~Break Force in lbs.) ~Break Force ln lbs.)
polyphenylene ether resin and said styrene resin.
I The polyphenylene ether resins are known and described in numerous publications, including Hay, U.S.3,306,874 dated February 28, 1967 and 3,306,875 dated February 28; 1967 : and stamatoff, U.S. 3,257,357 dated June 21, 1966 and 3,257,358 dated June 21, 1966. In Cizek, U.S. 3,383,435 ; dated ~ay 14, 1968 , it is disclosed that polyphenylene ethers and polystyrene resins, including many modified polystyrenes, : are combinable in all proportions to provide compositions having many properties impro~ed over those of either the polyphenylene ether resin or the polystyrene resin alone.
Compositions of polyphenylene ether and polystyrene are useful for many commercial applications and because they are thermoplastic, they can be shaped into various articles by compression molding, extrusion, or the like. The shaped articles can then, in turn, be joined with other parts in plastics welding operations.
Ultrasonic methods o~ assembly provide an especially use~ul means for welding or bonding plastics to plastics. In general, ultrasonic vibrations above the audible range are used *~
~ 3.~ 8 CH ~335 to generate localized heat by vibrating one plastic surface against the other. Sufficient frictional heat is released, usually within a fraction of a second, to cause most thermoplastic materials to melt~ flow and fuse. Ultrasonic methods of assembly are cleaner, faster, and more economical than conventional bonding methods, and they avoid the need or applied heat, solvents, adhesives, curing times, and the like.
The ultrasonic bonding o~ thermoplastic materials is described in further detail in the "Encyclopedia o Polymer lQ Science and Technolo~y", ~olume 1~, John Wiley & Sons, Inc., 1971, pages 116-124.
Although ultrasonic bonding provides numerous advan~
tagesl as mentioned above, when molded parts made of polyphenylene ether/polystyrene compositions have heretofore been joined or welded to acrylic or to polvcarbonate polymers using ultrasonic techni~ues, it has been possible to form only relatively weak bonds. For most practical applications, a bond strength of about -3QO lbs. or greater is required. ~owever, when prior art poly~
phenylene ether/polystyrene compositions are ultrasonically -~
2Q bonded to acrylic or to polycarbonate polymers, bond strengths of far less than 300 lbs. are typically obtained.
It has now been surprisingly discovexed that if at least a portion of the polystyrene component in polyphenylene ; ether/polystyrene compositions is replaced by a component which is polar in relation to the polystyrene compon~nt, the resulting thermoplastic compositions can be ultrasonically bonded to acrylic or to polycarbonate polymers with unexpectedly improved bond strengths in the ultrasonically formed bond.
Accordingly, the present invention, in its broadest aspects, provides thermoplastic molding compositions which are ultrasonically bondable or weldable in the molded state, i.e., after being compression molded, ~xtruded, or the li3~e, to acrylic or to polycarbonate polymers with improved bond 8 C~l 2335 strength in the ultrasonically formed bond, the compositions comprising an admixture of:
(a) a polyphenylene ether resin;
(b) a styrene resin; and (c~ a polymeric material which is polar in relation to styrene resin (b) The polyphenylene ether resins of this invention are described in detail in the above-mentibned Hay and Stamatoff ~i patents. In general, the polyphenylene ether resin (a~ is a self-condensation product of monohydric, monocyclic phenols which can be produced, for example, by reacting the phenols with oxygen in the presence of complex copper catalysts. The molecular weight can be controlled by reaction time, longer times providing a higher average number of repeating units.
A preferred family of polyphenylene ethers will have repeating structural units of the formula:
20 ~ Q ~n ~I~
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent sub-stituent selected from the group consisting of hydro~en, halo- -gen, hydrocarbon radlcals;free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least -~wo carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy xadicals and halohydrocarbonoxy radicals having at least t~o carbon atoms between the halogen atom and the phenyl nucleus.
~ For purposes of the present lnvention an especially .~ , ~3~3 ~ 8 CH 2335 preferred family of polyphenylene ethers include those having alkyl substitution in the two positions ortho to the oxygen e-ther atom, i.e., those of the above formula wherein each Q
is alkyl, most preferably having from 1 to 4 carbon atoms.
Examples include poly (2,6-dimethyl-1,4-phenylene)ether, poly (2,6-diethyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4-phenylene)ether, poly(2 methyl-6-propyl-1, 4-phenylene)ether, poly(2,6-dipropyl-1,4-phenylene)ether, and poly(2-ethyl-6-propyl-1,4-phenylene~ether. Especially preferred is poly ;
(2,6-dimethyl-1,4-phenylene)ether.
The styrene resin (b), in general, will be selected from those having at least 25% by weight of the polymer units -~
- derived from a vinyl aromatic monomer, e.g., one having the ..
formula: --RC=jH
(II) wherein R is hydrogen, (lower) alkyl, e.g., of from 1 to 4 carbon atoms or halogen; Z is hydrogen, vinyl, halogen or (lower) alkyl; and p is 0 or a whole number of from 1 to 5. Illustrative polystyrene resins include homopolymers of polystyrene, poly-chlorostyrene, poly-2 methylstyrene, and the like; styrene-containing copolymers, such as styrene-acrylonitrile copolymers, copolymers of ethylvinylbenzene and divinylbenzene, styrene-acrylonitrile-a-methylstyrene terpolymers, and the like.
Preferred polystyrene resins of this class are i~
rubber-modified, high impact styrene resins, i.e., polystyrene which has been modified with natural or synthetic ma~erials ~whic~ a~e el~s~tomers~ at room tem~erature~ e g~ 20 to 25 C.
The term "rubber" therefore includes polybutadiene, polyiso-. ~ .
~ 3 !~ 8 CH 2335 prene, rubbery copolymers of dienes with other comonomers, such as styrene, acrylonitrile, acrylic esters and the li~e, including block sopolymers of the A-B-A and A-B type wherein A is a vinyl aromatic, such as styrene, and B is a diene such as butadiene, as well as EPDM rubber and the like. Most preferably, the polystyrene is modified with a butadiene rubber.
Component (c) is a polymeric ma~terial which is characteristically polar in relation to polystyrene resin (b).
The presence of polar component (c) is essential for the achieve-ment of improved bond strengths in the ultrasonic bonding ofpolyphenylene ether/ polystyrene blends with acrylics or polycarbon-ates. The nature of polar component (c) can vary, provided the requisite property of polariky relative to polystyrene component (b) is always present. Especially preerred polar materials in-clude copolymers of a vinyl aromatic compound ànd an ~ un-saturated cyclic anhydride, e.g., styrene-maleic anhydride co-polymers; copolymers of a vinyl aromatic compound and an acrylic ester, e.g., styrene-methyl methacrylate copolymers; and terpoly-~ers of a vinyl aromatic compound, an acrylic ester and a diene, e.g., styrene-methylmethacrylate-butadiene.
As is described in Cizek, U.S. 3,383,435 dated May 14, 1968, polyphenylene ethers and polystyrene resins are combinable with each other in all proportions. Thus, the present compositions can comprise from 1 to 99% by weight `~
polyphenylene ether resin and from 99 to 1% by weight polystyrene resin, on a rubber-free basis, and these are included within the scope o~ the invention.
Polar component (c) is present in amounts of at leas-t 40 and up to about 150 parts by weight, based on 100 parts by weight of components (a) and (b). Such amounts are necessary in order to achieye u~able bon~ stren~ths in ~ltrasonically ~orm~
ed bonds with acrylic polymers~ ~mounts o~ polar compone~t ~c) ~3~ 8 CH 2335 of ~rom about 40 to 120 parts by weight per 100 parts by weight of (a~ and (b) are especially preferred. Higher amounts may be employed but impact strength may be adversely afected. ;~
In general, if more cyclic anhydride or acrylate is present in the copolymer or terpolymer component (c), less of component (c) need be combined with (a) and (b) to produce the desired degree of bondability.
Other ingredients, such ~s plasticizexs, pigments, flame retardants, reinforcing agents, stabilizers, and the like, can be added for their conventionally employed purposes. In such cases, all concentrations and ratios of the resinous ingredients disclosed herein, and the like, will be adjusted accordingly to `~
. .
reflect the presence of such additives.
The method of forming the compositions of the invention is not critical and ~arious conventional means can be employed. The preferred method is one in which the ingredients are admixed to form a preblend, the preblend is processed through an extruder and the extrudate is molded to any desired shape such as by extrusion, hot molding or the like.
The invention is further illustrated by the following examples, which are not to be construed as limiting.
Unless otherwise indicated, all compositions are prepared by blending, then passing the blend through a variable pitch, twin screw extruder with extrusion temperature maintained between 500 and 600F. The emerging strands are cooled, chopped into pellets and molded into test bars using a Newbury injection molding machine. The test bars are tested ~ox physical properties according to ASTM test methods. All parts o the compositions shown in the examples are by welght.
3a Examples 1-7 The following composi-tions were prepared, molded into test bars and tested for physical properties.
~34~3 L
(Parts by Examples Components We'i~ht~ 1 2* 3 4* 5 6 7 Polyphenylene ether resina 25 25 40 35 30 20 30 Rubber modified, high-impact poly-styrene resin -- 65 -- 40 -- -- --Styrene-butadiene-styrene resinC 15 -- 20 -- 20 20 20 Styrene-methyl-methacrylate co-polymer (60:40)d 60 -- -- -- -- -- --Styrene-maleic anhydride co-polymere -- -- 40 25 50 60 50 Triphenyl phosphate -- -- 4 -- -- -- 4 Acryflic copoly-mer -- 10 -- -- -- -- --* Control Experiments a Poly(2,6-dimethyl-1,4-phenylene)ether, intrinsic viscosity about 0.45 dl/g in CHC13 at 30C., PPO, General Electric Co., b Foster Grant Co., Leominster, Mass., FG 834 c Shell Chemical Co., Houston, Texas, Kraton 1101 d The Richardson Co., Des Plaines, Ill., NAS 8L ' e ARCO Polymers, Inc., Pittsburgh, Pa., Dylark 232 f Rohm & Haas Co., Philadelphia, Pa., Acryloid KM 611 Properties 1 2 3 4 5 6 Heat DOeflection temp.( F.) 203 220 237 247 245 234 225 Izod impact (in.
lbs~/in.n.) 1.6 4.0 4.6 2.0 2.5 2.6 2.7 M.V. (poise~ 2050 1950 1900 1400 1700 Test pieces molded from the compositions of Examples 1-7 were ultrasonically welded to molded ~est pieces of a polyphenylene ether resin high impact polystyrene resin and test pieces of an acrylic resin, respectively. The welded pieces were tested for bond strengths at failure under tensile type loading conditions, using an Instron testing machine. The ~3~;i3~
bond strengths at break, in units of pounds, are shown in Table I (for comparison purposes, an acrylic-to-acrylic ultrasonic bond strength is 425 lbs.):
ULTRASONICALLY WELDED BOND STRENGTHS
Bonded to polyphenylene ether/polystyrene Bonded to Acrylic Example No~ ~Break Force in lbs.) ~Break Force ln lbs.)
2* 625 200 -
3 825 300
4* 425 200 * Control Experiments A bond strength of at least about 300 pounds is generally accepted;to be necessary for practical applications.
Compositions 1-3 and 5-7, according to this invention, equal ;
or exceed this value. If less than 40 parts of (c) per 100 parts of ~a) and (b~ are used, Control Example 4 (36 parts), it is seen that the bond strength falls below the minimum.
EXAMPLES~8 - 10 The general procedure of Examples 1-7 is repeated, substituting a styrene-maleic anyydride-butadiene rubber for component (c). The formulations used and the physical propexties obtained are set forth as folIows:
Compositions (parts by weight) poly(2,6-dimethyl-1,4-phenylene 0 ether (as is Examples 1-7) 25 25 35 Rubber modified high impact polystyrene resin (as in Examples 1-7) 25 25 20 ~3~3 ~ 8 CH 2335 Styrene-butadiene-styrene resin (as in Examples 1-7) 5 3 Styrene-maleic anhydride-butadiene terpolymer resin (80:10-10)a 50 50 45 Properties -Heat distortion temperature, F. 236 235 246 Izod impact strength, ft.lbs./
in Notch 2.8 1.9 3.0 Melt viscosity, poise 1,600 1,400 1,600 .
a ARCO Polymers, Inc., Pittsburgh, Pa., Dylark 240 The bond strengths at break, in units of pounds, are shown in Table 1 for ultrasonic bonds to acrylic and to poly-carbonate (Lexan 103) substrates:
ULTRASONICALLY WELDED BOND STRENGTHS ' Bonded to Acrylic Bonded to Polycarbonate Example No. (Break Forc_ in Pounds) (Break Force in Pounds) 9 425 (not deter~ined) It is seen that highly efficient, ultrasonically bondable compositions according to this invention are obtained.
Obviously, other variations are possible in the light of the above description. It is to be understood, therefore r that modifications may be made in the compositions disclosed herein which are within the full intended scope of the present invention as defined in the appended claims.
Compositions 1-3 and 5-7, according to this invention, equal ;
or exceed this value. If less than 40 parts of (c) per 100 parts of ~a) and (b~ are used, Control Example 4 (36 parts), it is seen that the bond strength falls below the minimum.
EXAMPLES~8 - 10 The general procedure of Examples 1-7 is repeated, substituting a styrene-maleic anyydride-butadiene rubber for component (c). The formulations used and the physical propexties obtained are set forth as folIows:
Compositions (parts by weight) poly(2,6-dimethyl-1,4-phenylene 0 ether (as is Examples 1-7) 25 25 35 Rubber modified high impact polystyrene resin (as in Examples 1-7) 25 25 20 ~3~3 ~ 8 CH 2335 Styrene-butadiene-styrene resin (as in Examples 1-7) 5 3 Styrene-maleic anhydride-butadiene terpolymer resin (80:10-10)a 50 50 45 Properties -Heat distortion temperature, F. 236 235 246 Izod impact strength, ft.lbs./
in Notch 2.8 1.9 3.0 Melt viscosity, poise 1,600 1,400 1,600 .
a ARCO Polymers, Inc., Pittsburgh, Pa., Dylark 240 The bond strengths at break, in units of pounds, are shown in Table 1 for ultrasonic bonds to acrylic and to poly-carbonate (Lexan 103) substrates:
ULTRASONICALLY WELDED BOND STRENGTHS ' Bonded to Acrylic Bonded to Polycarbonate Example No. (Break Forc_ in Pounds) (Break Force in Pounds) 9 425 (not deter~ined) It is seen that highly efficient, ultrasonically bondable compositions according to this invention are obtained.
Obviously, other variations are possible in the light of the above description. It is to be understood, therefore r that modifications may be made in the compositions disclosed herein which are within the full intended scope of the present invention as defined in the appended claims.
Claims (10)
1. A thermoplastic molding composition which, after molding, is ultrasonically bondable to an acrylic polymer or an aromatic polycarbonate resin with improved bond strength in the ultrasonically formed bond, said composition comprising, in admixture:
(a) a polyphenylene ether resin;
(b) a styrene resin; and (c) from about 40 to about 150 parts by weight of a polymeric material which is polar in relation to styrene resin (b), based on 100 parts by weight of (a) and (b).
(a) a polyphenylene ether resin;
(b) a styrene resin; and (c) from about 40 to about 150 parts by weight of a polymeric material which is polar in relation to styrene resin (b), based on 100 parts by weight of (a) and (b).
2. A composition as defined in Claim 1 wherein the polyphenylene ether resin (a) is of the formula:
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent sub-stituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent sub-stituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.
3. A composition as defined in Claim 1 wherein the styrene resin (b) is one having at least 25 percent, by weight, polymer units derived from a monomer having the formula:
wherein R is selected from the group consisting of hydrogen lower alkyl and halogen, Z is a member selected from the group consisting of hydrogen, lower alkyl, chlorine and vinyl, and p is a number from O to 5.
wherein R is selected from the group consisting of hydrogen lower alkyl and halogen, Z is a member selected from the group consisting of hydrogen, lower alkyl, chlorine and vinyl, and p is a number from O to 5.
4. A composition as defined in claim 3 wherein said styrene resin (b) is a rubber-modified high impact polystyrene.
5. A composition as defined in claim 4 wherein said rubber-modified high impact polystyrene is an A-B-A block copolymer.
6. A composition as defined in claim 5 wherein said A-B-A block copolymer is a styrene-butadiene-styrene resin.
7. A composition as defined in claim 1 wherein said;
polar polymeric material (c) is a copolymer of a vinyl aromatic compound and an ?,.beta. unsaturated cyclic anhydride.
polar polymeric material (c) is a copolymer of a vinyl aromatic compound and an ?,.beta. unsaturated cyclic anhydride.
8. A composition as defined in claim 7 wherein said polar polymeric material (c) is a copolymer of styrene and maleic anhydride.
9. A composition as defined in claim 7 wherein said polar polymeric material (c) is a terpolymer of styrene, maleic anhydride and a diene.
10. A composition as defined in claim 1 wherein said polar polymeric material (c) is a copolymer of a vinyl aromatic compound and an acrylic ester.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75351276A | 1976-12-21 | 1976-12-21 | |
| US753,512 | 1976-12-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134531A true CA1134531A (en) | 1982-10-26 |
Family
ID=25030954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000292811A Expired CA1134531A (en) | 1976-12-21 | 1977-12-09 | Ultrasonically bondable polyphenylene ether compositions |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5379944A (en) |
| AU (1) | AU3179777A (en) |
| BR (1) | BR7708522A (en) |
| CA (1) | CA1134531A (en) |
| DD (1) | DD134539A5 (en) |
| DE (1) | DE2751328A1 (en) |
| FR (1) | FR2375295A1 (en) |
| GB (1) | GB1562540A (en) |
| IT (1) | IT1088918B (en) |
| NL (1) | NL7712905A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4405753A (en) * | 1982-02-03 | 1983-09-20 | Monsanto Company | Polyblends |
| NL8303497A (en) * | 1983-10-12 | 1985-05-01 | Gen Electric | ARTICLE WHOLLY OR PARTLY MANUFACTURED FROM A POLYMER MIXTURE AND INCLUDED WITH A POLYURETHANE LAYER OR POLYURETHANE GLUE. |
| DE3346304A1 (en) * | 1983-12-22 | 1985-07-04 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| DE3346302A1 (en) * | 1983-12-22 | 1985-07-11 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| DE3346303A1 (en) * | 1983-12-22 | 1985-07-11 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| DE3444435A1 (en) * | 1984-12-06 | 1986-06-12 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| US5156920A (en) * | 1986-09-05 | 1992-10-20 | General Electric Company | Polyphenylene ether resin compositions having improved adhesion for decorative and protective coatings |
| CA2031376A1 (en) * | 1989-12-04 | 1991-06-05 | Bahram Farhadieh | Single layer transdermal drug administration system |
| US6165309A (en) * | 1998-02-04 | 2000-12-26 | General Electric Co. | Method for improving the adhesion of metal films to polyphenylene ether resins |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5148130B2 (en) * | 1972-06-01 | 1976-12-18 | ||
| US4124654A (en) * | 1974-06-07 | 1978-11-07 | General Electric Company | Thermoplastic molding compositions of vinyl aromatic compound alpha, beta unsaturated cyclic anhydride copolymers |
-
1977
- 1977-11-17 DE DE19772751328 patent/DE2751328A1/en not_active Withdrawn
- 1977-11-23 NL NL7712905A patent/NL7712905A/en not_active Application Discontinuation
- 1977-12-08 FR FR7737045A patent/FR2375295A1/en active Pending
- 1977-12-09 CA CA000292811A patent/CA1134531A/en not_active Expired
- 1977-12-13 GB GB5191077A patent/GB1562540A/en not_active Expired
- 1977-12-15 IT IT3074877A patent/IT1088918B/en active
- 1977-12-16 JP JP15232777A patent/JPS5379944A/en active Pending
- 1977-12-19 DD DD20276777A patent/DD134539A5/en unknown
- 1977-12-20 BR BR7708522A patent/BR7708522A/en unknown
- 1977-12-20 AU AU31797/77A patent/AU3179777A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NL7712905A (en) | 1978-06-23 |
| BR7708522A (en) | 1978-08-08 |
| IT1088918B (en) | 1985-06-10 |
| JPS5379944A (en) | 1978-07-14 |
| DD134539A5 (en) | 1979-03-07 |
| AU3179777A (en) | 1979-06-28 |
| DE2751328A1 (en) | 1978-06-29 |
| GB1562540A (en) | 1980-03-12 |
| FR2375295A1 (en) | 1978-07-21 |
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