CA1220295A - Polyphenylene ether compositions having improved processability - Google Patents

Polyphenylene ether compositions having improved processability

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Publication number
CA1220295A
CA1220295A CA000475234A CA475234A CA1220295A CA 1220295 A CA1220295 A CA 1220295A CA 000475234 A CA000475234 A CA 000475234A CA 475234 A CA475234 A CA 475234A CA 1220295 A CA1220295 A CA 1220295A
Authority
CA
Canada
Prior art keywords
resins
polyphenylene ether
resin
compositions
weight
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
Application number
CA000475234A
Other languages
French (fr)
Inventor
James M. Vaughan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GE Chemicals Inc
Original Assignee
Borg Warner Chemicals Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Borg Warner Chemicals Inc filed Critical Borg Warner Chemicals Inc
Application granted granted Critical
Publication of CA1220295A publication Critical patent/CA1220295A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12Polyphenylene oxides
    • C08L71/123Polyphenylene oxides not modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02Polyalkylene oxides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/905Polyphenylene oxide

Abstract

POLYPHENYLENE ETHER COMPOSITIONS
HAVING IMPROVED PROCESSABILITY

ABSTRACT:

Compositions comprising polyphenylene ether resins and high impact polystyrene resins exhibit improved processability and reduced adhesion to heated metal surfaces when a minor but effective amount of an ethy-lene oxide - propylene oxide copolymer is included therein.

Description

;~2~ 35 POLYPHENyLENE ETHER COMPOS I TI ONS
HAVING IMPROV D PROCESSABILITY

Description This invention relates to polyphenylene ether (PPE) blends having improved processability and reduced adhesion to metal surfaces, and more particularly t~ a method for improving the processability of PPE blend compositions.

Polyphenylene ether (PPE~ resins and particularly PPO, or poly(2,6-dimethyl-1,4-phenylene ether), have long been known as high temperature thermoplastics.
These resins are typically prepared by the oxidative coupling of a monohydric phenol such as 2,6-dimethyl phenol, as taught for example in US patents 3,134,753 and 3,306,874. PPE resins soften or melt only at very high temperatures, normally well above 500F, which may exceed the upper limit of thermal stability for such materials. The resins also exhibit a very high melt viscosity, and are very difficult to melt process in conventional processing equipment without substantial thermal degradation. Commonly the resins are blended with lower melt temperature resins to improve their melt processability and to achieve commercially acceptable molding characteristics. For example, polyphenylene ether resins may be blended with styrenic resins as is disclosed in US patents 3,356,761 and 3,383,435 or with polyolefins such as polyethylene as described in US
3,361,851 to achieve improved processability.

More recently, in US patent 4,038,543, there were disclosed phenylene ether copolymer resins (PEC~ having z~

improved thermal resistance, high temperature oxidative stability and resistance to heat aging. These resins, copolymers of 2,6-dialkyl phenols and 2~3,5 trialkyl phenols containing up to 50 wt~ of the trialkyl monomer component, are more stable at the melt processing temperature, but exhibit a high melt viscosity and are also difficult to melt process alone. Blending these copolymers with other resins such as styrenic polymers is therefore desirable to achieve adequate process ability and a useful balance of mechanical properties for commercial molding applications.

Although combining polyphenylene ether resins or phenylene ether copolymer resins with styrenic resins achieves an improvement in processability and when further formulated produces molding resins with a useful balance of mechanical properties, such blends generally require the further addition of processing aids to acheive practical thermal processability characteristics in molding and extrusion equipment. For example, polyolefins have long been added to such compositions as processing aids, and the use of hydrocarbon waxes to improve melt flow is disclos~d in US Patent 4,4~0,654. The mold release characteristics of such compositions are also said to be good when a minor amount of a low molecular weight polyamide or alkylene glycol is substituted for the polyolefin, according ~o US Patent 4,433,088.

The use of polyolefins, hydrocarbon waxes, amides and other such processing aids has been successful in providing processable blends. However, when used at levels sufficient to improve processing without signiEi-cantly lowering the heat distortion temperature charac-teristics of these blends, the resulting formulations exhibit an undesirable degree of adhesion to hot metal surfaces and sticking to the surfaces of dies, molds and the like. A reduction in mold-sticking characteristics has hereto~ore been accomplished by further increasing the level of the processing aid, thereby reducing the heat distortion characteristics of the blend.

This invention is a composition having improved processability and reduced mold-sticking character-istics, and a method for improving the processing characteristics of compositions comprising a polypheny-lene ether resin and a polystyrene. The improvement is accomplished by including a minor amount of a block copolymer of ethylene oxide and propylene oxide suffi-cient to provide improved processability and reduce adhesion to hot metal surfaces such as the surfaces of heated molds, extrusion dies, and ~he flights of screw injection molding machines and extruders. The addition of as little as 0.5 parts by weight of the copolymer to such compositions effects a substantial improvement in processability without deleteriously affecting the physical properties and particularly the heat distortion characteristics of the molded article. The compositions may further comprise conventional processing aic~s such as polyolefins and the like.

The PPE blend compositions which are improved according to the teachings of this invention comprise from 5 to 95 wt% of a phenylene ether resin (PPE) and from 95 to 5 wt% of an styrenic resin. The improved compositions may further comprise polyolefins, impact modifiers, plasticizers and stabilizers as convention-ally practiced in the compounding art.

~L2;~32~S
~, The phenylene ether resins useful for the purpose of this invention are, in general, polymers of a 2,~-dialkyl phenol such as for example 2,6-dimethyl phenol, and copolymers thereof with a 2,3,6-trialkyl phenol such as for e~ample 2,3,6-trimethyl phenol. The proportion of 2,3,6-trialkyl phenol in such cop~lymers will lie in the range of from about 2 to 50 wt~ based on total phenylene ether copolymer. However, the preferred copolymers will comprise from about 2 to 20, more preferably from about 2 to about 10 wt% 2,3,6-trialkyl phenol and correspondingly from about 98 to about 80, more preferably from about 98 to about 90 wt~ 2,6-dialkyl phenol. The synthesis of these resins from the corresponding phenols by an oxidative coupling process is well known and is well described and set forth in the art, for example in US 4,011,200.

The styrenic resins useful in the practice of this invention include the homopolymers of styrene, vinyl toluene, chlorostyrene, bromostyrene and the like as well as copolymers thereof, and high impact or HIPS
versions thereof, which commonly include graft copoly-mers of said monomers on rubbery subs~rates and blends of said homopolymers or copolymers with rubbery impact modifiers. A great variety of these styrenic resins are readily available commercially.

Blends of PPE homopolymer and copolymer resins with styrenic resins are widely available commercially, and include the Noryl R resins sold commercially by the General Electric Company and Prevex TM resins sold by Borg-Warner Chemicals, Inc. As sold, these commercial blends are formulated with plas~icizers, pigments, flame retardants, lubricants, stabilizers and the like such as aromatic phosphates, polyolfeins, phosphites, phenolic stabilizers/ ans so forth.

The ethylene oxide - propylene o~ide block copoly-mers useful in the practice of this invention, are also readily available from commercial sources. The block copolymers of ethylene oxide and propylene oxide having from 20 to 90 wt% ethylene oxide and a molecular weight of from 2,000 to 10,000 are generally prepared in a controlled, caustic-initiated polymerization of the two monomers to provide well-def-ned homopolymeric sequences of the ethylene oxide component and the propylene oxide component. These block copolymers may thus be tailored to provide particularly desired physical characteristics such as hydrophilicity, crystallinity, melting point and the like. Such block copolymers are widely recognized in the art as a distinct class of ether copolymers, quite different in physical properties from random copolymers of the two components or homopolymers of either component alone. Such materials are widely sold under a variety of trade names including the Pluronic R
series of surfactants sold by Wyandotte Chemical Co., and the Pegol TM series of surfactants sold by Borg-Warner Chemicals, Inc.

The compositions of this invention will comprise from 0.01 to 2.0 parts by weight of the ethylene oxide -propylene o~ide block copolymer per hundred parts by weight of the PPE resin - styrenic resin blend. Al-though the beneficial effects of the additive will be apparent at any level of additive, at very low levels the effect on mold-sticking will be small and possibly o~ little real benefit, while at levels much above about 1 0 pbw an undesirable degree oE depression of the HDT
value for the blend will be noted. For practical reasons, the most preferred level will be in the range of from about 0.1 to about 0.75 pbw. These blend compositions may be prepared by any of a variety of methods well known in the polymer art. For example, an intimate mixture of the powdered resins and the ethylene oxide - propylene oxide block copolymer may be prepared by dry-blending or by thermally-processing in a melt-mixing device such as a Banbury mixer or a heated roll-mill, or by feeding the mixed components to a single or twin-screw extruder at an elevated temperature of from about 450 to 600F. The resulting resin blend 1~ may then be chopped or ground into particles and molded, for example by use of a ram or screw-fed injection molding machine. The extrusion and molding of the improved resins of this invention i6 accomplished readily and with less troublesome die-sticking and mold-sticking problems, as compared with conventional PPE-styrenic resin formulations.

The practice of this invention will be better understood by consideration of the following examples.
These examples are not offered in limitation of the
2~ invention but rather in illustration of preferred embodiments.

EXAMPLE 1. A powdered commercial polyphenylene ether - high impact styrene resin blend formulation, - obtained a6 Prevex TM VF1 resin from Borg-Warner Chemicals, Inc., was melt compounded with O.S pbw ethylene oxide - propylene oxide polymer obtained as v~s Pegol F88 grade from Borg-Warner Chemicals, Inc. and then extruded in a Werner Pfleiderer twin-screw extruder at 500F. The extrudate, in the form of pellets, was then melt-pressed between two ferrotype plates at 500F
in a heated~platen hydraulic press for 20 sec. at 30tO00 psi. The plates were removed from the press and chilled in a water bath for about lO sec. The plates were easily separated to provide a pressed disc of the resin.

As a control, the Prevex VFl grade resin, extruded a5 before, was pressed between ferrotype plates withou~
being first compounded with F88. The plate could not be separated by twisting, prying with screw drivers or pulling with vice-grip type pliers.

Prevex TM VFl grade resin comprises 50 wt~ pheny-lene ether resin, 45 wt% high impact styrene resin, and approximately by 1 wt% polyolefin, based on total polymeric components, together with impact modifiers~
stabilizers, an aromatic phosphate and pigments.

EXAMPLES 2-11. Blends of PQA grade and sJA grade Prevex TM resins were prepared by mixing the powdered resins with varying levels of processing aids, extruding into pellets as in Example 1, then injection molding the pellets to form test specimens. The physical properties of these blends are summarized in Table I.

2~ PQA and BJA grades of Prevex resins include the same components as the VF1 grade of Example 1, hut in different proportions. Both grades include greater than 0.5 pbw polyolefin.

2~

Control blends without F88 are included as Control Examples A and B.

EBS wax, or ethylene bis stearamide, an amide-type additive commonly used as a processing aid fnr resins~
was also compounded with these resins in place of the F88 to provide comparison Examples 5, 6, lO and 11.

~2~ s g Table I

Ex No: A 2 3 4 5 6 Resin( ) PQ~ PQ~ PQA PQ~ PQA PQA
Additive - F88 F88 F88 EBS EBS
pbw - 0.25 0.50 1.0 0.5 1.0 HDr, F 237 236 236 236 236 231 Izod Impact3.8 3.9 3.7 4.0 3.8 3.8 Tens Str psi 7435 7335 7520 7510 7715 7525 E % 50 38 43 37 39 30 Ex No: B 7 8 9 10 11 Resin( ) BJA EJA EJA BJA BJA ~JA
~ditive - F88 F88 F88 E3S EBS
pbw - 0.25 0.5 1.0 0.5 1.0 HDT, F 185 183 181 181 180 173 Izod Impact5.1 5.5 6.1 6.5 5.8 5.8 Tens Str psi 6115 6050 5980 6090 6360 6205 E ~ 45 47 38 50 48 43 . . _ . _ . . . _ . . _ . _ . __ otes: (1) PQA and ~JA are grades of Prevex TM resin.
See test. F88 is Pegol TM F88 grade ethylene oxide - propylene oxide block copolymer resin. See text.

~2~ss - 1 o -lt will be apparent that the addition of F88 has little effect on the physical properties of phenylene ether blends, with only minimal lowering of HDT value at a level of 1.0 pbw. The effect on processability, however, is great. The blend of Example 3, in a produc-tion run in an extruder, was processed continuously for three hours without difficulty. The blend of Control A, containing no F88, produced substantial particle build-up in the die area, forcing the shaping die out of adjustment and requiring peroxidic adjustments of the die over the same time period.

Prevex compositions 5, 6, 10 and 11, having ethy-lene bis stearamide (EBS) as the added processing aid, were subject to the same limitations as the Control A
example in extrusion runs, producing substantial build-up in the die area. Additionally, the use of EBS will be seen in Examples 6 and 11 to produce a marked de-crease in HDT values. Compositions containing EBS at these levels exhibited only marginal improvement in the metal plate sticking test described in Example 1, demonstrating that the use of an amide-type lubricant is ineffective in this application.

The instant invention will thus be seen to be a method for improving the processing characteristics oE a 2~ PPE resin blend comprising a polyphenylene ether - high impact styrene comprising blending therewith from 0.01 to 1.0 parts by weight ethylene oxide - propylene oxide copolymer per hundred parts by weight of said PPE resin blendl and an improved PPE resin blend. The composi-
3~ tions of the foregoing examples are provided by way of z~s illustration of the method and the improved compositionsof this invention and not in limitation thereof, and the scope of this invention will be understood by those skilled in the art as defined by the appended claims.

Claims (3)

1. In a composition comprising a polyphenylene ether resin and a high impact polystyrene, the improve-ment wherein an ethylene oxide - propylene oxide block copolymer is included in an amount effective to reduce adhesion to metals.
2. A phenylene ether resin composition consisting of 100 parts by weight of a blend comprising a poly-phenylene ether and a high impact polystyrene and from 0.01 to 1.0 parts by weight of an ethylene oxide -propylene oxide block copolymer.
3. A method for reducing the adhesion of composi-tions comprising a polyphenylene ether resin and a high impact polystyrene resin to hot metal surfaces, said method consisting of the step of blending with said composition from .01 to 1.0 parts by weight of an ethylene oxide - propylene oxide block copolymer per hundred parts by weight of said composition.
CA000475234A 1984-08-24 1985-02-27 Polyphenylene ether compositions having improved processability Expired CA1220295A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US643,939 1984-08-24
US06/643,939 US4524179A (en) 1984-08-24 1984-08-24 Polyphenylene ether compositions having improved processability

Publications (1)

Publication Number Publication Date
CA1220295A true CA1220295A (en) 1987-04-07

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ID=24582777

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CA000475234A Expired CA1220295A (en) 1984-08-24 1985-02-27 Polyphenylene ether compositions having improved processability

Country Status (5)

Country Link
US (1) US4524179A (en)
EP (1) EP0176653B1 (en)
JP (1) JPS6155141A (en)
CA (1) CA1220295A (en)
DE (1) DE3577867D1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634732A (en) * 1985-08-06 1987-01-06 Borg-Warner Chemicals, Inc. Thermoplastic molding compositions

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3631126A (en) * 1970-08-10 1971-12-28 Uniroyal Inc Polyphenylene oxide resins modified with polyhydroxy ethers
US4224209A (en) * 1978-09-05 1980-09-23 General Electric Company Polyphenylene ether resin compositions containing poly(alkylene oxides) and phosphate plasticizer
AU564528B2 (en) * 1981-02-26 1987-08-13 General Electric Company Polyphenylene ether compositions and process
DE3116491A1 (en) * 1981-04-25 1982-11-11 Basf Ag, 6700 Ludwigshafen "THERMOPLASTIC MOLDS"

Also Published As

Publication number Publication date
DE3577867D1 (en) 1990-06-28
JPS6155141A (en) 1986-03-19
US4524179A (en) 1985-06-18
EP0176653B1 (en) 1990-05-23
EP0176653A1 (en) 1986-04-09

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