CN1774476A - Poly(arylene ether) compositions - Google Patents
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Abstract
A poly(arylene ether) composition comprises a first poly(arylene ether) resin having an intrinsic viscosity greater than or equal to about 0.3 dl/g, as measured in chloroform at 25 DEG C and a second viscosity poly(arylene ether) resin having an intrinsic viscosity less than or equal to about 0.17 dl/g, as measured in chloroform at 25 DEG C wherein the composition is essentially free of plasticizers.
Description
Cross reference to related application
The sequence number that the application requires on February 28th, 2003 to submit to is 60/319,980 U.S. Provisional Application No., incorporates it into this paper by reference at this.
Background of invention
The disclosure relates to poly (arylene ether) composition, and it has the combination of low melt viscosity and high heat deflection temperature (HDT).
Because the polyarylene ether resin has stability to hydrolysis, high dimensional stability, toughness, thermotolerance and dielectric properties, so the polyarylene ether resin is the very useful high-performance engineering thermoplastic material of a class.They also show good mechanical performance and high second-order transition temperature value, and this value is generally 150 ℃～210 ℃.This particular performances combination makes the poly (arylene ether) based composition be applicable to the application of wide range.The polyarylene ether polymer has high relatively molecular weight usually and has high melt viscosity, measures in 25 ℃ chloroform, and its inherent viscosity is usually greater than about 0.3dl/g.
The melt viscosity capability of improving poly (arylene ether) composition is an ideal.Melt viscosity capability is composition at high temperature free-pouring ability during the various process segments (for example extruding and molding).Melt viscosity can influence the size and the type of the parts of being made by described composition.Advised improving by the molecular weight that reduces the polyarylene ether polymer melt viscosity of poly (arylene ether) composition, still, lower molecular weight influences for example shock strength of other performances sometimes unfriendly.Perhaps, often use flow improver additive or softening agent (for example polystyrene, particularly crystal polystyrene, saturated poly-alicyclic resin and terpene phenol) preparation poly (arylene ether) composition, to give the composition that obtains with high flowability.Polystyrene, terpene phenol and other this flow improver additives reduce the heat deflection temperature (HDT) (HDT) of product.In addition, some fire retardants also are used as softening agent and improve melt viscosity capability.
Improving poly (arylene ether) resin flow characteristic, simultaneously minimum ground or do not lose the HDT value and effort has been made in the impact property aspect.A kind of method suggestion adds the hydrocarbon that contains the resin additive of vi-ny l aromatic monomers or contain the aromatic units of at least 35 weight %.
Additive method comprises the blend that contains two or more polyarylene ether resins, and a kind of resin has high inherent viscosity and other resin has low limiting viscosity.Although these methods are likely, they are primarily aimed at contains a large amount of compositions to influential fire retardant of heat deflection temperature (HDT) and/or softening agent.
Summary of the invention
A kind of poly (arylene ether) composition contains the limiting viscosity that records and be less than or equal to the second viscosity polyarylene ether resin of about 0.17dl/g more than or equal to the first polyarylene ether resin of about 0.3dl/g and the limiting viscosity that records in 25 ℃ chloroform in 25 ℃ chloroform, wherein said composition is substantially free of softening agent.
In another embodiment, poly (arylene ether) composition is given birth to the second viscosity poly (arylene ether) resin that viscosity is less than or equal to about 0.17dl monk by the limiting viscosity that records more than or equal to the first polyarylene ether resin of about 0.3dl/g and the spy that records basically and is formed in 25 ℃ chloroform in 25 ℃ chloroform.
Description of drawings
Fig. 1 is the figure that describes melt viscosity data.
Fig. 2 is the figure that describes the heat deflection temperature (HDT) data.
Fig. 3 is the figure that describes the heat deflection temperature (HDT) data.
Fig. 4 is the figure that describes melt viscosity data.
Fig. 5 is the figure that describes melt viscosity data.
Embodiment
A kind of poly (arylene ether) composition contains the limiting viscosity that records and be less than or equal to the second polyarylene ether resin of about 0.17dl/g more than or equal to the first polyarylene ether resin of about 0.3dl/g and the limiting viscosity that records in 25 ℃ chloroform in 25 ℃ chloroform, wherein said composition is substantially free of softening agent.Here " being substantially free of " is defined as containing the softening agent less than about 1 weight %, preferably less than about 0.5 weight %, and 0 weight % more preferably, wherein the amount of softening agent is based on the gross weight of composition.
Poly (arylene ether) composition described herein has the combination of so far unknown low melt viscosity and high heat deflection temperature (HDT).
Measure with multiple spot capillary rheology method of masurement, the composition that does not contain filler is at 1500s
-1With 320 ℃ show usually and be less than or equal to approximately 190, preferably be less than or equal to approximately 180, be more preferably less than or equal the melt viscosities of about 170 pascal-seconds.Measure with multiple spot capillary rheology method of masurement, the composition that contains filler is at 1500s
-1With 320 ℃ show usually and be less than or equal to approximately 270, preferably be less than or equal to approximately 250, be more preferably less than or equal the melt viscosities of about 230 pascal-seconds.
Utilize ASTM D648 to measure, the composition that contains or do not contain filler has under 264 pounds/square inch (psi) more than or equal to about 130 ℃, be preferably greater than or equal about 140 ℃, more preferably greater than or equal about 150 ℃, most preferably more than or equal to about 165 ℃ heat deflection temperature (HDT).Poly (arylene ether) composition had not obtained the combination of low melt viscosity and high heat deflection temperature (HDT) in the past.
Low melt viscosity poly (arylene ether) composition in the past uses the softening agent of restriction heat deflection temperature (HDT).
Measure under 25 ℃ and 1 kilo hertz or 10 kilo hertzs or 100 kilo hertzs or 1 megahertz according to ASTM D 150, said composition also shows and is less than or equal to approximately 0.02, preferably is less than or equal to approximately 0.01, is more preferably less than or equals about 0.005 loss factor.In one embodiment, at 25 ℃ and measure under 1 kilo hertz, 10 kilo hertzs, 100 kilo hertzs and 1 megahertz respectively, curing composition shows and is less than or equal to about 0.005 loss factor according to ASTM D 150.
Measure according to ASTM D149, said composition also shows the dielectric strength of improvement.For example, the limiting viscosity that records in 25 ℃ chloroform that contains 90 weight % is that the limiting viscosity that records in 25 ℃ chloroform of the poly (arylene ether) of 0.4dl/g and 10 weight % is that the composition of the poly (arylene ether) of 0.12dl/g has the average dielectric strength value of 28 kilowatts/millimeter (kv/mm), and standard deviation is 2.02kv/mm.In order to contrast, the limiting viscosity that records in 25 ℃ chloroform that contains 90 weight % is that the composition of the polystyrene of the poly (arylene ether) of 0.4dl/g and 10 weight % has the average dielectric strength value of 25.6kv/mm, and standard deviation is 1.37kv/mm.The weight percent of test polymer is based on the gross weight of composition.
The term poly (arylene ether) comprises polyphenylene oxide (PPE) and poly (arylene ether) copolymer; Graft copolymer; Poly (arylene ether) ether ionomer; And the segmented copolymer of alkenyl aromatic compounds, vinyl aromatic compounds and poly (arylene ether) etc.; And comprise above-mentioned at least any combination; Or the like.Poly (arylene ether) itself is known polymkeric substance, and it comprises a plurality of structural units with general formula (1):
Wherein for each structural unit, each Q
1Be independently hydrogen, halogen, uncle or secondary low alkyl group (for example, contain the alkyl of 7 carbon atoms at the most), phenyl, haloalkyl, aminoalkyl group,-oxyl (hydrocarbonoxy), halo-oxyl, wherein at least two carbon atoms separate halogen and Sauerstoffatom, or the like; And each Q
2Be hydrogen, halogen, uncle or secondary low alkyl group, phenyl, haloalkyl,-oxyl, halo-oxyl independently, wherein at least two carbon atoms separate halogen and Sauerstoffatom, or the like.Preferably, each Q
1Be alkyl or phenyl, C particularly
1-4Alkyl, and each Q
2Be hydrogen.
Homopolymer and multipolymer poly (arylene ether) are all included.Preferred homopolymer is to contain 2, the unitary homopolymer of 6-dimethylphenylene ether (2,6-dimethylphenylene ether).Suitable copolymers comprises and for example contains said units and 2,3,6-trimethylammonium-1, and the random copolymers of 4-phenylene ether units, perhaps derived from 2,6-pseudocuminol and 2,3, the multipolymer of the copolyreaction of 6-pseudocuminol.Also comprise the poly (arylene ether) that contains the part that obtains by grafting vinyl monomers or polymkeric substance (for example polystyrene), and the coupling poly (arylene ether), wherein coupling agent (for example low-molecular polycarbonate, quinone, heterocycle and formal) in a known way with the hydroxyl reaction of two poly (arylene ether) chains to produce more high-molecular weight polymer.Poly (arylene ether) further comprises the combination that contains at least a above-mentioned substance.
Poly (arylene ether) composition uses two kinds of poly (arylene ether)s.Measure in 25 ℃ chloroform, the first polyarylene ether resin has the limiting viscosity greater than about 0.30dl/g.These polymkeric substance have the repeating unit of the above-mentioned general formula I more than 50 usually, use gel permeation chromatography measurement, and number-average molecular weight is about 3,000-40,000 and weight-average molecular weight be 20,000-80,000.Measure in 25 ℃ chloroform, the second polyarylene ether resin has the limiting viscosity that is less than or equal to about 0.17dl/g, preferably is less than or equal to about 0.15dl/g, is more preferably less than or equals about 0.13dl/g.Here be used in reference to term first and second for the polyarylene ether resin only with marking, do not represent to hint or interpolation order that needs are specific.The first and second polyarylene ether resins can have identical or different chemical structure.
Poly (arylene ether) normally passes through for example 2 or 2,3 of at least a monohydroxy aromatic substance of oxidative coupling, and the 6-pseudocuminol prepares.Catalyst system is generally used for this coupling; Described catalyst system contains at least a heavy metal compound for example copper, manganese or cobalt compound usually, usually with various other materials combinations.
The useful especially poly (arylene ether) that is used for multiple purpose is the poly (arylene ether) that contains the molecule with at least one end group that contains aminoalkyl group.Described aminoalkyl groups is usually located at the ortho position of hydroxyl.By introducing suitable uncle or secondary monoamine (for example Di-n-Butyl Amine or dimethylamine) wherein a kind of component, can obtain to contain the product of this end group as the oxidative coupling reaction mixture.What also often provide is 4-xenol end group, and it comes from the reaction mixture that has the by product phenoquinone usually, particularly in copper-halogenide-second month in a season or tertiary amine system.Usually the major part up to the polymer molecule of about 90 weight % that constitutes polymkeric substance can contain at least a in described end group that contains aminoalkyl group and the 4-xenol end group.
The poly (arylene ether) of imagination comprises many present known substances and is that those skilled in the art can learn apparently from top content no matter how structural unit or auxiliary chemical feature change.
In poly (arylene ether) composition, the weight ratio of first poly (arylene ether) and second poly (arylene ether) can change on a large scale, is preferably greater than about 1: 1, more preferably greater than about 1.25: 1.About 1: 5 to about 20: 1 weight ratio or even preferred, about 9: 1 to about 2: 1 weight ratio be most preferred.Under high density, the second polyarylene ether resin provides hard brittle material.Therefore, the second polyarylene ether resin preferably uses with about 40 weight % of total composition or amount still less, more preferably uses with the amount of about 1～about 30 weight % of total composition, most preferably uses with the amount of about 3～about 25 weight % of total composition.
Poly (arylene ether) composition can contain other components that content can wide variation.The most frequent consumption of the combination of first and second poly (arylene ether)s is about 5～about 95 weight %, preferred about 50～about 95 weight %, and above-mentioned consumption is with total restatement of composition.But the composition that contains 100 weight % poly (arylene ether)s is special imagination.
In specific embodiment, poly (arylene ether) composition can contain just like United States Patent(USP) Nos. 5,981, and 656 and 5,859,130 disclosed polymeric amide are as U.S. Patent No. 5,290,881 disclosed poly (arylene sulfide)s are as U.S. Patent No. 5,916,970 disclosed polyphthalamides are as U.S. Patent No. 5,231,146 disclosed polyetheramides are as U.S. Patent No. 5,237,005 disclosed polyester, the combination of polyetherimide and above-mentioned substance.
Poly (arylene ether) composition can further contain additive, for example impact modifying agent, oxidation inhibitor, filler, conductive filler material (for example conductive carbon black, carbon fiber, Stainless Steel Fibre, tinsel, metal-powder etc.), toughener (for example glass fibre), stablizer (for example, oxidation, heat and UV stabilizer), static inhibitor, lubricant, tinting material, dyestuff, pigment, Antidrip agent and releasing agent.
The material (impact modifying agent) that improves the shock strength of poly (arylene ether) composition is not critical, but often needs.Suitable material comprises natural and synthetic elastomeric polymer for example natural rubber, synthetic rubber and thermoplastic elastomer.They are usually derived from monomer for example alkene (for example ethene, propylene, 1-butylene, 4-methyl-1-pentene), alkenyl aromatic monomer (for example vinylbenzene and alpha-methyl styrene), conjugated diolefine (for example divinyl, isoprene and chloroprene) and vinyl carboxylic acid and derivative (for example vinyl-acetic ester, vinylformic acid, alkyl acrylic, ethyl propylene acid esters, methyl methacrylate, vinyl cyanide) thereof.They can be homopolymer and multipolymer, and that described multipolymer comprises is random, block, grafting and core-shell copolymerized thing, and described blend is derived from the various suitable monomers of following special discussion.
The polyolefine that can be contained in the poly (arylene ether) composition has structure C
nH
2n, and comprising polyethylene, polypropylene and polyisobutene, preferred homopolymer is polyethylene, LLDPE (linear low density polyethylene), HDPE (high density polyethylene(HDPE)) and MDPE (medium-density polyethylene) and complete in (isotatic) polypropylene.Polyolefin resin with this structure and preparation method thereof is well known in the art and is described in for example United States Patent(USP) Nos. 2,933,480,3,093,621,3,211,709,3,646,168,3,790,519,3,884,993,3,894,999,4,059,654,4,166, in 055 and 4,584,334.
Can also use polyolefinic multipolymer, for example the multipolymer of ethene and alpha-olefin (as propylene and 4-methyl-1-pentene).Ethene and C
3-C
10The multipolymer of monoolefine and non-conjugated diene (being called the EPDM multipolymer here) also is suitable for.The appropriate C that is used for the EPDM multipolymer
3-C
10The example of monoolefine comprises propylene, 1-butylene, 2-butylene, 1-amylene, 2-amylene, 1-hexene, 2-hexene and 3-hexene.Suitable diene comprises 1,4-hexadiene and monocycle and many cyclic diolefines.Ethene and other C
3-C
10The mol ratio of monoolefine monomer can be 95: 5～5: 95, and wherein diene units exists with the amount of 0.1～10 mole of %.Can carry out functionalizedly to the EPDM multipolymer with being used to be grafted to acyl group on the poly (arylene ether) or electrophilic group, as U.S. Patent No. 5,258,455 is disclosed.
Based on the gross weight of composition, polyolefine exists with the amount of about 0.1%～about 10% weight usually.When polyolefine was EPDM, its amount was generally 0.25% weight～about 3% weight of composition.
Be used for impact modified suitable material and comprise conjugated diene homopolymers and random copolymers.Example comprises polyhutadiene, butadiene-styrene copolymer, butadiene-acrylic acid ester copolymer, isoprene-isobutylene copolymers, chloroprene polymer, butadiene acrylonitrile polymkeric substance and polyisoprene.These impact modifying agents can account for about 1～30 weight % of total composition.
Have conjugated diolefine-the useful especially impact modifying agent of class comprises AB (diblock), (AB) m-R (diblock) and ABA ' (three blocks) segmented copolymer.Block A and A ' be alkenyl aromatic units normally, and B block is conjugated diene unit normally.For the segmented copolymer with general formula (AB) m-R, integer m is at least 2, and R is the multifunctional coupling agent that is used for the block of AB structure.
The core-shell graft copolymer of alkenyl aromatic compounds and conjugated diene compound also is useful.Specially suitable is the multipolymer that contains styrene block and divinyl, isoprene or ethene-butylene blocks.Suitable conjugated diene block comprise above-mentioned can be by currently known methods partially or completely hydrogenant homopolymer and multipolymer, they can be represented as ethylene-propylene block etc. thus, and have the character similar to olefin block copolymers.Suitable alkenyl aromatic compounds comprises vinylbenzene, alpha-methyl styrene, p-methylstyrene, Vinyl toluene, vinyl-dimethyl benzene and vinyl naphthalene.Segmented copolymer preferably contains 15～50% the alkenyl aromatic units of having an appointment.The example of such triblock copolymer is polystyrene-poly divinyl-polystyrene (SBS), hydrogenated polystyrene-polyhutadiene-polystyrene (SEBS), polystyrene-poly isoprene-polystyrene (SIS) and poly-(alpha-methyl styrene)-polyisoprene-poly-(alpha-methyl styrene).The example of the commercial triblock copolymer that can obtain is the CARIFLEX from Shell ChemicalCompany, KRATON D and KRATON G series.
The impact modifying agent that also comprises star-like (radial) segmented copolymer that contains vi-ny l aromatic monomers and conjugate diene monomer.Such multipolymer contains the polymerization of vinyl aromatic monomer of 60～95 weight % that have an appointment and the polymerized conjugated diene monomer of about 40～5 weight % usually.Described multipolymer has at least three polymer chains that form star-like configuration.Each chain all with stiff segment termination basically, is connected with the elastomeric polymer segment on this segment.
As U.S. Patent No. 4,097,550 is described, and these segmented copolymers are called " branching " polymkeric substance sometimes, and use with the amount similar to other conjugated diene impact modifying agents.
Be used to improve the normally about 2～about 10 weight % of consumption of material of the shock strength of composition, with total restatement of composition.
Have been found that and use the advantage of above-mentioned low limiting viscosity poly (arylene ether) resin also to be provided in the fibre-reinforced poly (arylene ether) composition.Toughener comprises fiber and nonfibrous filler.Poly (arylene ether) composition can contain for example glass fibre of fiber reinforced material, and it can significantly improve with the flexural strength of its moulding compound that obtains, dimensional stability and modulus and tensile strength.Usually, the relative lime-alumina borosilicate glass (" E " glass) that does not contain soda is preferred.Though can use woven glass roving fabric, staple fibre (cut fiber) and milled fiber often are preferred.Normally at least 3 millimeters of the length of this staple fibre (mm), the length of milled fiber is less than or equal to about 1.5mm.Preferred length is about 3mm～about 13mm.The preferred diameter of fiber is about 0.002mm～about 0.015mm (promptly 15 microns).The consumption of glass fibre is 0 of total composition～about 60 weight %, is preferably about 3%～about 30 weight %, in the weight of whole compositions.When end-use needs higher hardness and intensity, use the greater amount glass fibre.More preferably, in the weight of whole compositions, the amount of glass fibre is about 6%～about 25 weight %.
The graphite fibre of carbon fiber, carbon filament, carbon dust, Kevlar fiber, Stainless Steel Fibre and metallizing also can use with the amount of 0～about 60 weight %, preferably use, more preferably use with the amount of 3～about 15 weight % with the amount of about 1.5～about 25 weight %.The length of carbon fiber is generally 3mm at least, preferably about 3mm～about 13mm.The example that is used for the metal of coated graphite fiber comprises nickel, silver, brass, copper and gold, and wherein nickel is preferred.The fiber of metal (for example aluminium, nickel, iron and bronze) and the suitable amounts of small pieces are about 60 weight % at the most, with total restatement of composition.
Suitable non-fiber mineral filler comprises hydrate, lime carbonate, silica, kaolin, barium sulfate, talcum and the Calucium Silicate powder (wollastonite) of mica, clay, granulated glass sphere, sheet glass, graphite, aluminium.According to used particular agent, significant quantity can be different, but are generally about 0.25%～about 60 weight %, are more typically about 1～about 30 weight %, are preferably about 3%～about 12 weight %, in the weight of whole compositions.The micaceous example comprises white mica, phlogopite, biotite, fluorophlogopite and synthetic mica.During use, the micaceous consumption is preferably about 0.25%～about 30 weight %, in the weight of whole compositions.During use, the preferable amount of clay is about 0.25%～about 30 weight %, in the weight of whole compositions.
Suitable pigment comprises pigment well known in the art, for example titanium dioxide (TiO
2) and carbon black.Suitable stabilizers comprises zinc sulfate, zinc oxide and magnesium oxide.
Suitable oxidation inhibitor comprises but is not limited to azanol; Hindered phenol is alkylation monohydric phenol and polyphenol for example; Benzofuranone, for example 3-aryl benzofuranone; Alkyl and aromatic yl phosphite, for example 2,4-DI-tert-butylphenol compounds phosphorous acid ester and tridecyl phosphite; Hindered amine, for example dioctyl methylamine oxide compound and other tertiary amino oxides.These oxidation inhibitor preferably use with the amount of 0.1～1.5 weight % that accounts for composition weight.
Suitable UV stabilizer comprises 4,6-dibenzoyl resorcinols, alkanolamine, (morpholenes) and benzotriazole.
Poly (arylene ether) composition can be by the method preparation of knowing.Described preparation method's a example is dry blend first and second poly (arylene ether)s at first, and with compound this mixture of known technology (for example in forcing machine), to form poly (arylene ether) composition.Can with extra component for example filler add with poly (arylene ether) composition or in the mixing of back or composite steps, add.Compare with the previously known poly (arylene ether) composition that contains softening agent, this poly (arylene ether) composition has lower melt viscosity, provides higher H DT value and impact property simultaneously.This poly (arylene ether) composition can or be extruded with other component blend, quenching and be cut into bead.Can melt these beads then and it is molded as the goods with desired shape and size, perhaps the preparation finished product additional processing before compound once more with other component blend.
Poly (arylene ether) composition is specially adapted to form Electronic Packaging system for handling (electronicpackaging handling system) for example surface-mounted integrated circuit and head suspension assembly dish (head gimbalassembly trays).The material require excellent size stability of using in the Electronic Packaging system for handling particularly is being higher than under about 130 ℃ temperature, is being greater than or equal under about 150 ℃ temperature in some applications.
Further set forth the present invention with reference to following non-limiting example.
Embodiment 1-6
The limiting viscosity that in 25 ℃ chloroform, records be the poly (arylene ether) (SA120) of 0.12g/dl with the bead form available from GE Plastics, pulverize to reduce granularity.Then with the SA120 of 20wt% pulverizing and the poly (arylene ether) melt blending (as shown in table 2) of high inherent viscosity.The comparative example uses the crystal polystyrene (XPS) of 20wt% as flow promoter/plasticizer.Use multiple spot capillary rheology method of masurement on the Kayeness rheometer, under 340 ℃, to use the melt viscosities of 4 minutes retention time measurement embodiment.The shearing rate value is a unit with the inverse of second, and the melt viscosity value is being pascal-second unit.Data as depicted in figs. 1 and 2.Fig. 1 illustrates remarkable similar viscosity between the comparable compositions that contains the composition that hangs down limiting viscosity poly (arylene ether) (SA120) and contain polystyrene plasticizer.Use ASTM D648 measurement heat deflection temperature (HDT) under 264psi (℃), data are as shown in Figure 2.
Table 1
| | 1 | 2 | 3 | 4 * | 5 * | 6 * |
| SA120 | X | X | X | |||
| Novacore2272 | X | X | X | |||
| Poly (arylene ether) (IV=0.30) | X | X | ||||
| Poly (arylene ether) (IV=0.40) | X | X | ||||
| Poly (arylene ether) (IV=0.46) | X | X |
*The comparative example
Table 2
| | 1 | 2 | 3 | 4 * | 5 * | 6 * |
| 48.6 | 367 | 999 | 1344 | 381 | 886 | 1114 |
| 97.3 | 347 | 816 | 1001 | 333 | 741 | 918 |
| 255.4 | 278 | 585 | 675 | 285 | 526 | 613 |
| 498.6 | 245 | 439 | 489 | 237 | 374 | 449 |
| 754 | 209 | 362 | 402 | 207 | 321 | 362 |
| 997.2 | 192 | 314 | 344 | 186 | 268 | 313 |
| 1495.8 | 164 | 255 | 276 | 155 | 215 | 254 |
| 1994.5 | 144 | 217 | 237 | 135 | 182 | 215 |
| 2505.2 | 129 | 190 | 207 | 121 | 172 | 188 |
*The comparative example
By Fig. 1 and table 2 as can be seen, compare, contain the poly (arylene ether) (SA120) of low limiting viscosity and do not use the compositions table of softening agent to reveal suitable melt viscosity with the comparable compositions that contains polystyrene.Fig. 2 shows that the compositions table that contains the poly (arylene ether) of low limiting viscosity reveals than the obvious high heat deflection temperature (HDT) of the comparable compositions of using flow promoter/plasticizer.
Embodiment 7-16
Prepare embodiment 7-16 in the mode identical with embodiment 1-6.Embodiment 7-12 uses high heat-resisting (high heat) poly (arylene ether), and recording its limiting viscosity in 25 ℃ chloroform is 0.33g/dl.The variation of the SA120 in the composition and the amount of crystal polystyrene is as shown in table 3.As mentioned above, measure the heat deflection temperature (HDT) of composition.Use multiple spot capillary rheology method of masurement on the Kayeness rheometer, under 340 ℃, to use the melt viscosities of 4 minutes retention time measurement embodiment.The shearing rate value is a unit with the inverse of second, and the melt viscosity value is being pascal-second unit.Data such as table 3 and 4 and shown in Figure 3.The amount of component is to represent based on the weight percent of composition gross weight.
Table 3
| Embodiment | 0.33IV PPO | SA120 | HH PPO | XPS | HDT(℃) |
| 7 | - | 5 | 95 | - | 185 |
| 8 | - | 10 | 90 | - | 184 |
| 9 | - | 15 | 85 | - | 181 |
| 10 | - | 20 | 80 | - | 177 |
| 11 * | - | - | 95 | 5 | 177 |
| 12 * | - | - | 85 | 15 | 166 |
| 13 | 90 | 10 | - | - | 180 |
| 14 | 90 | 10 | - | - | 179 |
| 15 | 95 | 5 | - | - | 182 |
| 16 * | 95 | - | - | 5 | 177 |
*The comparative example
Table 4
| Shearing rate | 7 | 8 | 9 | 10 | 11 * | 12 * | 13 | 14 | 15 | 16 * |
| 97.3 | 605.8 | 521.9 | 464.5 | 348.6 | 623.5 | 414.3 | 247.9 | 203.6 | 263.8 | 242.6 |
| 206.7 | 467.3 | 421.2 | 373.9 | 287.1 | 492.4 | 340.1 | 209.1 | 192.5 | 238.3 | 223.3 |
| 304 | 425.2 | 380.5 | 335.2 | 253.8 | 446.2 | 303 | 189.2 | 174.5 | 213.6 | 206.2 |
| 498.6 | 348 | 314.3 | 283.8 | 222.8 | 368.5 | 259.3 | 168.6 | 157.9 | 191.7 | 184.5 |
| 705.4 | 300.4 | 278.8 | 246.1 | 195.7 | 315.3 | 223.9 | 150.9 | 145.1 | 173.9 | 168 |
| 997.2 | 256.8 | 232.7 | 214.7 | 171.4 | 270.4 | 193.7 | 139.1 | 133 | 158.1 | 154.4 |
| 1495.8 | 214.7 | 199.5 | 185 | 145.7 | 227.2 | 163.7 | 122.8 | 120.1 | 141.3 | 132.2 |
| 1994.5 | 191.3 | 179.6 | 160.4 | 129.1 | 200.3 | 144.32 | 109.3 | 108 | 124 | 119.9 |
| 2505.2 | 171.1 | 164.2 | 143.8 | 116 | 183.4 | 127.9 | 99 | 98.2 | 113.2 | 107.7 |
| 3003.8 | 159.4 | 152 | 133.1 | 106.7 | 168.8 | 118.7 | 92.9 | 92.2 | 105.2 | 101.3 |
*The comparative example
From table 3 and 4 and Fig. 3 as can be seen, replace crystal polystyrene to cause heat deflection temperature (HDT) significantly to raise with the poly (arylene ether) of low limiting viscosity, show the melt viscosity similar simultaneously to the composition that contains crystal polystyrene.
Embodiment 17-23
Embodiment 17-23 uses above-mentioned materials and 0.5 weight account polyethylene, 11 weight part glass fibre and 7 weight part carbon fibers, and wherein wt part is based on 100 parts of poly (arylene ether)s.Used glass fibre can obtain from Owens Corning by trade(brand)name 122Y-14P.Used carbon fiber can obtain from Akzo by trade(brand)name Fortafil202.Polyethylene can obtain from Novapol by trade(brand)name G12024A as releasing agent.
The composition of embodiment 17-23 is as shown in table 4.Use standard injection amount (shot size), transferring position (transfer position) and injection rate, measure the mold transfer pressure (mold transferpressure) of embodiment.According to ASTM D648, under 264psi and 66psi, measure the heat deflection temperature (HDT) of embodiment, measure tensile strength according to ASTM D638, measure modulus in flexure according to ASTM D790, measure notched izod shock strength (notched Izod) according to ASTM D256, measure the non-incision izod impact strength according to ASTM D4812, use multiple spot capillary rheology method of masurement to measure melt viscosity.The unit of heat deflection temperature (HDT) is ℃.The unit of tensile strength, mold transfer pressure and modulus in flexure is MPa (mpa).The unit of otch and non-incision izod impact strength value is kilojoule/square metre (ki/m
3).The data of embodiment 17-23 are shown in table 5 and Figure 4 and 5.
Table 5
| Embodiment | HH PPO | 0.33dl/g poly (arylene ether) | SA120 | XPS | Mold transfer pressure | HDT (264 psi， ℃) | HDT (66 psi， ℃) | Tensile strength | Modulus in flexure | Notched izod impact strength | Unnotched Izod impact strength |
| 17 * | - | 80 | - | 20 | 4.6 | 172 | 178 | 91 | 8176 | 4.0 | 22.1 |
| 18 | - | 80 | 20 | - | 4.7 | 193 | 199 | 90 | 7762 | 4.1 | 29.0 |
| 19 | - | 90 | 10 | - | 6.1 | 198 | 205 | 87 | 7597 | 4.5 | 24.8 |
| 20 | 90 | - | 10 | - | 12.1 | 202 | 204 | 96 | 7849 | 5.1 | 27.9 |
| 21 | 80 | - | 20 | - | 10.2 | 199 | 208 | 88 | 7693 | 3.8 | 27.9 |
| 22 | - | 70 | 30 | - | - | 179 | - | - | 7723 | 3.9 | - |
| 23 | - | 60 | 40 | - | - | - | - | 84 | 7865 | 3.9 | - |
*The comparative example
From table 4 and Figure 4 and 5 as can be seen, in filled compositions, use the poly (arylene ether) of low limiting viscosity to replace polystyrene to obtain particular performances combination, promptly similar melt viscosity and the heat deflection temperature (HDT) that is significantly higher than the composition that contains polystyrene to the composition that contains polystyrene.
Embodiment 24-38
The limiting viscosity that in 25 ℃ chloroform, records be the poly (arylene ether) (SA120) of 0.12g/dl with the bead form available from GE Plastics, pulverize to reduce granularity.Then with the SA120 and poly (arylene ether) (PPO) melt blending with inherent bisphosphate dihydroxyphenyl propane ester (BPADP) of the amount shown in the table 6 with pulverizing.All amounts are to represent based on the weight percent of composition gross weight.Use multiple spot capillary rheology method of masurement on the Kayeness rheometer, under 300 ℃, to use the melt viscosities of 4 minutes retention time measurement embodiment.The shearing rate value is a unit with the inverse of second, and the melt viscosity value is being pascal-second unit.According to ASTMD648, under 264psi, measure the heat deflection temperature (HDT) of embodiment, measure tensile strength according to ASTM D638, measure modulus in flexure according to ASTM D790.Data are as shown in table 6.The unit of heat deflection temperature (HDT) value is ℃.The unit of tensile yield strength values is kilogram force/square centimeter (kgf/cm
2).The unit of pinblock (crosshead) elongation at break is %.The unit of modulus in flexure and bend yield strength noted value is kgf/cm
2
Table 6
| 24 * | 25 * | 26 * | 27 * | 28 * | 29 * | 30 * | 31 * | 32 * | 33 * | 34 * | 35 * | 36 * | 37 | 38 | |
| PPO | 69.5 | 78.5 | 66 | 82 | 57 | 66 | 61.5 | 86.5 | 80.25 | 67.75 | 91 | 82 | 57 | 80 | 70 |
| SA120 | 17.5 | 17.5 | 30 | 5 | 30 | 30 | 30 | 5 | 11.25 | 23.75 | 5 | 5 | 30 | 20 | 30 |
| BPADP | 13 | 4 | 4 | 13 | 13 | 4 | 8.5 | 8.5 | 8.5 | 8.5 | 4 | 13 | 13 | ||
| Modulus in flexure | 29880 | 28550 | 28634 | 28519 | 28288 | 28129 | 29009 | 28806 | 28258 | 28994 | 27321 | 28388 | 28600 | 26838 | 27573 |
| Bend yield strength noted | 668 | 928 | 817 | 13178 | 337 | 813 | 555 | 1301 | 1292 | 600 | 1263 | 1320 | 375 | 1155 | 832 |
| Heat deflection temperature (HDT) | 128 | 162 | 156 | 134 | 123 | 155 | 140 | 151 | 146 | 142 | 150 | 132 | 123 | 172 | 167 |
| Tensile yield strength | 463 | 625 | 534 | 812 | 268 | 440 | 365 | 788 | 796 | 651 | 723 | 794 | 279 | 771 | 258 |
| The pinblock elongation at break | 3.75 | 5.40 | 4.81 | 7.83 | 2.03 | 3.84 | 2.99 | 7.82 | 7.98 | 5.58 | 7.02 | 7.68 | 2.13 | 8.32 | 2.93 |
| Shearing rate=1496 | 113 | 258.8 | 164 | 176.7 | 65.8 | 56.9 | 102.6 | 260.8 | 210.5 | 127.4 | 298.6 | 160.2 | 63.5 | 330 | 234.9 |
*The comparative example
By the melt viscosity of embodiment 24-36 and heat deflection temperature (HDT) as can be seen, the introducing of BPADP has significantly reduced melt viscosity and heat deflection temperature (HDT).On the contrary, the similar composition embodiment 37 and 38 that does not contain BPADP shows good melt viscosity and higher heat deflection temperature (HDT) surprisingly.
Although described the present invention, it will be understood by those of skill in the art that under the situation that does not deviate from scope of the present invention and can make variation and replace its key element it with equivalent with reference to a plurality of embodiments.And, under the situation that does not deviate from essential scope of the present invention, can make many improvement so that particular case or material are fit to instruction of the present invention to the present invention.Therefore, the invention is not restricted to, but attempt to comprise all the interior embodiments of scope that drop on claims as the disclosed particular of optimum implementation.
All incorporate patent and other documents of all references into this paper by reference at this.
Claims (9)
1. poly (arylene ether) composition, it is included in the limiting viscosity that records in 25 ℃ the chloroform and is less than or equal to the second viscosity polyarylene ether resin of about 0.17dl/g more than or equal to the first polyarylene ether resin of about 0.3dl/g and the limiting viscosity that records in 25 ℃ chloroform, and wherein said composition is substantially free of softening agent.
2. the composition of claim 1, wherein the ratio of the first polyarylene ether resin and the second polyarylene ether resin was greater than 1: 1.
3. claim 1 or 2 composition, wherein said composition was at 1500 seconds
-1Be less than or equal to about 190 with the melt viscosity under 320 ℃ the temperature.
4. each composition among the claim 1-3, wherein said composition also comprises toughener.
5. the composition of claim 4, wherein said composition was at 1500 seconds
-1Be less than or equal to about 270 with the melt viscosity under 320 ℃ the temperature.
6. each composition among the claim 1-5 is wherein measured according to ASTM D648, and the heat deflection temperature (HDT) of described composition is more than or equal to about 130 ℃.
7. each composition among the claim 1-6 is wherein measured under 25 ℃ and 1 kilo hertz, 10 kilo hertzs, 100 kilo hertzs or 1 megahertz according to ASTM D150, and the loss factor of described composition is less than or equal to about 0.02.
8. each composition among the claim 1-7, it further comprises impact modifying agent.
9. the goods that comprise each composition among the claim 1-8.
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