CA2174908A1 - Thermoplastic elastomers having improved high temperature performance - Google Patents
Thermoplastic elastomers having improved high temperature performanceInfo
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- CA2174908A1 CA2174908A1 CA002174908A CA2174908A CA2174908A1 CA 2174908 A1 CA2174908 A1 CA 2174908A1 CA 002174908 A CA002174908 A CA 002174908A CA 2174908 A CA2174908 A CA 2174908A CA 2174908 A1 CA2174908 A1 CA 2174908A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/283—Halogenated homo- or copolymers of iso-olefins
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- 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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
Abstract
A thermoplastic elastomer comprising a triblend of engineering resin, dynamically vulcanized alloy of thermoplastic olefin polymer and elastomeric copolymer, and a compatibilizer for the engineering resin and alloy. The compositions retain structural integrity at high temperature, and have good tensile properties, elongation and fluid resistance.
Description
~ ~ ~4~8 S l~KMOPLASTIC ELASTOMERS HAVING IMPROVED
HIGH TEMPERATURE PERFORMANCE
BACKGROUND OF 1~ INVENTION
Field of the Invention This invention relates to thermoplastic elastomers based on çngin~ring th~ op~ ,5, and which have improved high tel"pelalule pe,follllance while ret-qining e~cP11Pnt elQn~PtiQn çhqr~cteri~ti~s- A thermoplastic elastomer is generally defined as a polymer or blend of polymers that can be plucessed and recycled in the same way as a co.~e~l~;onq1 the.l,loplastic material, yet has prope.~ies and ~,rolnlance similar to that of -15 vul~qni7~d rubber at service telllpel~tures. Blend4 or alloys of plastic and elastomeric rubber have become incl~singly il"~l~1t in the productiol- of high pelful,l,ance thermoplastic elastu"l~ , particularly for the rep1~cennent of thermoset rubber in various applications.
Description of the Related Art Polymer blends which have a combination of both thermoplastic and elastic pro~llies are gene~11y obtdined by combining a thermoplastic with an elastomeric collll)osi~ion in a way such that the elastlJ~I.er is intim~t~ly and uniforrnly dispersed as a discrete particulate phase within a cQntinUous phase of the thermoplastic. Early work with vu1c~ni7edcc~--po~;~;Qm is found in U.S. Pat. No. 3,037,954 which ~ oses static vu1ç~ni7~tion as well 2 1 ~90~
as the technique of dynamic vul-~ni7~tion wherein a vulc~ni7~hle elastomer is dispersed into a ~nous ll~...op~ ic polymer and the elastomer is cured while continuously mixing and ~hP~. ;ng the IJolyl,lc~ blend. The reslllting colll~silion is a micro-gel dispersion of cured cl~tulllc~, such as butyl rubber, chlorinated butyl rubber, polybut~iPne or polyisobutene in S an ~.n.~ ,d mat~L~c of thermoplastic polymer such as polypropylene.
U. S. Pat. No. 5,003,003 is dil~ted to blends of polyamide resin with cla~lu"l~.ic ethylene-propylene polymers which have been function~li7P~, then cros~link~ after di~c~;on in the polyamide resin. The resul~ing blend has improved tensile strength, elt~ ti~n and oil resist~nce.
PCT Published Appli~tion WO 92/02582 describes blends of thermoplastic ~ngjnP~ resin with an elastomeric halogen-con~ining copolymer of a C4 7 isomonoolefin and a para-alkylstyrene. The elastomer component of the blend may be cured or uncured.
U.S. Pat. No. S,238,990 discloses a thermoplastic blend of polyamide with a grafted - polymer which is a reaction product of (a) a copolymer or halogen-cont~ining copolymer of a 5 C4 7 i~,--ol oolefin and an alkylstyrene, and (b) an unsaturated carboxylic acid or a derivative thereof. The blend is said to have improved impact strength while m~int~ining the high flP-II~I modlllus of the polyamide.
In U.S. Pat. No. 5,244,961, a process is described for the preparatiûn of a blend of tl~e....op!~ctic polyamide and halogen-cont~ining copolymer of C~, isomonoolefin and para-20 alkylsly~ne, in the presence of a metal compound. The blend has improved impactreCict~n~e at low le~llpe~atu~s.
21 74~0~
--SUMMARY OF THE INVENTION
The present invention is based on the discovery that a thermoplastic elastomer co!..po~;l;on having eycpll~ont physical propellies at elevated te-~lpeldtures is provided by blending (a) a th~l"oplastic çnginçering resin with (b) a dyn~mi~lly v--lç~ni7~d alloy (DVA) S c~"l~,rising a thermoplastic olefinic polymer and an olefinic elastomer having reactive cure sites, in the p~n~ of (c) a co,.~p;~lihilizer for the enein~ g resin and the DVA.
The c~,~.~s;l;~ns retain their structural integrity at high tellll)eldtule, and have good tensile pr~ ies, e1c~n&~tion and fluid rçcist~nce They have utility in applications where pe.roll..dnce at elevated te."pe.dl-lre is illlpol~lt, such as automobile under-hood parts.
DESCRIPIION OF THE PREFERRED EMBODIMENTS
r;n~;n~ in~ Resin The thermoplastic engine~ring resins used in the compositions of the invention are al"ol~hous or semicrystalline m~tPri~lc usually polar in nature, with a glass tr~ncition .nl~ (T,) or melting point above about 15~C, preferably above about 200C. They may be used singly or in colllbination, and are sel~tçd from polyamides, polycarbonates, polyesters, polysulfones, polyl~tones, polyacetals, acrylonitrile-but~ ne-styrene (ABS) resins, polyphenylene oxide (PPO), polyphenylene sulfide (PPS), styrene-acrylonitrile (SAN) resins, polyimides, styrene maleic anhydride (SMA) and aromatic polyketones. Preferred ~hc.",oplastic engineering resins are polyamides. The more preferred polyamides are nylon 6, nylon 6,6, nylon 11, nylon 12 and mixtures or copolymers thereof.
Suitable thermoplastic polyamides (~ylo~ns) include crystalline or resinous, high mn~ r weight solid polymers (including copolymers and terpolymers) having recurring 21 74~03 ~- amide units within the pol~ chain. Polyamides may be prepared by polym~ri7~ion of one or more epsilon lactams such as caprolactam, pyrrolidone, lauryllactam and ~...;no..ml~ lactam, or amino acid, or by condçn~ion of dibasic acids and di~mines Both fiber-forming and mol~ing grade nylons are suitable. Examples of such polyamides are 5 polyca~ ^t~m (nylon 6), polylauryllactam (nylon 12), polyhPY.~n ethylçn~ir~mide (nylon 6,6), polyh~ .ylPn~ de (nylon 6,9), polyheY~methyl~neseb~mi~e (nylon 6,10), polyh. ;t..~ cisoph~ mide (nylon 6,IP) and the conden~ion product of 11-amino-nnic acid (nylon 11). Additional examples of s~icf~tory polyamides (çspeci~lly those having a s~te ing point below 275C) are described in Kirk-Othmer, Encyclopedia of ChPn~ir~1 Te~hnolegy, 3d edition, vol. 18, pages 406-409, and Encyclopedia of Polymer Science and Fng;,~ ;ng, 2d edition, vol. 11, pages 445-450. Commercially available th~.lllopla~lic polyamides may be advantageously used in the practice of this invention, with linear crystalline polyamides having a softening point or melting point between 160 and - 230C being plefell~d.
The amount of engin~ring resin found to provide useful compositions is generally from about 10 to about 50 parts by weight, and more preferably from about 10 to about 40 parts by weight, based on the weight of the composition comprising enginePring resin, DVA
and col..l ~;hilizer.
Dynamically Vulcanized Alloy The DVA component of the composition comprises a thermoplastic olefinic polymer and an ~ o.l-~ (rubber) which have been melt blended in the presence of a curative to dynqmi~lly v~ ni7e the elastomer. The resnlting DVA is a polyolefin matrix having 21 749Q~
micron or s~lbmir~on size e1~ctompr particles dispersed therein. The elastomer is desirably at least partially cured (crocclinkPd) during the dynarnic vulc~ni7~tion, and preferably is fully or completely cured.
As used in the speçifir~tion and claims, the term "dynamic vlllc~ni7~tion" means a S process wllclcin the elasloll-e is vl~ ni7ed or cured in the presence of the polyolefin under c~ nc of high shear and at a te.llpcla~lre above the melting point of the polyolefin. The e~ is thus cimull;.n~usly crocclink~d and is usually dispersed as fine particles within the polyolefin, ~lth~u~h co-continuous phase morphologies or a Illi~Lwc of discrete and co-conl;n~ou~ phase morphologies are also possible. Dynamic vulc~ni7~tion is effected by 10 mLlcing the co",poncnls at elevated te"~pel~ture in conventional mixing e4uip"lcnt such as roll mills, l~nb.l~ mixers, Brabender mixers, continuous mixers, mixing extruders and the like.
The unique Çh~ tçrictic of dyn~mic~lly cured colllpo~itions is that, notwithct~n~ing the fact that the el ~`t~ f ~ COn~pOI~ nt is partially or fully cured, the compositions can be process~d - and ~,ùcessed by conventional plastic processing techniques such as extrusion, injection 5 mol ling and compression molding. Scrap or fl~ching can be salvaged and reprocessed.
The terms "fully vu~ ni7ed" and "completely vulc~ni7ed" as used in the specific~tion and claims means that the ela~lu,ll~ l colllponent to be vulc~ni7P~ has been cured to a state in which the ela~tù,lle,ic ~r~lties of the crocclinked rubber are similar to those of the ela~to",~r in its conventional vlllc~ni7ed state, apart from the thermoplastic elastomer 20 co",posilion. Simply stated, fully vul~ni7P~ means that subs~nti~lly all of the rubber ~"~po~.ent which is capable of being vul~ni7P~, has been v-~ ni7ed. The degree of cure can be d~ ;bed in terms of gel content or, conversely, extractable co~ onents.
2~ 7~8 ~- ~lt~nqtively the degree of cure may be eApl~ssed in terms of crosslink density. All of these ~liplions are well known in the art, for example in U.S. Pat. Nos. 5,100,947 and5,157,081, both of which are fully inco,~l~ted herein by this reference.
The amount of DVA found useful in the present compositions is generally from about 90 to about S0 parts by weight, and more p~efelably from about 90 to about 60 parts by weight, based on the weight of the colll~si~ion comprising engil-~ ;.-g resin, DVA and co...p~lil.ilizer.
Thermoplastic Olefin Polymer Polyolefins suitable for use in the compositions of the invention include non-polar lh~,llloplaslic, crystalline or semi-crystalline polyolefin homopolymers and copolymers.
They are ~)lC~a~d from monoolefin monomers having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene and the like, with ethylene, propylene and ul~ thereof being p~fe.,cd. The polyethylene can be low density, ultra-low density or - high density m~teli~l. The term polypropylene includes homopolymers of propylene as well as reactor copolymers of polypropylene which can contain about 1 to about 20 weight percent of ethylene or an -olefin comonomer of 4 to 16 carbon atoms, and mixtures thereof. The polypropylene can be isotactic or syndiotactic, usually having a narrow range of Tg.
Col..l"e~;ally available polyolefins may be used in the practice of the invention.
The amount of polyolefin found to provide useful DVA compositions is generally 20 from about 10 to about 90 weight percent, based on the weight of the polyolefin and elaslo--,er. Preferably, the polyolefin content will range from about 10 to about S0 percent by weight.
Curable Elastomer Fl~t~!l..e.~ suitable for use in the co",positions of the invention are co~palible with the th~".~op1~c~ir olefin polymer and have reactive cure sites. Such cure sites can either be an integral part of the elas~ ,ler backbone or can be incol~latcd by the q~dr~i~ion of S functionql groups. A prcfcllcd group of elastomers is that prepared from copolymers of C4 7 c~in~ and para-alkylstyrene. These copolymers are more fully desrrihed in U.S. Pat.
No. 5,162,445, the ~ os~llc of which is inco~ ed herein by this refercnce. A
particularly pl~f.,.l~ ela~toln~,~ species is rel,r~sellted by the halogcnatcd copolymer of isobutylene and para-methylstyrene. Elastomers of ethylene-propylene (EPR) and 10 poly(ethylene-co-propylene-co-diene), also known as EPDM rubber, have also been shown to ol", well in the compositions, either alone or in combination with copolymers of i~o]~ and para-alkylstyrene.
The amount of olefinic elastomer useful in the DVA compositions is generally from about 90 to about 10 weight percent, based on the weight of the polyolefin and elastomer.
5 ~lefe.ably, the elastomer content will range from about 90 to about 50 percent by weight.
Curing System In the cG",~ilions of the invention, the elastomer co,--ponent of the DVA will generally be at least partially vul~ni7ed, or crosclink~d~ Those ordinalily skilled in the art will applo~iale the appropliate qu~ntities~ types of cure systems and vulcanization conditions 20 ~uir~d to carry out the vlllc~ni7~1ion of the rubber. The elastomer can be vlllc~ni7~d using varying ~moun~ of curative, varying ~---p~atures and varying time of cure in order to obtain the optimum cro~linkinv desired. Any known cure system can be used, so long as it is ~ P under the v--l~ni7~tion con~liti()nc for the elastomer or combination of elastomers being used and is co,l,pa~ible with the thermoplastic polyolefin co-"ponent of the DVA.
These Cu~ S include sulfur, sulfur donors, metal oxides, resin systems, m~l.oimi~ec pero~cide-based ~st~ .,ls, high energy radiation and the like, both with and without S ~ Ol~ and co-agents. Phenolic resin curatives are prefelled for the preparation of the DVA co~c;l;~c of the invention, and such cure systems are well known in the art and l;t~ m." of vlllr~-li7~ion of elastomers. Their use in DVA compositions is more fully d~ il~d in U.S. Pat. No. 4,311,628, the ~licclosllre of which is fully incol~,ated herein by this l~f~nce.
10 Compatibilizin~ A~ent The engin~ring resin and dynamically vulcanized alloy of the composition are co"lbilled in the presence of a compatibilizer for these components. Absent the c~-..p--~;bilizer, blends of ellg;~ .ing resin and DVA have poor "~ech~nical and elongation - pl~,Lies, due to the lack of interfacial adhesiolrbetween the components. Under stress, the weak interfaces may fail and the co",ponents del~min~te. The addition of an interfacially active colllpatibilizer overcomes this deficiency. The compatibilizer is designed so that each ~ ,.rnt or fun~tiQn~l group is compatible with one of the major component phases, and in~"")alible with the other. The compatibilizer improves interfacial adhesion by connecting the co",ponent phases, forrning a stable blend.
The co",patibilizer can be formed by the direct interaction of segments containing the functional groups present in the major components, i.e. the engineering resin and the DVA, or by interaction with another bi- or multi-functional compound. Compatibilizers are known ~in the art, e.g. in U.S. Pat. No. 4,555,546 and Journal of Macromolecular Science Chemistry, A26 (8), 1211 (1989). ~lefelled compatibilizers include the reaction product of nylon and fun-~ nqli7~d polypropylene, p~a~d by melt mixing nylon 6 with polypropylene grafted with 0.1-2.0 wt percent maleic anhydride, in a ratio of nylon:m~ t~ polypropylene Ianging from 9S:5 to SO:S0. See J. Appl. Polym. Sci., 18, 963 (1974) and Eur. Polym. J., 26, 131 (1990).
The col~.p~t;bilizer may be present in the compositions of the invention in the range of about 2 to about 35 parts by weight based on- the e ne;nf~ ;ng resin, DVA and co,l,patibilizer.
~,f~,.~ly it is present in the range of about 2 to about 20 parts by weight.
Additives In ~ itiot~ to the engine~ring resin, DVA and co-"palibilizing agent, the compositions of the invention may also include reinforcing and non-reinforcing fillers, pl~ctici7ers for the e/~ f~. ;n~ resin and polyolefin, antioxidants, stabilizers, rubber p~ces~ing oil, extender oils, lubricants, antiblocking agents, ~ntict~tic agents, waxes, foaming agents, pigments, flame r~ ~ants and other processing aids known in the rubber compounding art. The additives can be added during the preparation of the DVA or the p,e~aldtion of the finiche~
co...~ ;Qn or both, provided that the total amount of the additives does not exceed about 50 weight percent, pr~felàbly about 25 weight percent, based on the total thermoplastic eldstul" r colll~ n~ including additives.
Fillers and e~ nd~ ~ which can be utilized include conventional inorganics such as r~lrium c~l~onale, clays, silica, talc, titanium dioxide, carbon black and the like. The rubber pf~s~;ng oils are generally paraffinic, napthenic or aromatic oils derived from petroleum fr:-ctions. The type will be that ordinarily used in conjunction with the specific elaslul.lc~ or claslo",el~ present in the DVA, and the quantity based on the total rubber content may range from zero to a few hundred parts per hundred parts rubber (phr).
General ~lu~
S The general p~lure for plcpaldLion of the compositions of the invention has two stages. In the first stage, a rubber having reactive curesite functionality is dyn~mic~lly vul(~ni7Pd in the presence of an olefinic thermoplastic which is inert to the rubber curesites, using appl~liate curing systems. In the second stage, this dyn~mi~lly vulc~ni7~dlul~r/plaslic alloy (DVA) is blended with an engin~ring resin in the pre~nce of a co.~ t;~ilizing agent. The two stages can be carried out independently in separate steps or sequentially in the same plocessing equipment.
More specifi~lly, the DVA is prepared by blending the thermoplastic olefinic polymer, the elastomeric copolymer and zinc oxide in a Brabender mixer of 60 cc capacity at a t~ lule of about 180C. The speed of the-mixer is in the range of about 60 to about 200 rpm. After the co"~ponehl~ are well dispersed the curative system is added to initiate dynamic v~ ni7~tion Mixing is continued until a maximum of mixing torque in~ic~tes that v~ ni7~tion has occurred, usually between one and five minutes, then the speed of the mixer is increased to maximum and mastication is continued for an additional two to three ~,inul~. The v-llc~ni7~ co"~position is removed from the mixer, cold pressed, and then is l~lu~lled to the mixer for an additional one to two minutes of mixing at 180C and 100 rpm.
The co",~libilizer is prepared separately by melt mixing the components, for example nylon and m~ ted polypropylene, in a Brabender plasticorder. The components 21 74~0'~
~are added to the mixer bowl at about 20 rpm, and when the bowl is filled the mixing speed is incl~ to about 200 rpm. The le~pel~ture is increased to about 220-225C, and the mixing speed is then reduced to about 100 rpm. The torque of the mixer is monitored to det~ ."-inf completion of the end group reaction. When the reaction is complete, the S co~ alibiliær coml o~;~ion is removed from the mixer and cold pressed.
In the final step, the en~;nf~;ng resin, DVA and compatibilizer are blended at high shear in a Br'-endçr mixer. The te,.,~,~ture is increased to about 225C and the speed to about 200 rpm. After the m~t~ri~l~ melt, mixing is continued until the stock telllpGl~lulG
reaches about 235C. The speed is then reduced to about 100 rpm and m~ctin~ion continued 10 for two to three i~ f s The stock is removed from the mixer, cold pressed, then returned to the mixer for an additional two minutes of mixing at 225C and 100 rpm. The cG~Ipo~ilion is removed from the mixer and co."~ ssion molded at about 240C into plaques of about 2 mm thickness for physical testing.
The following examples serve to illustrate-but not limit the present invention.
Example 1 Following the general procedure outlined above, dyn~mi~lly vulcanized alloys of polypropylene and an elastomer comprising a brominated copolymer of isobutylene and para-methylstyrene were prepared. The polypropylene, elastomer and curative were melt mixed in a heated Brlben-le- mixer of 60 cc capacity at 100 rpm. The mix was masticated at a t~lllpel~:ltUl~ in the range of 180 to 190C to dynamically v-llc~ni7e the rubber. Mixing was cont;n~ for about two minutes, or until the cure was complete (as indicated by a rapid inel~ in torque of the mixer). Mixing was then continued for about two minutes, or until 2~ 7490,~
the torque became relatively con~t~nt The conlposition was removed from the mixer, sheets were co,llp~s~ion molded at 190C and the physical propellies were measured.
R~l~nt~ e DVA coll~:,itions and thelr physical prope,lies are set forth in Table I.
TABLE I
#1 #2 Polypropylene'(parts/lOOpartsrubber)(phr)33.3 66.6 Elaslolll~ 100 100 Zinc oxide 2 2 Curative3 7.5 7.5 Hardness (Shore) 78A 44D
Tensile strength (psi) 1920 3310 F1ong~tion (%) 350 530 ~ s 100% (psi) 765 1740 Tension set (%) - 14 40 Oil swell (%) - 22 hr/125C, No. 3 oil 168 110 Colllpres~ion set (%) - 22 hr/125C 22 60 'PP D0008 (Ari tech Chemic-l) 'I ' - ' i yl...c/~, yt~t~ - copolymer (Exxpro~ elastomer, E~xon Chemical) '~ - yl~l F ~ tylphonol (~
The physical p~.lies of the compositions were determined according to the following m-~ho~c-Tensile strength, elongation, modulus 100% and tension set - ASTM D412 Oil swell - ASTM D471 Colll~ ssion set - ASTM D395B
The DVA co~l~sitions of this Example were incorporated into the blends of the invention according to the following examples.
~ 747~B
.
Example 2 CGI~PGS;I;OnC of the invention were prepaled by the procedure described above.
C~l--pos;l;onc A and B are co,l"~ tive examples wherein blends of engin~ring S resin/el~ct~....~ r and eng;n~ ;ng resin/DVA were evaluated without the compatibilizer cO~ n- --l CG~ o~;l;onc C-E lC~ S~Ent the triblend col"positions of the invention, in~lnr1in~ the cG",~Iibilizer. Physical pro~llies were co,l-par~d and are set forth in Table II.
Co~Pnl-~t;onc of the components are in the prol)Gllions e~plessed in the Table.
2 1 74~
TABLE II
A B C D E
Nylon 61 104.7 50 25 25 25 Compqtihilizer 13 - - 25 25 Co!.. p--~;hilizer 24 - - - - 25 Fl-c~.. ~ C 100 Zinc Oxide 2 Curative6 7.5 pl~ctil i7~r7 8 IIar~lness (Shore D) 50 43 44 39 44 Tensile sll~nglh (psi) 1790 1550 2580 2250 2680 Fk!n~tiQn (%) 10 120 230 360 230 Modulus 100æ (psi) - 1550 1980 1440 2060 Tension set (96) - Fail 46 38 47 Oil swell (æ) 24 - 83 80 69 Co",pr~ssion set (5~) 80 - 61 61 61 ' CapronX 8202 (Allied Signal) 2 DVA #1 from Example 1 3 60/40 ~,ol.~l.._r of Nylon 6/Polybond~ maleic anhydride modified pol~
(Uniroyal Chemical Co.) ' 80/20 interpolymer of Nylon 6/Polybond maleic anhydride modified pol~ o~ ,nc (Uniroyal Chemical Co.) 51~ ' isob-llyl~ c/p-u.~ C copolymer (Exxpro~, Exxon Chemical) 6 dimethylol-p-octyl phenol (nonhalogenated) 7 K~tj~nfl~ 8 (Akzo Chemie) As can be seen from the data in Table II, the compositions of the invention (C, D and E) have improved tensile strength and elongation pro~llies at ambient te~l,peldture. In a further test tensile ~lupellies~ and particularly elongation plu~llies, were found to be retained at ~ n~res up to 165C as shown by the data for Cûmposition E set forth in Table IIA.
TABLE IIA
Te~ lu~ 100 C 150 C 160 C
Tensile ~ ngll, (psi) 1615 880 530 Flong~t~ (%) 280 275 215 S Modulus 100% (psi) 920 S00 345 The ~ddi~ioll of antioxidants can further improve the heat aging pn)pelties of the c4~ ;0nc of the invention. A co,..po~ilion of nylon 6 (25 parts by weight), compatibilizer 2 (25 parts) and DVA #1 (100 parts) was prepared as described above, and the following additives were includ~: m~gn~cium oxide (1.25 parts); 2-melcdplotolylimidazole (2 parts); bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (1 part); and tris (3,5-di-tert butyl-4-hydroxybenzyl) isoc~dm,ldte (O.S part). Physical p,~pel~ies were determined immeAi~teiy after p~~ tion and again after hot air aging at 150 C for 168 and 336 hours. The results are shown in Table ILB.
TABLE IIB
Heat aging (hours) 0 168 336 Tensile strength (psi) 2580 2400 2080 Elongation (%) 220 lS0 120 Modulus 100% (psi) 2070 2100 1985 21 7it9Q8 Example 3 The effect of col.lpatibiliær level was studied in compositions of the invention.
C~ ~si~ n F ~p~nts a comparative example cont~ining no compatibilizer, while colll~,lions G-I contain compatibilizer over a range of concentrations. Physical p~opellies S were c~ll,par~ and are set forth in Table III.
TABLE III
F G H
Nylon 61 (grarns) 20 17.2 14.4 11.6 DVA2 (grarns) 40 40 40 40 Compatibilizer 23 (grams) 0 2.8 5.6 8.4 IIar~n~s (Shore D) 43 45 44 43 Tensile s~ngth (psi) 1550 2230 2500 2470 ~ (%) 120 177 220 230 Mod~ 100% (pSi) 1570 1935 1975 1915 - Tension set (%) Fail - 40 43 48 Oil swell (%) 60 61 60 60 Colllpr~ssion set (~) 60 62 60 60 ' Capron 8202 (Allied Signal) 2 DVA #l from Example I
3 80/20 I,ol~ of Nylon 6/PolybondD maleic anhydr.de modified pol~ e (Uniroyal Chemical Co.) The co",~silions of the invention (G, H and I) demonstrate the importance of thecolnp~tibilizer in obtaining the unexpectedly improved tensile strength and elongation pr~pe.lies.
21 749û~
Example 4 Col..po~;l;onc were p,e~a-ed with various compatibilizers using the general method il,ad above. Co~-~p~ibilizers consisting of interpolymers of nylon and maleic anhydride --o~1if;~ pol~p~;lene at dirrelei~t ratios, and interpolymers of nylon and a bromin~
S copolymer of isobutylene and para-methylstyrene, were co---paled. Physical pn)pe,Lies of the hed co~ r c were determined and are set forth in Table IV.
TABLE IV
J K
Nylon 61 (grams) 10 10 10 DVA2 (grams) 40 40 40 Co~ ilJilizer 13 (grams) 10 -- --Colllpalibilizer 24 -- 10 --Comp-q-tibilizer 35 -- -- 10 plqcti~i7P,4 (grams) 8 8 8 - Hardness (Shore D) 39 - 39 40 Tensile strength (psi) 2430 2460 1450 FlongqtiOn (%) 320 310 160 Mod~ ls 100% (psi) 1530 1570 1430 Tension set (%) 38 32 30 Oil swell (%) 57 47 72 Co,llyl~sion set (%) 57 57 53 ~ Capron 8202 (Allied Signal) 2 DVA #1 from E~ample 1 3 60/40 ~ ~~ of Nylon 6/Polybond maleic '~ydride modified polypropylene (Uniroyal Chemical Co.) 4 80l20 r'l~ of Nylon 6/Polybond maleic anhydride modified polypropylene (Uniroyal Chemical Co.) ~ T ~ of Nylon 6~.~ ' copolymer of isobutylene and para-methylstyrene (E~u~pro~, E~on Chemical) 6 R. tj. n. ~ 8 (Alczo Chemie) 21 749QI~
Example 5 CO~ ;Qn~ were pl~alGd wherein ethylene-propylene-diene monomer (EPDM) rubher was the elastomer co"~ponGI~t of the DVA. The DVA was plc~a~ed as ~ ;l~d ahove, with a formulation of 33.3 parts of polypropylene (PP D0008, Aristech S ChPmi~l), 100 parts of EPDM, and a cure system of 2 parts zinc oxide, 1.26 parts ~nnous chl- ri~le and 7 parts dimethylol-p-octyl phenol. DVA #3 was ~le~aled using Vistalon0 7000 EPDM (E~cxon Ch~mir~l) and DVA #4 was pre~)a,e~ using Vistalon0 4608 (Exxon Chlq-mic~l).
The co,~ ;hilized l,ibl^nll compositions of the invention were ~lel~alcd and physical plopcllies are set forth in Table V.
TABLE V
M N O
Nylon 6' (grams) 10 10 10 Co~ ;1.iliær2 (grams) 10 10 10 DVA #1 (grams) 40 -- ---15 DVA #3 - -- 40 --DVA #4 -- -- 40 II~lness (Shore D) 43 49 46 Tensile sll~n~ (psi) 2620 3020 2940 Fl~ng~tiorl (%) 230 225 240 Mo~ s 100% (psi) 2060 2340 2180 Tension set (%) 48 60 40 Oil swell (%) 61 70 72 Co",~lession set (%) 59 52 54 ' Capron 8202 (Allied Signal) 2 80/20 interpolymer of Nylon 6/Polybond maleic anhydride modified polypropylene (Uniroyal Chemical Co.) 21 749~3 While the best mode and ~lefelred embodiment of the invention have been set forth in accord with the Patent Statutes, the scope of the invention is not limited thereto, but rather is defined by the claims which follow.
HIGH TEMPERATURE PERFORMANCE
BACKGROUND OF 1~ INVENTION
Field of the Invention This invention relates to thermoplastic elastomers based on çngin~ring th~ op~ ,5, and which have improved high tel"pelalule pe,follllance while ret-qining e~cP11Pnt elQn~PtiQn çhqr~cteri~ti~s- A thermoplastic elastomer is generally defined as a polymer or blend of polymers that can be plucessed and recycled in the same way as a co.~e~l~;onq1 the.l,loplastic material, yet has prope.~ies and ~,rolnlance similar to that of -15 vul~qni7~d rubber at service telllpel~tures. Blend4 or alloys of plastic and elastomeric rubber have become incl~singly il"~l~1t in the productiol- of high pelful,l,ance thermoplastic elastu"l~ , particularly for the rep1~cennent of thermoset rubber in various applications.
Description of the Related Art Polymer blends which have a combination of both thermoplastic and elastic pro~llies are gene~11y obtdined by combining a thermoplastic with an elastomeric collll)osi~ion in a way such that the elastlJ~I.er is intim~t~ly and uniforrnly dispersed as a discrete particulate phase within a cQntinUous phase of the thermoplastic. Early work with vu1c~ni7edcc~--po~;~;Qm is found in U.S. Pat. No. 3,037,954 which ~ oses static vu1ç~ni7~tion as well 2 1 ~90~
as the technique of dynamic vul-~ni7~tion wherein a vulc~ni7~hle elastomer is dispersed into a ~nous ll~...op~ ic polymer and the elastomer is cured while continuously mixing and ~hP~. ;ng the IJolyl,lc~ blend. The reslllting colll~silion is a micro-gel dispersion of cured cl~tulllc~, such as butyl rubber, chlorinated butyl rubber, polybut~iPne or polyisobutene in S an ~.n.~ ,d mat~L~c of thermoplastic polymer such as polypropylene.
U. S. Pat. No. 5,003,003 is dil~ted to blends of polyamide resin with cla~lu"l~.ic ethylene-propylene polymers which have been function~li7P~, then cros~link~ after di~c~;on in the polyamide resin. The resul~ing blend has improved tensile strength, elt~ ti~n and oil resist~nce.
PCT Published Appli~tion WO 92/02582 describes blends of thermoplastic ~ngjnP~ resin with an elastomeric halogen-con~ining copolymer of a C4 7 isomonoolefin and a para-alkylstyrene. The elastomer component of the blend may be cured or uncured.
U.S. Pat. No. S,238,990 discloses a thermoplastic blend of polyamide with a grafted - polymer which is a reaction product of (a) a copolymer or halogen-cont~ining copolymer of a 5 C4 7 i~,--ol oolefin and an alkylstyrene, and (b) an unsaturated carboxylic acid or a derivative thereof. The blend is said to have improved impact strength while m~int~ining the high flP-II~I modlllus of the polyamide.
In U.S. Pat. No. 5,244,961, a process is described for the preparatiûn of a blend of tl~e....op!~ctic polyamide and halogen-cont~ining copolymer of C~, isomonoolefin and para-20 alkylsly~ne, in the presence of a metal compound. The blend has improved impactreCict~n~e at low le~llpe~atu~s.
21 74~0~
--SUMMARY OF THE INVENTION
The present invention is based on the discovery that a thermoplastic elastomer co!..po~;l;on having eycpll~ont physical propellies at elevated te-~lpeldtures is provided by blending (a) a th~l"oplastic çnginçering resin with (b) a dyn~mi~lly v--lç~ni7~d alloy (DVA) S c~"l~,rising a thermoplastic olefinic polymer and an olefinic elastomer having reactive cure sites, in the p~n~ of (c) a co,.~p;~lihilizer for the enein~ g resin and the DVA.
The c~,~.~s;l;~ns retain their structural integrity at high tellll)eldtule, and have good tensile pr~ ies, e1c~n&~tion and fluid rçcist~nce They have utility in applications where pe.roll..dnce at elevated te."pe.dl-lre is illlpol~lt, such as automobile under-hood parts.
DESCRIPIION OF THE PREFERRED EMBODIMENTS
r;n~;n~ in~ Resin The thermoplastic engine~ring resins used in the compositions of the invention are al"ol~hous or semicrystalline m~tPri~lc usually polar in nature, with a glass tr~ncition .nl~ (T,) or melting point above about 15~C, preferably above about 200C. They may be used singly or in colllbination, and are sel~tçd from polyamides, polycarbonates, polyesters, polysulfones, polyl~tones, polyacetals, acrylonitrile-but~ ne-styrene (ABS) resins, polyphenylene oxide (PPO), polyphenylene sulfide (PPS), styrene-acrylonitrile (SAN) resins, polyimides, styrene maleic anhydride (SMA) and aromatic polyketones. Preferred ~hc.",oplastic engineering resins are polyamides. The more preferred polyamides are nylon 6, nylon 6,6, nylon 11, nylon 12 and mixtures or copolymers thereof.
Suitable thermoplastic polyamides (~ylo~ns) include crystalline or resinous, high mn~ r weight solid polymers (including copolymers and terpolymers) having recurring 21 74~03 ~- amide units within the pol~ chain. Polyamides may be prepared by polym~ri7~ion of one or more epsilon lactams such as caprolactam, pyrrolidone, lauryllactam and ~...;no..ml~ lactam, or amino acid, or by condçn~ion of dibasic acids and di~mines Both fiber-forming and mol~ing grade nylons are suitable. Examples of such polyamides are 5 polyca~ ^t~m (nylon 6), polylauryllactam (nylon 12), polyhPY.~n ethylçn~ir~mide (nylon 6,6), polyh~ .ylPn~ de (nylon 6,9), polyheY~methyl~neseb~mi~e (nylon 6,10), polyh. ;t..~ cisoph~ mide (nylon 6,IP) and the conden~ion product of 11-amino-nnic acid (nylon 11). Additional examples of s~icf~tory polyamides (çspeci~lly those having a s~te ing point below 275C) are described in Kirk-Othmer, Encyclopedia of ChPn~ir~1 Te~hnolegy, 3d edition, vol. 18, pages 406-409, and Encyclopedia of Polymer Science and Fng;,~ ;ng, 2d edition, vol. 11, pages 445-450. Commercially available th~.lllopla~lic polyamides may be advantageously used in the practice of this invention, with linear crystalline polyamides having a softening point or melting point between 160 and - 230C being plefell~d.
The amount of engin~ring resin found to provide useful compositions is generally from about 10 to about 50 parts by weight, and more preferably from about 10 to about 40 parts by weight, based on the weight of the composition comprising enginePring resin, DVA
and col..l ~;hilizer.
Dynamically Vulcanized Alloy The DVA component of the composition comprises a thermoplastic olefinic polymer and an ~ o.l-~ (rubber) which have been melt blended in the presence of a curative to dynqmi~lly v~ ni7e the elastomer. The resnlting DVA is a polyolefin matrix having 21 749Q~
micron or s~lbmir~on size e1~ctompr particles dispersed therein. The elastomer is desirably at least partially cured (crocclinkPd) during the dynarnic vulc~ni7~tion, and preferably is fully or completely cured.
As used in the speçifir~tion and claims, the term "dynamic vlllc~ni7~tion" means a S process wllclcin the elasloll-e is vl~ ni7ed or cured in the presence of the polyolefin under c~ nc of high shear and at a te.llpcla~lre above the melting point of the polyolefin. The e~ is thus cimull;.n~usly crocclink~d and is usually dispersed as fine particles within the polyolefin, ~lth~u~h co-continuous phase morphologies or a Illi~Lwc of discrete and co-conl;n~ou~ phase morphologies are also possible. Dynamic vulc~ni7~tion is effected by 10 mLlcing the co",poncnls at elevated te"~pel~ture in conventional mixing e4uip"lcnt such as roll mills, l~nb.l~ mixers, Brabender mixers, continuous mixers, mixing extruders and the like.
The unique Çh~ tçrictic of dyn~mic~lly cured colllpo~itions is that, notwithct~n~ing the fact that the el ~`t~ f ~ COn~pOI~ nt is partially or fully cured, the compositions can be process~d - and ~,ùcessed by conventional plastic processing techniques such as extrusion, injection 5 mol ling and compression molding. Scrap or fl~ching can be salvaged and reprocessed.
The terms "fully vu~ ni7ed" and "completely vulc~ni7ed" as used in the specific~tion and claims means that the ela~lu,ll~ l colllponent to be vulc~ni7P~ has been cured to a state in which the ela~tù,lle,ic ~r~lties of the crocclinked rubber are similar to those of the ela~to",~r in its conventional vlllc~ni7ed state, apart from the thermoplastic elastomer 20 co",posilion. Simply stated, fully vul~ni7P~ means that subs~nti~lly all of the rubber ~"~po~.ent which is capable of being vul~ni7P~, has been v-~ ni7ed. The degree of cure can be d~ ;bed in terms of gel content or, conversely, extractable co~ onents.
2~ 7~8 ~- ~lt~nqtively the degree of cure may be eApl~ssed in terms of crosslink density. All of these ~liplions are well known in the art, for example in U.S. Pat. Nos. 5,100,947 and5,157,081, both of which are fully inco,~l~ted herein by this reference.
The amount of DVA found useful in the present compositions is generally from about 90 to about S0 parts by weight, and more p~efelably from about 90 to about 60 parts by weight, based on the weight of the colll~si~ion comprising engil-~ ;.-g resin, DVA and co...p~lil.ilizer.
Thermoplastic Olefin Polymer Polyolefins suitable for use in the compositions of the invention include non-polar lh~,llloplaslic, crystalline or semi-crystalline polyolefin homopolymers and copolymers.
They are ~)lC~a~d from monoolefin monomers having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene and the like, with ethylene, propylene and ul~ thereof being p~fe.,cd. The polyethylene can be low density, ultra-low density or - high density m~teli~l. The term polypropylene includes homopolymers of propylene as well as reactor copolymers of polypropylene which can contain about 1 to about 20 weight percent of ethylene or an -olefin comonomer of 4 to 16 carbon atoms, and mixtures thereof. The polypropylene can be isotactic or syndiotactic, usually having a narrow range of Tg.
Col..l"e~;ally available polyolefins may be used in the practice of the invention.
The amount of polyolefin found to provide useful DVA compositions is generally 20 from about 10 to about 90 weight percent, based on the weight of the polyolefin and elaslo--,er. Preferably, the polyolefin content will range from about 10 to about S0 percent by weight.
Curable Elastomer Fl~t~!l..e.~ suitable for use in the co",positions of the invention are co~palible with the th~".~op1~c~ir olefin polymer and have reactive cure sites. Such cure sites can either be an integral part of the elas~ ,ler backbone or can be incol~latcd by the q~dr~i~ion of S functionql groups. A prcfcllcd group of elastomers is that prepared from copolymers of C4 7 c~in~ and para-alkylstyrene. These copolymers are more fully desrrihed in U.S. Pat.
No. 5,162,445, the ~ os~llc of which is inco~ ed herein by this refercnce. A
particularly pl~f.,.l~ ela~toln~,~ species is rel,r~sellted by the halogcnatcd copolymer of isobutylene and para-methylstyrene. Elastomers of ethylene-propylene (EPR) and 10 poly(ethylene-co-propylene-co-diene), also known as EPDM rubber, have also been shown to ol", well in the compositions, either alone or in combination with copolymers of i~o]~ and para-alkylstyrene.
The amount of olefinic elastomer useful in the DVA compositions is generally from about 90 to about 10 weight percent, based on the weight of the polyolefin and elastomer.
5 ~lefe.ably, the elastomer content will range from about 90 to about 50 percent by weight.
Curing System In the cG",~ilions of the invention, the elastomer co,--ponent of the DVA will generally be at least partially vul~ni7ed, or crosclink~d~ Those ordinalily skilled in the art will applo~iale the appropliate qu~ntities~ types of cure systems and vulcanization conditions 20 ~uir~d to carry out the vlllc~ni7~1ion of the rubber. The elastomer can be vlllc~ni7~d using varying ~moun~ of curative, varying ~---p~atures and varying time of cure in order to obtain the optimum cro~linkinv desired. Any known cure system can be used, so long as it is ~ P under the v--l~ni7~tion con~liti()nc for the elastomer or combination of elastomers being used and is co,l,pa~ible with the thermoplastic polyolefin co-"ponent of the DVA.
These Cu~ S include sulfur, sulfur donors, metal oxides, resin systems, m~l.oimi~ec pero~cide-based ~st~ .,ls, high energy radiation and the like, both with and without S ~ Ol~ and co-agents. Phenolic resin curatives are prefelled for the preparation of the DVA co~c;l;~c of the invention, and such cure systems are well known in the art and l;t~ m." of vlllr~-li7~ion of elastomers. Their use in DVA compositions is more fully d~ il~d in U.S. Pat. No. 4,311,628, the ~licclosllre of which is fully incol~,ated herein by this l~f~nce.
10 Compatibilizin~ A~ent The engin~ring resin and dynamically vulcanized alloy of the composition are co"lbilled in the presence of a compatibilizer for these components. Absent the c~-..p--~;bilizer, blends of ellg;~ .ing resin and DVA have poor "~ech~nical and elongation - pl~,Lies, due to the lack of interfacial adhesiolrbetween the components. Under stress, the weak interfaces may fail and the co",ponents del~min~te. The addition of an interfacially active colllpatibilizer overcomes this deficiency. The compatibilizer is designed so that each ~ ,.rnt or fun~tiQn~l group is compatible with one of the major component phases, and in~"")alible with the other. The compatibilizer improves interfacial adhesion by connecting the co",ponent phases, forrning a stable blend.
The co",patibilizer can be formed by the direct interaction of segments containing the functional groups present in the major components, i.e. the engineering resin and the DVA, or by interaction with another bi- or multi-functional compound. Compatibilizers are known ~in the art, e.g. in U.S. Pat. No. 4,555,546 and Journal of Macromolecular Science Chemistry, A26 (8), 1211 (1989). ~lefelled compatibilizers include the reaction product of nylon and fun-~ nqli7~d polypropylene, p~a~d by melt mixing nylon 6 with polypropylene grafted with 0.1-2.0 wt percent maleic anhydride, in a ratio of nylon:m~ t~ polypropylene Ianging from 9S:5 to SO:S0. See J. Appl. Polym. Sci., 18, 963 (1974) and Eur. Polym. J., 26, 131 (1990).
The col~.p~t;bilizer may be present in the compositions of the invention in the range of about 2 to about 35 parts by weight based on- the e ne;nf~ ;ng resin, DVA and co,l,patibilizer.
~,f~,.~ly it is present in the range of about 2 to about 20 parts by weight.
Additives In ~ itiot~ to the engine~ring resin, DVA and co-"palibilizing agent, the compositions of the invention may also include reinforcing and non-reinforcing fillers, pl~ctici7ers for the e/~ f~. ;n~ resin and polyolefin, antioxidants, stabilizers, rubber p~ces~ing oil, extender oils, lubricants, antiblocking agents, ~ntict~tic agents, waxes, foaming agents, pigments, flame r~ ~ants and other processing aids known in the rubber compounding art. The additives can be added during the preparation of the DVA or the p,e~aldtion of the finiche~
co...~ ;Qn or both, provided that the total amount of the additives does not exceed about 50 weight percent, pr~felàbly about 25 weight percent, based on the total thermoplastic eldstul" r colll~ n~ including additives.
Fillers and e~ nd~ ~ which can be utilized include conventional inorganics such as r~lrium c~l~onale, clays, silica, talc, titanium dioxide, carbon black and the like. The rubber pf~s~;ng oils are generally paraffinic, napthenic or aromatic oils derived from petroleum fr:-ctions. The type will be that ordinarily used in conjunction with the specific elaslul.lc~ or claslo",el~ present in the DVA, and the quantity based on the total rubber content may range from zero to a few hundred parts per hundred parts rubber (phr).
General ~lu~
S The general p~lure for plcpaldLion of the compositions of the invention has two stages. In the first stage, a rubber having reactive curesite functionality is dyn~mic~lly vul(~ni7Pd in the presence of an olefinic thermoplastic which is inert to the rubber curesites, using appl~liate curing systems. In the second stage, this dyn~mi~lly vulc~ni7~dlul~r/plaslic alloy (DVA) is blended with an engin~ring resin in the pre~nce of a co.~ t;~ilizing agent. The two stages can be carried out independently in separate steps or sequentially in the same plocessing equipment.
More specifi~lly, the DVA is prepared by blending the thermoplastic olefinic polymer, the elastomeric copolymer and zinc oxide in a Brabender mixer of 60 cc capacity at a t~ lule of about 180C. The speed of the-mixer is in the range of about 60 to about 200 rpm. After the co"~ponehl~ are well dispersed the curative system is added to initiate dynamic v~ ni7~tion Mixing is continued until a maximum of mixing torque in~ic~tes that v~ ni7~tion has occurred, usually between one and five minutes, then the speed of the mixer is increased to maximum and mastication is continued for an additional two to three ~,inul~. The v-llc~ni7~ co"~position is removed from the mixer, cold pressed, and then is l~lu~lled to the mixer for an additional one to two minutes of mixing at 180C and 100 rpm.
The co",~libilizer is prepared separately by melt mixing the components, for example nylon and m~ ted polypropylene, in a Brabender plasticorder. The components 21 74~0'~
~are added to the mixer bowl at about 20 rpm, and when the bowl is filled the mixing speed is incl~ to about 200 rpm. The le~pel~ture is increased to about 220-225C, and the mixing speed is then reduced to about 100 rpm. The torque of the mixer is monitored to det~ ."-inf completion of the end group reaction. When the reaction is complete, the S co~ alibiliær coml o~;~ion is removed from the mixer and cold pressed.
In the final step, the en~;nf~;ng resin, DVA and compatibilizer are blended at high shear in a Br'-endçr mixer. The te,.,~,~ture is increased to about 225C and the speed to about 200 rpm. After the m~t~ri~l~ melt, mixing is continued until the stock telllpGl~lulG
reaches about 235C. The speed is then reduced to about 100 rpm and m~ctin~ion continued 10 for two to three i~ f s The stock is removed from the mixer, cold pressed, then returned to the mixer for an additional two minutes of mixing at 225C and 100 rpm. The cG~Ipo~ilion is removed from the mixer and co."~ ssion molded at about 240C into plaques of about 2 mm thickness for physical testing.
The following examples serve to illustrate-but not limit the present invention.
Example 1 Following the general procedure outlined above, dyn~mi~lly vulcanized alloys of polypropylene and an elastomer comprising a brominated copolymer of isobutylene and para-methylstyrene were prepared. The polypropylene, elastomer and curative were melt mixed in a heated Brlben-le- mixer of 60 cc capacity at 100 rpm. The mix was masticated at a t~lllpel~:ltUl~ in the range of 180 to 190C to dynamically v-llc~ni7e the rubber. Mixing was cont;n~ for about two minutes, or until the cure was complete (as indicated by a rapid inel~ in torque of the mixer). Mixing was then continued for about two minutes, or until 2~ 7490,~
the torque became relatively con~t~nt The conlposition was removed from the mixer, sheets were co,llp~s~ion molded at 190C and the physical propellies were measured.
R~l~nt~ e DVA coll~:,itions and thelr physical prope,lies are set forth in Table I.
TABLE I
#1 #2 Polypropylene'(parts/lOOpartsrubber)(phr)33.3 66.6 Elaslolll~ 100 100 Zinc oxide 2 2 Curative3 7.5 7.5 Hardness (Shore) 78A 44D
Tensile strength (psi) 1920 3310 F1ong~tion (%) 350 530 ~ s 100% (psi) 765 1740 Tension set (%) - 14 40 Oil swell (%) - 22 hr/125C, No. 3 oil 168 110 Colllpres~ion set (%) - 22 hr/125C 22 60 'PP D0008 (Ari tech Chemic-l) 'I ' - ' i yl...c/~, yt~t~ - copolymer (Exxpro~ elastomer, E~xon Chemical) '~ - yl~l F ~ tylphonol (~
The physical p~.lies of the compositions were determined according to the following m-~ho~c-Tensile strength, elongation, modulus 100% and tension set - ASTM D412 Oil swell - ASTM D471 Colll~ ssion set - ASTM D395B
The DVA co~l~sitions of this Example were incorporated into the blends of the invention according to the following examples.
~ 747~B
.
Example 2 CGI~PGS;I;OnC of the invention were prepaled by the procedure described above.
C~l--pos;l;onc A and B are co,l"~ tive examples wherein blends of engin~ring S resin/el~ct~....~ r and eng;n~ ;ng resin/DVA were evaluated without the compatibilizer cO~ n- --l CG~ o~;l;onc C-E lC~ S~Ent the triblend col"positions of the invention, in~lnr1in~ the cG",~Iibilizer. Physical pro~llies were co,l-par~d and are set forth in Table II.
Co~Pnl-~t;onc of the components are in the prol)Gllions e~plessed in the Table.
2 1 74~
TABLE II
A B C D E
Nylon 61 104.7 50 25 25 25 Compqtihilizer 13 - - 25 25 Co!.. p--~;hilizer 24 - - - - 25 Fl-c~.. ~ C 100 Zinc Oxide 2 Curative6 7.5 pl~ctil i7~r7 8 IIar~lness (Shore D) 50 43 44 39 44 Tensile sll~nglh (psi) 1790 1550 2580 2250 2680 Fk!n~tiQn (%) 10 120 230 360 230 Modulus 100æ (psi) - 1550 1980 1440 2060 Tension set (96) - Fail 46 38 47 Oil swell (æ) 24 - 83 80 69 Co",pr~ssion set (5~) 80 - 61 61 61 ' CapronX 8202 (Allied Signal) 2 DVA #1 from Example 1 3 60/40 ~,ol.~l.._r of Nylon 6/Polybond~ maleic anhydride modified pol~
(Uniroyal Chemical Co.) ' 80/20 interpolymer of Nylon 6/Polybond maleic anhydride modified pol~ o~ ,nc (Uniroyal Chemical Co.) 51~ ' isob-llyl~ c/p-u.~ C copolymer (Exxpro~, Exxon Chemical) 6 dimethylol-p-octyl phenol (nonhalogenated) 7 K~tj~nfl~ 8 (Akzo Chemie) As can be seen from the data in Table II, the compositions of the invention (C, D and E) have improved tensile strength and elongation pro~llies at ambient te~l,peldture. In a further test tensile ~lupellies~ and particularly elongation plu~llies, were found to be retained at ~ n~res up to 165C as shown by the data for Cûmposition E set forth in Table IIA.
TABLE IIA
Te~ lu~ 100 C 150 C 160 C
Tensile ~ ngll, (psi) 1615 880 530 Flong~t~ (%) 280 275 215 S Modulus 100% (psi) 920 S00 345 The ~ddi~ioll of antioxidants can further improve the heat aging pn)pelties of the c4~ ;0nc of the invention. A co,..po~ilion of nylon 6 (25 parts by weight), compatibilizer 2 (25 parts) and DVA #1 (100 parts) was prepared as described above, and the following additives were includ~: m~gn~cium oxide (1.25 parts); 2-melcdplotolylimidazole (2 parts); bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (1 part); and tris (3,5-di-tert butyl-4-hydroxybenzyl) isoc~dm,ldte (O.S part). Physical p,~pel~ies were determined immeAi~teiy after p~~ tion and again after hot air aging at 150 C for 168 and 336 hours. The results are shown in Table ILB.
TABLE IIB
Heat aging (hours) 0 168 336 Tensile strength (psi) 2580 2400 2080 Elongation (%) 220 lS0 120 Modulus 100% (psi) 2070 2100 1985 21 7it9Q8 Example 3 The effect of col.lpatibiliær level was studied in compositions of the invention.
C~ ~si~ n F ~p~nts a comparative example cont~ining no compatibilizer, while colll~,lions G-I contain compatibilizer over a range of concentrations. Physical p~opellies S were c~ll,par~ and are set forth in Table III.
TABLE III
F G H
Nylon 61 (grarns) 20 17.2 14.4 11.6 DVA2 (grarns) 40 40 40 40 Compatibilizer 23 (grams) 0 2.8 5.6 8.4 IIar~n~s (Shore D) 43 45 44 43 Tensile s~ngth (psi) 1550 2230 2500 2470 ~ (%) 120 177 220 230 Mod~ 100% (pSi) 1570 1935 1975 1915 - Tension set (%) Fail - 40 43 48 Oil swell (%) 60 61 60 60 Colllpr~ssion set (~) 60 62 60 60 ' Capron 8202 (Allied Signal) 2 DVA #l from Example I
3 80/20 I,ol~ of Nylon 6/PolybondD maleic anhydr.de modified pol~ e (Uniroyal Chemical Co.) The co",~silions of the invention (G, H and I) demonstrate the importance of thecolnp~tibilizer in obtaining the unexpectedly improved tensile strength and elongation pr~pe.lies.
21 749û~
Example 4 Col..po~;l;onc were p,e~a-ed with various compatibilizers using the general method il,ad above. Co~-~p~ibilizers consisting of interpolymers of nylon and maleic anhydride --o~1if;~ pol~p~;lene at dirrelei~t ratios, and interpolymers of nylon and a bromin~
S copolymer of isobutylene and para-methylstyrene, were co---paled. Physical pn)pe,Lies of the hed co~ r c were determined and are set forth in Table IV.
TABLE IV
J K
Nylon 61 (grams) 10 10 10 DVA2 (grams) 40 40 40 Co~ ilJilizer 13 (grams) 10 -- --Colllpalibilizer 24 -- 10 --Comp-q-tibilizer 35 -- -- 10 plqcti~i7P,4 (grams) 8 8 8 - Hardness (Shore D) 39 - 39 40 Tensile strength (psi) 2430 2460 1450 FlongqtiOn (%) 320 310 160 Mod~ ls 100% (psi) 1530 1570 1430 Tension set (%) 38 32 30 Oil swell (%) 57 47 72 Co,llyl~sion set (%) 57 57 53 ~ Capron 8202 (Allied Signal) 2 DVA #1 from E~ample 1 3 60/40 ~ ~~ of Nylon 6/Polybond maleic '~ydride modified polypropylene (Uniroyal Chemical Co.) 4 80l20 r'l~ of Nylon 6/Polybond maleic anhydride modified polypropylene (Uniroyal Chemical Co.) ~ T ~ of Nylon 6~.~ ' copolymer of isobutylene and para-methylstyrene (E~u~pro~, E~on Chemical) 6 R. tj. n. ~ 8 (Alczo Chemie) 21 749QI~
Example 5 CO~ ;Qn~ were pl~alGd wherein ethylene-propylene-diene monomer (EPDM) rubher was the elastomer co"~ponGI~t of the DVA. The DVA was plc~a~ed as ~ ;l~d ahove, with a formulation of 33.3 parts of polypropylene (PP D0008, Aristech S ChPmi~l), 100 parts of EPDM, and a cure system of 2 parts zinc oxide, 1.26 parts ~nnous chl- ri~le and 7 parts dimethylol-p-octyl phenol. DVA #3 was ~le~aled using Vistalon0 7000 EPDM (E~cxon Ch~mir~l) and DVA #4 was pre~)a,e~ using Vistalon0 4608 (Exxon Chlq-mic~l).
The co,~ ;hilized l,ibl^nll compositions of the invention were ~lel~alcd and physical plopcllies are set forth in Table V.
TABLE V
M N O
Nylon 6' (grams) 10 10 10 Co~ ;1.iliær2 (grams) 10 10 10 DVA #1 (grams) 40 -- ---15 DVA #3 - -- 40 --DVA #4 -- -- 40 II~lness (Shore D) 43 49 46 Tensile sll~n~ (psi) 2620 3020 2940 Fl~ng~tiorl (%) 230 225 240 Mo~ s 100% (psi) 2060 2340 2180 Tension set (%) 48 60 40 Oil swell (%) 61 70 72 Co",~lession set (%) 59 52 54 ' Capron 8202 (Allied Signal) 2 80/20 interpolymer of Nylon 6/Polybond maleic anhydride modified polypropylene (Uniroyal Chemical Co.) 21 749~3 While the best mode and ~lefelred embodiment of the invention have been set forth in accord with the Patent Statutes, the scope of the invention is not limited thereto, but rather is defined by the claims which follow.
Claims (17)
1. A composition comprising a blend of (a) from about 10 to about 50 parts by weight of a thermoplastic engineering resin;
(b) from about 90 to about 50 parts by weight of a dynamically vulcanized alloy comprising (i) a thermoplastic olefinic polymer, and (ii) an elastomeric copolymer having reactive cure sites; and (c) from about 2 to about 35 parts by weight of a compatibilizer for (a) and (b).
(b) from about 90 to about 50 parts by weight of a dynamically vulcanized alloy comprising (i) a thermoplastic olefinic polymer, and (ii) an elastomeric copolymer having reactive cure sites; and (c) from about 2 to about 35 parts by weight of a compatibilizer for (a) and (b).
2. The composition of claim 1 wherein the blend comprises from about 10 to about 40 parts by weight of (a), from about 60 to about 90 parts by weight of (b) and from about 2 to about 20 parts by weight of (c), based on the total weight of the blend.
3. The composition of claim 1 wherein the thermoplastic engineering resin (a) is selected from the group consisting of polyamides, polyesters and mixtures thereof.
4. The composition of claim 1 wherein the thermoplastic engineering resin (a) is selected from nylon and copolymers thereof.
5. The composition of claim 1 wherein the thermoplastic olefinic polymer (i) is selected from the group consisting of polyethylene, polypropylene and copolymers or mixtures thereof.
6. The composition of claim 1 wherein the thermoplastic olefinic polymer (i) is polypropylene.
7. The composition of claim 1 wherein the elastomeric copolymer (ii) is selected from the group consisting of a functionalized copolymer of a C4-7 isomonoolefin and a para-alkylstyrene, EPDM rubber, or mixtures thereof.
8. The composition of claim 1 wherein the elastomeric copolymer (ii) is a halogenated copolymer of isobutylene and para-methylstyrene.
9. The composition of claim 1 wherein the elastomeric copolymer (ii) is EPDM rubber.
10. The composition of claim 1 wherein the dynamically vulcanized alloy (b) is fully vulcanized.
11. The composition of claim 1 wherein the dynamically vulcanized alloy (b) comprises from about 10 to about 90 weight percent of thermoplastic olefinic polymer (i) and from about 90 to about 10 weight percent of elastomeric copolymer (ii), based on the weight of (i) and (ii).
12. The composition of claim 1 wherein the compatibilizer (c) is a multi-functional compound having at least one segment which is compatible with the thermoplastic engineering resin (a) and incompatible with the alloy (b), and at least one segment which is compatible with the alloy (b) and incompatible with the thermoplastic engineering resin (a).
13. The composition of claim 1 wherein the compatibilizer (c) is the reaction product of a thermoplastic resin and a maleated olefinic polymer.
14. The composition of claim 13 whelein the ratio of engineering resin to maleated olefin polymer ranges from about 95:5 to about 50:50.
15. A composition comprising a blend of (a) from about 10 to about 40 parts by weight of nylon;
(b) from about 90 to about 60 parts by weight of a dynamically fully vulcanized alloy comprising (i) from about 10 to about 50 weight percent of polypropylene, and (ii) from about 90 to about 50 weight percent of a halogenated copolymer of isobutylene and para-methylstyrene, based on the weight of (i) and (ii); and (c) from about 2 to about 20 parts by weight of the blend of a compatibilizer for (a) and (b) comprising the reaction product of nylon and maleated polypropylene.
(b) from about 90 to about 60 parts by weight of a dynamically fully vulcanized alloy comprising (i) from about 10 to about 50 weight percent of polypropylene, and (ii) from about 90 to about 50 weight percent of a halogenated copolymer of isobutylene and para-methylstyrene, based on the weight of (i) and (ii); and (c) from about 2 to about 20 parts by weight of the blend of a compatibilizer for (a) and (b) comprising the reaction product of nylon and maleated polypropylene.
16. The composition of claim 1 in the form of a molded or extruded article.
17. The composition of claim 1 made by the steps of a) preparing a dynamically vulcanized alloy comprising a blend of thermoplastic olefinic polymer and an elastomeric copolymer having reactive cure sites;
b) blending the alloy from step (a) with an engineering resin in the presence of a compatilizer for the resin and alloy.
b) blending the alloy from step (a) with an engineering resin in the presence of a compatilizer for the resin and alloy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/439,738 | 1995-05-12 | ||
| US08/439,738 US5574105A (en) | 1995-05-12 | 1995-05-12 | Thermoplastic elastomers having improved high temperature performance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2174908A1 true CA2174908A1 (en) | 1996-11-13 |
Family
ID=23745940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002174908A Abandoned CA2174908A1 (en) | 1995-05-12 | 1996-04-24 | Thermoplastic elastomers having improved high temperature performance |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5574105A (en) |
| EP (1) | EP0742268B1 (en) |
| JP (1) | JPH0925370A (en) |
| KR (1) | KR960041261A (en) |
| CN (1) | CN1139686A (en) |
| AU (1) | AU697634B2 (en) |
| BR (1) | BR9602206A (en) |
| CA (1) | CA2174908A1 (en) |
| DE (1) | DE69611395T2 (en) |
| ES (1) | ES2153912T3 (en) |
| IL (1) | IL118072A0 (en) |
| MY (1) | MY132167A (en) |
| TW (1) | TW362106B (en) |
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-
1995
- 1995-05-12 US US08/439,738 patent/US5574105A/en not_active Expired - Lifetime
-
1996
- 1996-04-24 CA CA002174908A patent/CA2174908A1/en not_active Abandoned
- 1996-04-29 IL IL11807296A patent/IL118072A0/en unknown
- 1996-05-03 TW TW085105327A patent/TW362106B/en active
- 1996-05-07 ES ES96107186T patent/ES2153912T3/en not_active Expired - Lifetime
- 1996-05-07 DE DE69611395T patent/DE69611395T2/en not_active Expired - Fee Related
- 1996-05-07 EP EP96107186A patent/EP0742268B1/en not_active Revoked
- 1996-05-09 BR BR9602206A patent/BR9602206A/en not_active Application Discontinuation
- 1996-05-10 KR KR1019960015338A patent/KR960041261A/en not_active Application Discontinuation
- 1996-05-10 AU AU52216/96A patent/AU697634B2/en not_active Ceased
- 1996-05-10 CN CN96104476A patent/CN1139686A/en active Pending
- 1996-05-11 MY MYPI96001789A patent/MY132167A/en unknown
- 1996-05-13 JP JP8142271A patent/JPH0925370A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0742268A3 (en) | 1997-08-27 |
| EP0742268B1 (en) | 2001-01-03 |
| EP0742268A2 (en) | 1996-11-13 |
| AU5221696A (en) | 1996-11-21 |
| ES2153912T3 (en) | 2001-03-16 |
| CN1139686A (en) | 1997-01-08 |
| JPH0925370A (en) | 1997-01-28 |
| DE69611395T2 (en) | 2001-08-23 |
| BR9602206A (en) | 1998-04-07 |
| KR960041261A (en) | 1996-12-19 |
| IL118072A0 (en) | 1996-08-04 |
| DE69611395D1 (en) | 2001-02-08 |
| US5574105A (en) | 1996-11-12 |
| TW362106B (en) | 1999-06-21 |
| MY132167A (en) | 2007-09-28 |
| AU697634B2 (en) | 1998-10-15 |
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| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 20030424 |