CA1098241A - Compositions containing hydrogenated block copolymers and engineering thermoplastic resins - Google Patents

Abstract

A B S T R A C T
In a composition containing a partially hydrogenated block copolymer, a halogenated thermoplastic polymer and at least one dissimilar engineering thermoplastic resin at least two of the polymers form at least partial continuous interlocked networks with each other.

Description

1~98Z9Ll The invention rela.tes to a composition contai.ning a partially hy~rogenated block copolymer comprising at least two terminal polyrner blocks A of a monoa].kenyl arene having :.
an average molecular weight o~ f`rorn 5,000 to 125,000 and .-at least one i.ntermediate polymer block B Or a conjugate~d diene having an average molecular wei.ght Or from 10,000 to ; 300,000, in which the terminal polyrner blocks A constitute from 8 to 55~ by wei.ght of' the block copolymer and~no more than 25% of the arene doub1.e bonds Or the po'lymer b].ocks A
and at least 80% of the aliphatic double bonds oI' t}le '~
. polymer blocks B have been reduced by hydrogenation. :~
Engineering thermoplastic resins are a group of' polymers ;~
: that possess a balance of properties comprising strength, stif~ness, impact resistance, and'long term~dimensinnal~
':: 15 stabilit~ that make them useful as structural materlals. ~;
Engineering thermoplastic resins are especially attractive '~
as replacements for metals because:of the reduction 1n weight that can often be achieved as, for example, in automotive~applications.
.
: 20 For a particular application~ a sin~le t~i!rmoplast:ic '~
resin may not off'er the combinatlon~or properties des~ired and, therefore, means to correct this deficiency are of interest. One particularly appealing route i.s through blending together two or more polymers (which :i.ndividually : :~
have the properties sought) to give a material with the desired combination of properties. This approach has been ~'~' ":

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`"'`~;~ ;`' successful in limited cases, such as in the improvement of impact resistance for thermoplastic resins, e.g., ~;
polystyrene~ polypropylene and poly(vinyl chloride), using special blending procedures or additives for this purpose. However, in general, blending of thermoplastic resins has not been a successful route to enable one to combine into a single material the desirable individual characteristics of two or more palymers. Instead, it has often been found that such blending results in combining -: ~
the worst features of each with the result being a material of such poor properties as not to be Or any practical or commercial value. The reasons for this ~ailure are rather well understood and stem in part from ~ i ; the fact that thermodynamics teaches that most combinations of polymer pairs are not miscible, although a number Or notable exceptions are known. More importantly, most polymers adhere poorly to one another. As a result, the ~ ;
interfaces between component domains (a result of their immiscibility) represent areas of severe weakness in blends and, therefore, provide natural flaws and cracks which result in facile mechanical failure. Because of this, most polymer pairs are said to be "incompatible". In some instances the term compatibility is used synonymously with miscibility, however, compatibility is used here in a more general way that describes the ability to combine two polymers together for beneficial results and may or may not connote miscibility. ~ -~:

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, :' One method which may be used to circumvent this problem in polymer blends is to "cornpatibilize" the two , polymers by blending in a third componentg often re~erred to as a "compatibilizing agent", that possesses a dual ~
solubili.ty nature for the two polymers to be blended. ~ : .
Examples Or this third component are obtained in block or graft copolymers. As a result of this characteristic, this agent locates at the interface between components and greatly improves interphase adhesion and theref`ore ~10 increases stabili.ty to gross phase separation.
The invention covers a means~to stabilize multi-polymer blends that is independent of the prior art :
compatibilizing process and is not restricted to the necessity for restrictive dual solubility characteristics.
The materi.als used for this purpose are special block co- : `
. ~
polymers capable o.~ thermally reversible self-cross linking.
Their action in the present invention is not that visuallzed by the usual compatibilizing concept as ev1denced by the general ability of these mat,erials to perform similarly for a wide range of:blend components which do not conform to the solubility requirements of the previous concept.
Now, the invention provides a composition containing a partially hydrogenated block copolymer comprising at :~
~ - .
least t,wo terminal polymer blocks A of a monoalkenyl arene ~ :
having an average molecular weight of from 5,000 to 1253000, and at least one intermediate polymer block B of a con-_ F _ jugated diene having an average molecular weight of from 10,000 to 300,000, in which the terminal polymer blocks A
constitute ~rom 8 to 55~ by weight of the hlock copolymer and no more than 25% of the arene double bonds of the polymer blocks A and at least 80% of the aliphatic double bonds o~ the polymer blocks ~ have been reduced by hydrogen-ation, which composition is characterized in that the composition comprises:
(a) 4 to 40 parts by weight of the partially hydrogenated block copolymer; ~;
(b) a halogenated thermoplastic polymer having a generally crystalline structure and a melting point of over 120C;
(c) 5 to 48 parts by weight of at least one dissimilar engineering thermoplastic resln being selected from - ~
: the group consisting of polyamldes, polyolefins, ~ ~;
thermoplastic polyesters, poly(aryl ethers),~:poly-(aryl sulphones), polycarbonates, acetal resins, thermoplastic polyurethanes, and nitrile resins, in which the w~eight ratio of the halogenated thermoplastic ~ :
.` ~ polymer to the dissimilar engineering thermoplastic resln :~
is greater than 1:1 so as to form a polyblend wherein at .
least two of the polymers florm at least partial con- : ~
, tinuous interlocked networks with each other.
: 25 The block copolymer of the in~ertion effectively acts as a mechanical or structural stabilizer which interlocks :

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the var:ious po:Lymer structure networks and pre~ents the consequent separation of the polymers during processing and their subsequent use. As defined more fully hereln-afterg the resulting structure of the polyblend (short for 'Ipolymer blend") is that of at least two partial continuous interlocking networks. This interlocked structure results in a dimensionally stable polyblend that will not delaminate upon extrusion and subsequent use.
To produce stable blends it i.s necessary that at least two of the polymers have at least partial continuous networks which interlock with each other. Preferably, the block copolymer and at least one other polymer have partlal continuous interlocking network structures. In an ideal ~ -.~ ~
situation all of the polymers would have complete con- ~ ~
~, :
tinuous networks which interlock with each other. A
partial continuous network means that a porkion of the polymer has a continuous network phase structure whi]e the other portion has a disperse phase structure. Prefer~
ably, a major proportion (greater than 50% by weight) of the partial continuous network is continuousO As can be readily seen, a large variety of blend structures is possible since the structure Or the polymer in the blend may be completely continuous~ completely disperse, or partially continuous and partial]y disperse. Further yet, ~ -the disperse phase of one polymer may be dispersed in a ~ `~
~7~

second polymer and not i.n a third polymer. To i.llustrate .
some of the structures, the following lists the various combinations of polymer structures possible where all structures are complete as opposed to parti.al structures.
Three polymers (A, B and C) are involved. The subscript "c" signif'ies a continuous structure while the subscript "d" signifies a disperse structure. Thus, the designation "AcB" means that polymer A is continuous with polymer B, and the designation "BdC" means that polyrner B is disperse ::
in polymer C, etc.
AcB AcC BCC
AdB AcC BCC ~' A B AcC BdC
BdA AcC BCC ~ :.
, 15 BdC AcB AcC
CdA AcB ACC
, d AcB ACC
Through practice of the invention, it is possible to , :

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-7a-improve one type of physical property of the composite blend while not causing a significant deterioration in another phys;cal property. In the past this has not always been possible. For example, in the past it was expected that by adding an amorphous rubber such as an ethylene-propylene rubber to a thermoplastic polymer to improve impact strength, one would necessarily obtain ~ ~
a composite blend having a significantly reduced heat ` ~ ;
distortion temperature (HDT). This results from the fact that the amorphous rubber forms discrete particles in the composite and the rubber, aImost by definition, has an exceedingly low HDT, around room temperature.
However, in the present invention it is possible to ~s significantly improve impact strength while not de-tracting from the heat distortion -temperature. In fact, -when the relative increase in Izod impact strength is measured against the relative decrease in HDT, the value of the ratio is much higher than one would expect. ~ ;
~or example, in blends containing a halogenated thermo~
plastic block copolymer, and other engineering thermo~
plastics such as Nylon 6 and polycarbonates, this ratio is much greater than expected.
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It is part;cularly surprising that even just small amounts of the block copolymer are sufficient to stabilize the structure of the polymer blend over very wide relative concentrations. For example, as little as four parts by weight of the block copolymer is sufficient to stabilize a blend of 5 to 90 parts by weight halogenated thermo-plastic polymer with 90 to 5 parts by weight cf a dis-similar engineering thermoplastic.
In addition, it is also surprising that the block co-polymers are useful in stabilizing polymers of such a wide variety and chemical make-up. As explained more fully hereinafter, the block copolymers have this abiliky to stabilize a wide variety of polymer over a wide range of concentrations since they are oxidatively stable, possess essentially an infinite viscosity at zero shear stress, ~ ;~
and retain network or domaln structure in th~e melt.
Another significant aspect of the invention is that the ease of processing and forming the various polyblends is greatly improved by employing the block copolymers as ;20 stabilizers.
The block copolymers employed in ~he composition~
according to the invention may have a variety of geometrical structure, since the invention does not depend on any specific geometrical structure, but rather upon the chemical constitution of each of the polymer blocks. Thus, the block copolymers may be linear, radial or branched.
Methods for the preparation of such polymers are known in 3 ~9~324~

the art~ The structure of the polymers is determined by their methods of polymerizatiorl. For example, linear polymers result by sequential introduction of the -~
desired monorners into the reaction vessel when using such initiators as lithium-alkyls or dilithio-stilbene, ~ ;
or by coupling a two-segment block copolyrner with a difunctional coupling agent. Branched structures,on the other hand, may be obtalned by the use of suitable coupling agents having a ~unctionality with respect to the precursor polymers of three or more. Coupling may be effected with multifunctional coupling agents, such as ~, dihaloalkanes or -alkenes and divinyl benzene as well as ~
certain polar compounds, such as sil;con halldes, s LloXaneC; ~`
or esters of monohydric alcohols with carboxylic acids.
The presence Or any coupling residues in the polymer may -be ignored for an adequate description Or the polymers - ~ - :
forming a part of the compositions Or this invent;on. ;~
Likewise, in the generic sense, khe specific structures also may be ignored. The invention applies especially to khe use of~selectively hydrogenated polymers havlng the configuration before hydrogenation of the rollowing typical specles:
polystyrene-polybutadiene-polystyrene (SBS) polystyren~-polyisoprene-polystyrene (SIS) poly(alpha-methylstyrene)polybutadiene-poly(alpha-methylstyrene) and :

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poly(alpha-rnethylstyrene)polyisoprene~
poly(alpha-meti~ylstyrene).
Both polymer blocks A and B may be either homopolymer or random copolymer b]ocks as long as each polymer b:Lock predominates in at least one class of the mononlers charac-terizing the polymer blocks. The polymer block A may comprise homopolymers of a monoa]kenyl arene and co-polymers of a monoalkenyl arene with a conjugated diene as long as the po~ymer b]ocks A individually predominate in monoalkenyl arene units. The term "monoalkenyl arene"
will be taken to include especially styrene and its analo~ues and homologues ;ncluding alpha-methylstyrene and ring-substituted styrenes particularly xing-methyl-ated styrenes. The preferred monoalkenyl arenes are styrene and alpha-methylstyrene, and styrene is particularly preferred. The polymer blocks B may comprise homopolymers Or a conjugated diene, such as butadiene or ~ ;
isoprene~ and copolymers of a conjugated diene with~a monoalkenyl arene as long as the polymer blocks B pre~
dominate in conjugated diene unitæ. When the monomer employed is butadiene, it is preferred that between 35 and 55 mol. per cent of the condensed butadiene units in ;~
the butadiene po~ymer block have 1,2-confi~uration. Thus when æuch a block is hydro~enated the resulting ~roduct iæ~ or resembles, a regular copolymer block of ethylene and butene-1 (EB). If the conjugated diene employed is ~1~98;~

:

--11-- , isoprer,e, the resulting hydrogenated product is or resembles a regular copolymer block Or ethylene and ;
propylene (EP).
Hydrogenation of` the precursor block copolymers is prererably e~fected by use Or a catalyst comprising the reaction products of an aluminium alk~l compound with ~`
nickel or cobalt carboxylates or alkoxides under such conditions as to substantially completely hydrogenate at least 80% of the aliphatlc double bonds, while hydrogenating no more than 25% of the alkenyl arene :
aromatic double bonds. Preferred block copolymers are those where at least 99% of the aliphatic double bonds are hydrogenated while less than 5X of the aromatic double~bonds are hydrogenated.
The average molecular weights of the individual blocks may vary within certain limits. The block co-polymer present in the composition according to the invention has at Ieast two terminal polymer blocks A Or ^
a monoalkenyl arene having a number average molecular , ~
weight of from 5,000 to 125,000, preferably from 7,000 to 60,000~ and at least one intermediate polymer block B
of a conjugated diene having a number average molecular weight o~ ~rom 10,000 to 300,000, prererably frorn 30,000 to 150,000. These molecular weights are most accurately ~
determined by tritium counting methods or osmotic pressure ~;
measurements. ~

, ' , , " ' ' ' ' `~ " ' ' ' -12- ~ ~9~%~
' The proportion of` the polymer blocks A of the mono-alkenyl arene should be between 8 and 55% by weight of the block copolymer, preferably between 10 and 30% by ' weight.
The halogenated thermoplastics include homopo:Lymers and copolymers derived from tetrafluoroethylene, chloro-trifluoroethylene, bromotrifluoroethylene, vinylidene fluorideg and vinylidene chloride.
Polytetrafluoroethylene (PTFE) is the name given to fully fluorinated polymers of the basic chemical formula -CF2)n which contain 76% by welght fluorine. ~:
These polymers are highly crystalllne and have a crystalline \

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~ ~9 ~ 2 melting point of over 300C. Commercial P'l'~'E is ava:i]able under the trade ~ T~F'LON~ and under ttle trade ~m~
FLIJON ~ . Polychlorotrirluoroethylene (PCTl~E) arId po]y-brornotrifluoroethylene (PBTFE) are also available in hirrh 'i molecular weig~ts and can be employed :in the ~)reselll; in-vention.
Especially prcfe~rred halogenated polymers are homo-polymers and copolymers Or vinylidene f:Luoride. Poly-(vinylidene rluoride) homopolymers are the part;alIy fluor:inated polymer-3 Or the chemica] formula -~-C~12 - -Cl These polymers are tough linear polymers with a crystalLirIe melting point ~' 170C. Commercial homopolymer is availab~e under the trade ~4 KYNAR ~- The term "poly(v;nylidene fluoride)" as used herein refers not only to the norrnalIy -solid homopolymers of vinylidene rluoride, but also to the normally solid copolymers of vinylidene fluoride contalning at least 50 mol.% of polymerized vinylidene fluoride unita, preferably at least 70 mol.% vi~nylidene fluoride and more~
preferably at least 90 mol.%. Suitable comonomers are halogenated olef'ins containing up to 4 carbon atoms, rOr example, sym. dichlorodifluoroethylene, vinyl fluoride, vinyl chloride, vinylidene chloride, perfluoropropene,per-fluorobutadiene, chlorotrifluoroethylene~ trichloroethyl,ne and tetraf'luoroethylene. '~
~nother useful group of halogenated thermoplastics ~`
include homopoly~ers and copolymers derived f'rom vinylidene chlvride. Crystalline vinylidene chloride copolymers are ' ` ' ' , ,: :
' ' ' especially prererred. The normally crystalline v:inylidene chloride copolymers that are use~ul ln the present in-vention are those containing at least 70% by weight Or vinylldene chloride together with 30% or less Or a co-polymerizable monoethylenic monomer. Exemplary of such ;~
monomers are vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, alkyl and aralkyl acrylates having alkyl and aralkyl groups Or up to about 8 carbon atoms, acrylic acid, acrylamide, vinyl alkyl ethers,~ -vinyl alkyl ketones, acrolein, allyl ethers and others, butadiene and chloropropene. Known ternary composition~s -~
also may be employed advantageou~sly. Representative of such polymers are those composed of at least 70% by~weight of vinylidene chloride with the remainder made up of,~for example, acrolein and vinyl chloride~ acrylic acid and aorylonitrile, alkyl acrylates and alkyl methacrylates, acrylonitrile and butadiene, acrylonitrile and itaconic acid, acrylonitrile and vinyI acetate~ vinyl propionate or vinyl chloride, allyl est~ers or ethers and vinyl chloride, butadiene and vinyl acetate, vinyl propionate, or vinyl chloride and vinyl ethers and vinyl chloride.
Quaternary polymers o~ similar monomeric composition will also be known. Particularly useful for the purposes the present invention are copolymers of f'rom 70 to 95% by weight vinylidene chloride with the balance being vinyl chloride. Such copolymers may contain conventional amounts -15- ~ 2 ~

ancl types of plasticizers, stabilizers~ nucleators and extrusion aids. Further, blends of two or more of such norrnally crystalline vinylidene chloride polymers may be used as well as blends comprising such normally crystalline polymers in combination with other polymeric modifiers, e.g., the copolymers of ethylene-vinyl acetate, styrene-maleic anhydride~ styrene-acrylonitrile and poly-ethylene. ~;
The term "dissimilar engineering thermoplastic resin" ;
refers to engineering thermoplastic resins different from those encompassed by the halogenated thermoplastic polymer : .
present in the compositions according to the invention.
The term "engineering thermoplastic resin" encompasses ;~
the various polymers found in the classes llsted in Table A
below and thereafter defined~in the specification.
TABLE A
1. Polyolefins :
; 2. Thermoplastic polyesters 3. Poly(aryl ethers) and poly(aryl sulphones) ~20 4. -Polycarbonates 5. Acetal resins 6. Thermoplastic polyurethanes 7. Polyamides ô. Nitrile resins Preferably these engineer~ing thermoplastlc resins have glass transition temperatures or apparent crystalllne -'','' ~ :

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melting points (de~ined as that temperature at which the modulus, at lo~ stress9 shows a catastrophic drop) of over 120C, pre~erably between 150C and 350C, and are capable of forming a continuous network structure through a therma]ly reversible cross-linking mechanism.
Such thermally reversible cross-linking mechanisms in-clude crystallites, polar aggregations, ionic aggregations, lamellae, or hydrogen bonding. In a specific embodiment, where the viscosity of the block copolymer or blended bloc~ copolymer composition at processing temperature Tp and a shear rate of 100 s 1 is n, the ratio of the viscosity of the engineering thermoplastic resins, or blend of engineering thermoplastic resin with viscosity modifiers to n may be between 0.2 and 4.0, preferably o.8 and 1.2. ~s used in the specification and claims, the viscosity of the bloc~ copolymer, halogenated thermoplastic polymer and the thermoplastic engineering resin is the~
"melt viscosity" obtained by employing a piston-driven ~ ;
capillary melt rheometer at constant shear rate and at some consistent temperature above melting, say 260C.
The upper limit (350C) on apparent crystalline melting .
point or glass transition temperature is set so that the -~
resln may be processed in low to medium shear rate equipment at commercial temperature levels of 350C
or less.
The engineeringthermoplastic resin includes also , ~

blends of various engineering thermoplastic resins and blends with additional viscosity modifying resins.
These various classes of engineering thermoplastics are defined below. ?
The polyolefins, if present in the compositionsac-cording to the invention are crystalline or crystallizable.
They may be homopolyrners or copolymers and may be derived from an alpha-olefin or l-olefin having 2 to 5 carbon ;
atoms. Examples of particular useful polyolefins include low~density polyethylene, high-density polyethylene, iso-tactic polypropylene, poly(l-butene), poly(4-methyl-l-pentene), and copolymers of 4-methyl-l-pentene with linear or branched alpha-olefins. A crystalline or crystallizable structure is important in order for the polymer to be capable of forming a continuous structure with the other polyrners in the polymer blend according ~ ~;
to the invention. The number average molecular weight of the polyolefins may be above lO,OOO, preferably above 50,000. ;~
In addition, the apparen~ crystalline melting point may be above 100C, preferably between 100C and 250C, and more preferably between l40C and 250C. The preparatio~ of these various polyolefins are well known. See generally l'Olefin Polymers", Volume 14, Kirk-Othmer Encyclopedia of Chemical Technology~ pages 217-335 (1967).
When a high-density polyethylene is employed, 1~t has an approximate crystallinity of over 75% and a dens1ty in . ~

kilograms per litre (kg/l) Or between o.9LI and 1.0 while when a low density polyethylene is employed, it has an approximate crystallinity of over 35% and a density Or between 0.90 kg~l and o.9ll kg/l. The composition ac-cording to the invention may contain a polyethylene havinga number average molecular weight Or 50,000 to 500,000.
When a polypropylene is employed, it is the so-called isotactic polypropylene as opposed to atactic polypropylene. The number ~verage molecular weight of tho ~lO poly~ropyleneenployedr~Y~e in exc~ss o~ 100~000. Th( poly-propylene may be prepared using methods Or the prior art. Depending on the specific catalyst and polymer ization conditions employed, the polymer produced may contain atactic as well as isotactic, syndiotactic or so-called stereo-block molecules. These may be separatcd by selective solvent extraction to yield products ~, low atactic content that crystallize more completely.
The preferred oornmercial polypropylenes are generally prepared using a so]id, crystalline, hydrocarbon-in~
soluble catalyst made from a titanium trichloride com-position and an aluminium alkyl compound, e.g., tri~
ethyl aluminium or diethyl aluminium chloride. If desired, the polypropylene employed is a copolymer containing rninor (1 to 20 per cent by weight) amounts of ethylene or another alpha-olefin as comorlorner.

The poly(1-butene) preferably has an isotactic structure.
The catalys-ts used in preparing the poly(1-butene) are preferably organo-metall;c compounds commonly referred to as Ziegler-Natta catalysts. A typical catalyst is~the interacted product resulting from mixing equimolar quan~
tities of titanium tetrachloride and triethylaluminium.
The manufacturing process is normally carried out in an lnert diluent such as hexane. Manufacturlng operatlons 3 in all phases of polymer formation, are conducted in such : ~ -a manner as to guarantee rigorous exclusion o~f water~even in trace amounts. -One very sùitable polyolefin is poly(4-methyl-1-pentene).
Poly(4-methyl-1-pentene) has an~apparent crystalli~ne mel~t~
ing point of` between 240 and 250C and a~relatlve denslty ;~
of between 0.80 and 0.85. Monomeric 4-methyl-1-pentene is commerclally manufactured by~the alkall-metal oatalyzed ;~ dimerization of propylene. The homopolymerization Or ; 4-methyl-1-pentene with Ziegler-Natta catalysts is described in the Kirk Othmer Enclopedia of Chemical Technology, ~ ~ -.:
20 ~ Supplement volume, pages 789-792 (second edltion, 1971).
However, the isotactic homopolymer of 4-methy1-1-pentene -has certain technical defects, such as brittleness and :
inadequate transparency. Therefore, commercially available ~`
poly(4-methyl-1-pentene) is actually a copolymer with minor proportions of other alpha~olefins, together with the addition of suitable oxidation and melt stabilizer :,

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systems.These copolymers are described in the Kirk-Othmer Encyclopedia of Chemical Technology, Supplement volume, pages 792-907 (second edition, 1971), and are B available under the trade *Q~e TPX ~) resin. Typical alpha-olefins are linear alpha-olefins having from 4 to 18 carbon atoms. Suitable resins are copolymers of 4-methyl-1-pentene with from 0.5 to 30% by weight of a linear alpha-olefin.
If desired, the polyolefin is a mixture of various polyolefins. However, the much preferred polyolefin is isotactic polypropylene.
The thermoplastic polyesters, if present in the com-positions according to the invention, have a generally - -crystalline structure, a melting po1nt over 120C,~and are thermoplastic as opposed to thermosetting.
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' ' ' One particularly useful group oi' polyesters are those ~ :
thermoplasti.e polyesters prepared by eondensing a di-earboxylic aeid or the lower alkyl ester, aeid halide, or anhydride derivatives thereo~ with a glycol, aecording to methods well known in the art. .- -Among the aromati.c and aliphatic dicarboxylic aeids suitable for preparing polyesters are~oxa.lie:~acid~ malonie aeid, succinic acid, glutaric acid, adipi.c aeid? suberic aeld, azelaie aeld, sebaeie aeid, terephthalie acld, L50.
~phthalie aeid, p-earboxyphenoaeetlc acid,~p,p'~i.carboxydi.phenyl, :-.
p,p'-dicarboxydLphenylsulphone, p-carboxyphenoxyaoetic acLd~
~; p-earboxyphenoxypropi.oni.e aeid,~p-earboxyphenoxybutyr-ie:aeid, .
:
p-earboxyphenoxyvalerio acid, p-carboxyphenoxyhexdnoic aeid, : p9p'-di;oarboxydiphenylmc~thane, p,p-dicarboxyd;phenyl.propQne,, p,p'-dicarboxydiphenyloetane, 3-alkyl^-4~ earboxyethoxy~
~benzole aeld, 2,6:-naphthalene dlearboxylie aeid, and 2,'(~
~:: naphthalene diearboxylie acid~. Mixtures of dicarboxylie ~ ~ .`
aeids ean also be~employed. Terephthalle aeid~is partieularly :~
preferred.
20 : ~ The glDcols~suitable ror preparing the polyesters include straight-chain alkylene~glycols of 2 to 12 oarbon atoms, such as ethylene glycol, 1,3-propylene glycol~
1,6~hexylene glyeol, 1,10-deeamethylene glyeol, and 1,12~
dodeearnethylene glyeol. Aromatie glyeols ean be substltuted ~:
in whole or in part. Suitable aromatic dihydroxy compounds :~
inelude p~xylylene glyeol, pyroeateehol, resoreinol, hydroquinone~ or alkyl-substituted derivatives Or these compounds. Another su:itable glycol :is 1,4-cyclohexane dimethanol. Much preferred ~lycols are ~e straight-chain alkylene glycols having 2 to 4 carbon atoms.
A preferred group Or polyesters are poly(ethylene terephthalate), poly(propylene terephthalate), and poly-(butylene terephthalate). A much prererred polyester lS
poly(butylene terephthalate). Poly(~butylene terephthalat,~
a crystalline copolymer, may be formed by the polycondensation of 1,4-butanediol and dimethyl terephthalate or terophthal.ic ~.
~ acid, and has the~generalized formula~
, ~

~ ~ t~ o~
n ~ ~ -where n varies from 70 to 140. The avera~e molecular we ~,'rht - ~of the poly(butylene terephthalate~ preferably varles from ~ 20,000 to~25,000.
Commercially available poly(butylene terephthalat~e) is B available under the trade ~ VALOX ~ thermopla;stio~
poIyester. Other comrnercial polymers include CELANEX
TENITE ~ and VITUF ~
~ . .
Other useful polyesters include the cellulosic esters.
The thermoplastic cellulosic esters employed herein are ~ ~;
widely used as moulding, coating and film-forming materials .

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and are well known. These materials include the solid thermoplastic forms of cellulose nitrate, cellulose acetate (e.g., cellulose diacetate, cellulose tri-acetate), cellulose butyrate, cellulose acetate butyrate, : -cellulose prop:ionate, cellulose tridecanoate, carboxy~
methyl cellulose~ ethyl cellulose, hydroxyethyl cellulose and acetylated hydroxyethyl cellulose as described on pages 25-28 of Modern Plastics E:ncyclopedia~ l9ll-72, and references listed there;n.
Another useIul polyester is a po]ypivalolactono. Poly-pivalolactone is a lirlear polymer having recurring ester structural units mainly of the formula C~2 - C(CH3)2 -C(0)0 -i.e., units derived from pivalolactone. Preferably, the poly-ester is a pivalolactone homopolymer. Also included~ however, are the copolymers of pivalolactone with no more than ~() nlol.
:
~ preferably not more than lO mol.% Or another beta-propio-~!
lactone~ such as beta-propiolactone, alpha,alpha-d;athyl~
beta-propiolactone and alpha-methyl-alpha-ethyl-beta-propio~
lactone. The term ~îbeta-propiolactones" refers to beta ~ ~
propiolactone (2-oxetanone) and to derivatives thereof which -.
carry no substituents at the beta-carbon atom of the lactone ring. Preferred beta-propiolactones are -those containing a tertiary or quaternary carbon atom in the alpha-position relative to the carbonyl group. Especially preferred are the alpha~alpha-dialkyl-beta-propiolactones wherein each of the alkyl groups independently has from one to four carbon atoms.

' Examples Or useful monomers are:
alpha-ethyl-alpha-methyl-beta-propiolactone, alpha-methyl-alpha-isopropyl-beta-propiolactorle, alpha-ethyl-alpha~n-butyl-beta-propiolactone, alpha-chloromethyl-alpha-methyl-beta-propiolactone, alpha,alpha-bis(chloromethyl)-beta-propiolactone, and ~
alpha,alpha~dimethyl~be~a-propiolactone (`pivalolactone). :
These polypi.valolactones have an average molecular we:ight ln excess Or 20,000 and a meltlng point in excess of 120C.
~ Another useful polyester is a polycaprolactone~
Preferred poly(~~caprolactones)~are~substantially~llnear :~ polymers in which the repenting unit is~
. ,: , 0 - Cll~ - Cl12 - CH2 - ~ C~

These polymers have similar propertie~) to the polypivalo~:
~ lactones and may ~e prepared:by a similar po:lymerization :~
:mechanism.
Various polyaryl poIyether~s are also useful as enginee:r-ing thermoplastic~resins. The~poly(aryl polyethers) whlch :
: may be present in the composition according to the invention include the linear thermoplastic polymers composed Or re~curring units havin~ the formula~

0 - G - O - G'~
wherein Gisthe residuum of a dihydric phenol selected from ~.
the group consisting Or:

:

and ~ R ~ D 3 III

wherein R represents a bond between aromatic carbon atoms, - O , - S , - s-~s~-~or a d,ivalent hy~rocarbon radica1 ~:~
havin~ from l to 1R carbon~atoms inclusive, and G' is the ~', 5' residuurn of a dibromo or di-iodoben~enoid compound ~ ~
,.- .
selected ~rom the group consisting Or: ::

and R' ~ V

~wherein R' represents a bond between aromatiG carbon atoms, :
- O , - S - , - S- S - ,or a divalent hydrocarbon ,:
radical having from l to 18 carbon atoms inclusive:, w.ith :
the prov.isions that when R is O - , R' is other than : ~ :
O - , when R' is O , R is other than - O - ;
when G is II, G' is V~ and when G' is IV, G is III. :

:' Polyarylene polyethers Or thi.s type exhibit excellent physicalproperties as well as excellent thermal oxidative and chemical stability. Cornmercial poly(aryl po:Lyethers) are ~ available under the trade ~ ARYLON T ~ Polyaryl ethers~
having a melt temperature of between 280C and 310C.
Another group of useful engineering thermoplastic resins inc]ude aromati.c poly(sulphones) comprising re~
peating un;.ts of the formula:

- Ar - S02 in which Ar is a bivalent aromatic radical and may vary from unit to unit in the polymer chain (so as to form co-polymers Or various kinds~. Thermoplastic poly(sulphones) generally have at least some units of the structure:
~_Z-~

~ S2 in which Z is oxygen or sulphur or the residue of an aromatic diol, such as a 4,4'-bisphenol. One example of ~
such a poly(sulphone) has repeating units Or the formula: ~-~9-0 ~3so2- '~

-27~

another has repeatlng units of the forTnula: :
~9 s ~73 so;~ ~ ~ ~

~ and others have repeating units of the formula: `

_~_so ~ ~r~_~3c~
~ CH3 :~or copolymerized units in various proport:~ons Or the formula~

and ~ 9 - ~ - 502 : Ibe~lhermopl~stlc~poly(sulpbo-,s) nay also b~e~ epeat~g unlts having the formula~
~ 9 so~

PoIy(ether sulphones) having repeating units of~the following structure: :

:

t 3-o~so~

and poly(ether sulphones) having repeating units Or the following structure~
.~ _ ~_So~3-o~3-cc~l3~3o- _ : ~
:~ ~ ~ C113 ~ n : are also useful:as en~,ineering thermoplastic:res Ins : The~polycarbonat~s which may be presen t I n the com~
positions:according to the :invention are~of the:general~
formulae~

Ar- A- Ar- /-C - 0 Ar- O -C- 0 whereln Ar represents a phenylene~or nn~alkyl,~ alkoxy,~
halogen or nitro-substituted phenylene;group; A repres~ents a carbon-to-carbon bond or an alkyl~ldene, cycloalkylldene, alkylene, cycloalkylene~ azo,~imino, sulphur, oxygen,~
sulphoxide or sulphone group, and n is at least two.

' : ' -29- ~
' ~;','' The preparation Or the polycarbonates is we~ll known.
A pref`erred method of preparation ls based on the reaction carried out by disso]ving the dihydroxy component in a base, such as pyridine and bubbling phosgene into the stirrcd solution at the desired rate. Tertiary amirl~s may be used to catalyze the reaction as well as to act as acid acceptors throughout the reaction. Since the reaction is normally exothermic, the r'~te of phosgene addition can be used to control the reaction temperature. The reactions generally utllize equimolar amounts o~ phosgene and~di~
hydroxy reactants, however, the moLar ratios can be varl~d dependent upon thc reactlon conditions.
n the ~ormulae I and II ment~oned, Ar and A are, ;~
preferably~ p-phenylene~and lsopropyli~dene, respe~ctively.
This polycarbonate is prepared by reacting para,para'qso~
propylide~nediphenol with phosgene and~is sold under ti~e ;~
trade mark LEXAR~ and under the trade marh MERLON ~
This commercial polycarbonate has a molecular weight Or around 18,000~, and a melt t~emperature of over 230C.
~20 Other polycarbonates may be prepared by reacting other dihydroxy compounds, or mixtures of dihydroxy compounds, with phosgene. The dihydroxy compounds may lnclude aliphatlc~

::
dihydroxy compounds although ~or best hlgh temperature properties aromatic rings are essential. The dihydroxy compounds may include wlthin the structure diurethane linkages. Also, part Or the structure may be replaced by siloxane linkage.

The acetal resins wh:ich may be present in the com-positions according to the invention include the hi~h ~:
molecular weight polyacetal homopolymers madc by polymer-izing formaldehyde or trioxane. These polyacetal homo- :~
B polymers are commercial].y available under~the trade t~m~ :~
DELRIN A related polyether-type resin i.s ava;.lable under the trade ~ffle PENTON ~ and has the structure:
_ Cll2C~. : -_ _o ~ C~12 - G---Cll2- . .:~ :
: C~12Cl : ~ : n~

The acetal resin prepared from formaldehyde has a hi~h molecu~lar weight~and a struct:ure typlfied:by tbe r ~ - H- 0~ ( CH2- 0- Cll2- Oj~------H~

; lO where terminal groups are derived from controlled amounts Or water and~the x d~enotes a large (preferab:ly 1500) number of formaldehyde units linked in head-to-tail fashion~ To in~
crease thcrmal and chemlcal resistance, termina1~groups are typically converted~to esters~or ethers.
Also included in the term polyacetal resins are the polyacetal copolymers. These copolymers include block co~
polymers of formaldehyde with monomers:or prepolymers of :: :
other materials capable Or providing actlve hydro~ens, ~ :
:~

:'~ , . :, . : . ": ., such as alkylene glycols, polythiols, vinyl acetate-acrylic acid copolymers, or reduced butadiene/acrylonltrile polymers. ~
Celanese has commercially available a copolymer o~ -formaldehyde and ethylene oxide under the trade ~4 C~LCON (~
that is userul in the blends of the present invention. These copolymers typically have a structure comprising recurring units having the formula: ~ ~

wherein each R1 and R2 ls selected rrom the group consistlnC ~ ;
of hydrogen, lower alkyl and lower halogen substituted ~
alkyl radicals and wherein n is an lnte~er ~rom zero to three and wherein n is zero in from 85% to 99.9% of the recurrlng units.
:
Forma}dehyde and trioxane can be copolymerlzed~wlth ~ ;
other aldehydes~ cyclic ethers, vinyl compounds, ketenes, cyclic carbonates, epoxides, lsocyanates and ethers. These compounds include ethylene oxide, 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepene, epichlorohydrin, propylene oxide, isobutylene oxideg and styrene oxide. -~

-32~ 2~

Polyurethanes, otherwise known as isocyanate resins, also can be employed as engineering thermoplastic resin as long as they are thermoplastic as opposed to thermosetting.
~or example, polyurethanes formed from toluene di-iso-cyanate (TDI) or diphenyl methane L~,L~~di-isocyanate (MDI) and a wide range of polyols, such as polyoxyethylene glycol, polyoxypropylene glycol, hydroxy-termlnated polyesters, polyoxyethylene-oxypropylene glycols are suitable.
These thermoplastic polyurethanes are available under L~l the trade ~ Q THANE ~ and under the trade ~ ~ -PELLETHANE @ CPR.
By polyamide is meant a condensation product which contains recurring aromatic andtor aliphatic amide groups as integral parts of the main polymer chain, such products being known generically as "nylons". A polyamide may be obtained by polymerizing a mono-aminomonocarboxylic acid ~ ~ -or an internal lactam thereof having at least two carbon atoms between the amino and carboxylic acid groups; or by polymerizing substantially equimolar proportions of a diamine which contains at least two carbon atoms between ~ ~ .
the amino groups and a dicarboxylic acid; or by polymer-izing a mono~aminocarboxylic acid or an internal lactam thereof as defined above together with substantially equi- ;~
molar proportions of a diamine and a dicarboxylic acid.
The dicarboxylic acid may be used in the form of a functional derivative thereof, for example an ester.

The term "substantially equimolecular proportions"
(of the diamine and of the dicarboxylic acid) is used to ~:
cover both strict equimolecular proportions and the slight departures therefrom which are involved in conventional \\ ' ~., ~: :

;

:
~'~

techniques ror stabilizing the viscosity o~ the resultant ~-~
polyamides.
As examples of the said mono-aminomonocarboxylic acids or lactams thereor there may be mentioned those compounds containing ~rom 2 to ~6 carbon atoms between the amino and carboxylic acid group.s, said carbon atoms rorming a ring with the CO.NH- - group in the case o~ a lactam. As particular examples of aminocarboxylic acids and lactams there may be mentioned ~-aminocaproic acid~ butyrolactam, pivalolactam, caprolactam, capryl-lactam, enantholaotam, undecanolactam, dodecanolactam and 3- and 4-amino benzoic acids.
Examples o~ the said diamines are diamines of the general rormula H2N(C~I2)nNH21 wherein n is an integer Or ~rom 2 to 16, such as trimethylenediamine, tetramethylene-diamine, pentamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, hexadeca methylenediamine, and especially hexamethylenediamine.
C-alkylated diamine~sg e.g., 2,2-dimethylpentamethylene~
diamine and 2,2,4-and 2,4,l1-trimethylhexamethylenediamine are further examples. Other diamines which may be mentioned as examples are aromatic diamines, e.g., p-phenylene-diamine, 4~4'-diaminodiphenyl sulphone 9 4,4'-diaminodi- -~
phenyl ether and 4,41 -diaminodiphenyl sulphone, 4,4~-di-aminodiphenyl ether and 4,4'-diaminodiphenylmethane; and cycloaliphatic diamines, for example diaminodicyclohexyl-methane.

. :
. .: : , ' ' ~91~4~

The said dicarboxylic acids may be arornatic, for example isophthalic and terephthalic acids. Prererred dicarboxylic acids are of the ~ormula HOOC.Y.COOH, ~;~
wher-ein Y repre~ents a divalent aliphatic radical containing at least 2 carbon atoms, and examples o~
such acids are sebacic acid, octadecanedioic acid, suberic acid, azelaic acid~ undecanedioic acid, glutar:ic acid, pimelic acid, and especially adipic acid. Oxalic acid is also a pre~rerred acid. ~ -Speci~ically the following polyamldes may be ;n~
corporated in the thermoplastic polymer blends o~ the invention-polyhexamethylene adipamide (nylon 6:6) polypyrrolidone (nylon 4) ~ ~
polycaprolactam (nylon 6) ~ `
polyheptolactam (nylon 7) polycapryllactam (nylon 8) polynonanolactam (nylon 9) polyundecanolactam (nylon 11) polydodecanolactam (nylon 12) polyhexamethylene azelaiamide (nylon 6:9) polyhexamethylene sebacamide (nylon 6:10) polyhexamethylene isophthalamide (nylon 6:iP) polymetaxylylene~ipamide (nylon MXD:6) polyamide of hexamethylene diamine and n-dodecanedioic acid (nylon 6:12) -36- ~ :
' ~ '.' polyamide of dodecamethylenediamine and ~
n-dodecanedioic acid (nylon 12:12). : :
Nylon copolymers may also be used, for example co-: polymers Or the rollowing:
hexamethylene adipamide/caprolactam (ny:lon 6:6/6) r~
hexamethylene adipamide/hexamethylene-isophtha1amide (nyl.on 6:6/6ip) ~ i:
hexamethylene adipamide/hexamethylene-terephthal.amide i~
(nylon 6:6/6T) trimethylhexamethylene oxamide/hexamethylene oxamide: ~ ;:
(nylon tri.methyl-6:2/6:2) hexamethylene adipamide/hexamethylene-azelaia.mlde (nylon ~:6/6:9) hexamethylene adipamide/hexamethylene-azelaiamide~
caprolactam (nylon 6:6/6:9/6). :~
Also useful is nylon 6:3. This polyamide is the product of the dimethyl ester o~ terephthalic:acid and~a mixture~or :~
: isomeric trimethyl hexamethylenedlamine.
; :~:
Preferred nylons i.nclude nylon 6,6/6, 11, 12, 6/3 and 6/12.
The number average molecular weights of the polyamides may be above 10,000. ~ -~ , ,, .'; ' .
, `,'' . , . ' ' ':

, . ~ : ~:. ' , ' --37- ~ ~9 8 ~1 The nitrile resins useful as engineering therrnoplastic resin are those therrnoplastic materials having an alpha,beta-olefinically unsaturated mononitrile content of 50% by weight or grea~er. These nitrile resins rnay be homopolymers, copolymers, grafts of copolymers onto a rubbery substrate, or blends of homopolymers and/or copolymers.
The alpha,beta-olefinically unsaturated mononitriles encompassed herein have the structure C~2 C --CN

where R is hydrogen, an alkyl group having from 1 to 4 carbon atoms, or a halogen. Such compounds include a~ylo-nitrile, alpha-bromoacrylonitrile, alpha-fluoroacrylo-nitrile, methacrylonitrile and ethacrylonitrile. The most preferred olefinically unsaturated nitriles are acry:lo-nitrile and methacrylonitrile and mixtures thereof.
These nitrile resins may be divided into several classes on the basis of cornplexity. The simplest molecular ~ ~9

-3~-structure is a random copolymer, prcdominantly acrylc)nitrile or methacrylonitrile. The most common example ls a styrene-acrylonitrile copolymer. Block copolymers Or acrylonitrile, in which long segments of polyacrylonitrile alternate with segments Or polystyrene, or of polymethyl rnethacrylate, are also known.
Simultaneous polymerization of more than two co-monomers produces an interpolymer, or in the case Or -three components, a terpolymer. A ]arge number Or co~
monomers are known. These include alpha-olefins Or rrom 2 to 8 carbon atoms, e.g., ethylene, propylene, iso- `~
butylene, butene-1, pentene-1, and their`~halogen and aliphatic substituted derlvatives as represented by vinyl ; `
chloride and vinylidene chloride; monovinylidene aromatic hydrocarbon monomers Or the general formula~

2C~C \
2 ~ ;
wherein P1 lS hydrogen, chlo~ine or methyl and R2 is an aromatic radical of 6 to 10 carbon atoms which may also contain substituents, such as halogen and alkyl groups attached to the aromatlc nucleus, e.g., styrene, alpha~
methyl styrene, vinyl toluene, alpha-chlorostyrene, ortho~
chlorostyrene, para-chlorostyrene, meta-chlorostyrene, ~ ~ .
ortho-methyl styrene, para-methyl styrene, ethyl styrene, ~ ~ ~ 2 _~9_ :

isopropy]. styrene, d:ic~llorostyrelle arl(l viny:l n~)htha:Lorle.
Especially preferre(i comorlomers are i.sobutylene and st;yrene.
Anot}ler group of` comonomers are vinyl ester monorners Or the general rormula:

1~5C = (~
O
C=O

wherein R3 i~ selected f'rom the p,roup comprising hydroGer aLkyl groups o~ 'rom 1 to 10 carbon atoms, aryL groups from 6 to 10 carbon atoms including the carbon atoms in ring ~ubstituted alkyl substituents; e.g., v:inyl .rorm:ite, vinyl acetate, vinyl propionate and vinyl benzoate.
Similar to the l'oregoing and also useful are the vinyl ether monomers of' the general rorrnula:

l2C C~l- 0 -R4 wherein R4 is an alkyl group o~ from 1 to 8 carbon atoms, an aryL group of from 6 to io carbons, or a monovalent aliphatic radical of from 2 to 10 carbon atoms, which aliphatic radical may be hydrocarbon or oxygen-containing, e~g., an aliphatic radical with ether linkages, and may -also contain other substituents, such as halogen and carbonyl. Examples of these monomeric vinyl ethers include vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl 2-chloroethyl ether, vinyl phenyl ether, vinyl iso- .
:
': ~ ' ':

-l~o- : :

butyl ether, vinyl. cyclohexyl ether, p-butyl cyclohexyl ether, vinyl ether or p-chlorophenyl glycol.
Other comonorners are those comonomers which contain a mono- or dinitrile runction. Examples of these :i.ncIude methylene glutaronitr:ile, (2,4-dicyanobutene-l), vinyl-idene cyanide, crotonitrile, fumarodinitrile~ maleodl- ;~.
ni.trile.
Other comonorners include the esters Or olefi.ni.cally unsaturated carboxylic acids,preferably the lower alkyL
esters of alpha,beta o:1efin:ically unsaturated carboxy:Lic acids and more prererred the esters hav~ng the structure~

CH2--C--COOR2 `
R~

wherein Rl is hydrogen, an alkyl group having from l to 4 carbon atoms, or a halogen and R2 is an alkyl group l~av.~
rrom l to 2 carbon atoms. Compounds of this type include ..
methyl acryIate, ethyl acrylate, methyl methacrylate, ethyl methacrylate and methyl alpha-chloro acrylate. Most :~
preferred are methyl acrylate, ethyl acrylate,~ methyl me-tha~
crylate and ethyl methacrylate.
AnDther class of nitrile resins are the graft co- .
polymers which have a polymeric backbone on which branches o~ another polymeric chain are attached or gralted. . ~-Generally the backbone is preformed in a separate reactîon.
Polyacrylonitrile may be grafted with chains of styrene, ~8~

-L~l-vinyl acetate, or methyl methacrylate, ror example. The backbone may consist of one, two, three, or more com-ponents, and the grafted branches may be compose(:l Or one, two, three or more comonomers.
The most pronlis:in~ products are the nitrile ~o-polymers that are partially grarted on a preI`ormed rubbery substrate. This substrate contemplates the use o~ a synthetic or natllral rubber cornponent such as poly-butadiene, isoprene, neoprene, nitrile rubbers, natural rubbers, acrylonitrilo-butadiene copolymers, ethy~ene-propylene copolymers, and chlorinated rubbers which are used to strengthen or toughen the polymer. This rubbery component may be incorporated into the nitrile conta~ning polymer by any of` the methods which are well known~to~
those skilled in the art, e.g., direct polymerization Or monomers, gra~ting the acrylonitrile monomer mixture onto the rubber backbone or physical admixtures o~ the rubbery component. Especially pre~erred are polymer blends derived by mixing a graft copolymer of the acrylonitrile and co-monomer on the rubber backbone with another copolymer of acrylonitrile and the same comonomer. The acrylonitrile~
based thermoplastics are f`requently polymer blends of a grarted polymer and an ungrarted homopolymer.
Commercial exarnples of nitrile resins include BAREX
210 resin~ an acry]onitrile-based high n;triIe resin con taining over 65% nitrile, and LOPAC ~ resin containing ,!,; ' ' " ' ' , ~

- Ll 2 over 70% ni-trile, three-follrths of it derived from metha-crylonitrile.
In order to better match the viscosity characteristics Or the thermoplastic engineering resin, the halogenated therrnoplastic polymer and the block copolymer, it is some-times useful to first blend the dissimilar thermoplastic enineering resin with a viscosity modifier before blending the resulting mixture with the halogenated thermoplastic polymer and block copolymer. Suitable viscosity modifiers have a relatively high viscosity, a melt temperature Or over 230C, and possess a viscosity that is not very ~
sensitive to changes in temperature. Examples of suit- -able viscosity modifiers include poly(2,6-dimethyl~
~ .
phenylene)oxide and blends of poly(2,6-dimethyl-1,4-phenylene)oxide with poly~styrene.
The poly(phenylene oxides~ included as possible viscosity modifiers may be presented by the following formula~
t~

wherein R1 is a monovalent substituent selected from the group consisting of hydrogen, hydrocarbon radicals free Or a tertiary alpha-carbon atom~ halohydrocarbon radicals '.~

/

:

32~.

having at least two carbon atoms between the halogen atom and phenol nucleus and being free of' a tertiary alpha-carbon atom, hydrocarbonoxy radicals free of`
aliphatic, tertiary alpha-carbon atoms, and halohydro-carbonoxy radicals having at least two carbon atomsbetween the halo~n atom and phenol nucleus and be:ing free of an aliphatic, tertiary alpha carbon atom; R'1 is the same as R1 and may additionally be a halogen; m is an ;
integer equal to at least 50, e.g., from 50 to 800 and prererably 150 to 300. Included among these preferred ~ ~ ~
polymers are polymers having a molecular wei~ht in the ~ -ran~e of between 6,ooo and 100,000, preferably ~lO,OOO. ~ `
Preferably, the poly~phenylene oxide) is poly(2,6-di-methyl-1,4-phenylene)oxide.
Con~nerciaIly, the poly(phenylene oxide) is avallable ~ `~
as a blend with styrene resin. These blends typlcally comprise between 25 and 50% by weight polystyrene units~
B and are available under the -~
` tradeJ~a NORYL ~ thermoplastic resln. The preferred ~20 molecular weight when empioying a poly(phenylene oxide)/
polystyrene blend is between 10,000 and 50,0003 pre~erably around 30,000.
The amount of viscosity modif'ier employed depends primarily upon the d;f`f'erence between the viscosi~ties O:r the block copolymer and the engineerirlg thermoplastic resin at the tenlperature Tp. The amounts may range f'rom O to lOO

- ~I Ll _ parts by weight viscosity modifier per 100 parts by weight engineering thermoplastic resin, preferably from 10 to 50 parts by weight per 100 parts of engineering thermoplastic ;~
resin.
There are at least two methods (other than the absence of delamination) by which the presence of an interlocking net-work can be shown. In one method, an interlocking network is shown when moulded or extruded objects made from the blends of this invention are placed in a refluxing solvent that quantitatively dissolves away the block copolymer and . ;;~ .: -,,,:
other soluble components, and the remaining polymer structure ~ 5.' '~
(comprising the thermoplastic engineering resin and the halogenated thermoplastic polymer) still has the shape and continuity of the moulded or extruded object and is ~ntact structurally without any crumbling or delamination, and ~ -; the r-efluxing solvent carries no insoluble particulate ;
matter. If these criteria are fulfilled, then both the unextracted and extracted phases are interlocking and continuous. The unextr~acted phase must be continuous ~20 because it is geometrically and mechanically intact.
The extracted phase must have been continuous before extraction, since quantitative extraction of a dispersed phase from an insoluble matrix is highly unlikely.
Finally, interlocking networks must be present in order - ':
to have simultaneous continuous phases. Also, confirmation of the continuity of the unextracted phase may be _l~5-confirmed by rnicroscopic examination. In the present blends containing more than -two components, the inter-locking nature and continuity of each separate phase may be established by selective extraction.
In the second method, a mechanical property such as tensile modulus is measured and compared with that expected from an assumed system where each continuous iso-tropically distributed phase contributes a fraction of the mechanical response, proportional to its compositional fraction by volume. Correspondence of the two values indicates presence of the interlocking network, whereas, if the interlocking network is not present, the measured value is different than that of the predicted value.
An important aspect of the present invention is that the relative proportions of the various polymers in the blend can be varied over a wide range. The relative proportions of the polymers are presented below ln parts by weight (the total blend comprising 100 parts)~
Parts by Preferred weight parts by ~-~
~ weight Dissimilar engineering thermoplastic resin 5 to 48 10 to 35 Block copolymer 4 to 40 8 to 20 The halogenated thermoplastic polymer is present ln an amount greater than the amount of the dissimilar engineering thermoplastic, i.e. 3 the weight ratio of , ', . ': . , . : ~ :
, ,, ,, .~:

-L~6~ B2~

halogenated thermoplastic to dissimilar engineerlng thermoplastic is greater than 1:1. Accordingly, the amount of halogenated thermoplastic may vary from 30 parts by weight to 9~ parts by weight, preferably from

4~ to 70 parts by weight. Note that the rrlinimum amount of block copolymer necessary to achieve these blends May vary with the particular engineering thermoplastic.
The dissiMilar engineering therMoplastic resin, halogenated thermoplastic and the block copolymer may be blended in any manner that produces the interlocking network. For example, the resin~ halogenated therMoplastic and block copolyMer May be dissolved in a solvent coMmon for all and coagulated by admixing in a solvent in which none of the polymers are soluble. But, a particularly 15~ useful procedure is to intimately mix the polymers in the forM of granules and/or powder in a high shear mixer.
"IntiMately mixing" means to MiX the polyMers with sufficient mechanical shear and therMal energy to ensure - ~
that interlocking of the various networks is achieved.
Intimate mixing is typically achieved by employing high .
shear extrusion coMpounding machines, such as twin screw coMpounding extruders and therMoplastic extruders having at least a 20:1 L/D ratio and a coMpression ratio of 3 or 4 The Mixing or processing temperature (Tp) is selected in accordance with the particular polymers to be blended.

9 ~
-47- ..

~or exarnple, when melt blending the polymers instead of sol.ution blendlng, it ~ill be necessary to select a process;.ng temperature above the melting ~J~ t of the highest melting point polymer. In addition, as explained more fully hereinafter, the processing temperature may also be chosen so as to permit the isoviscous mixing of the polymers. The mixing or processing temp~rature may be between 150 C and 400C, preferably between 230C and 300C.
~nother parameter that is important in rnelt blending to ensure the formation of interlocking networks is matching .-the viscosities of the block copolymer, halogenated thermo-plastic and the dissimilar engineering thermoplastic resin (isoviscous mixing) at the temperature and shear stress of the mixing process. The better the interdispersion of the engineering resin and halogenated thermoplastic in the .~ ~
block copolymer network, the better the chance for f-orm- :~
ation of co-continuous interlocking networks on subsequent ~ :
cooling. Therefore, it has been found that when the block ~;
copolymer has a viscosity n poise at temperature Tp and~
shear rate of 100 s 1, it is preferred that the engineer1ng thermoplastic resin and/or the halogenated thermoplasti.c have such a viscosity at the temperature Tp and a shear~
rate of 100 s 1 that the ratio of the viscosity of the ~. ;-block copolymer divided by the Viscoslty of the eng1neer-ing thermoplastic and/or halogenated thermoplastic be between 0.2 and L~.o, preferably between o.8 and 1.2. .~ ~:

~' ' Accordingly, as used herein, isoviscous mixing means that the viscosity of the block copolymer divided by the viscosity of the other polymer or polymer blend at the ~
temperature Tp and a shear rate of 100 s 1 is between ; ~-0.2 and ll.o. It should also be noted that within an extruder, there is a wide distribution of shear rates.
Therefore, isoviscous mixing can occur even though the viscosity curves of two polyrners differ at some of the shear rates.
In some cases, the order of mixing the polymers is critical. Accordingly, one may choose to mix the block copolymer with the halogenated thermoplastic or other polymer first~ and then mix the resulting blend with the dissimilar engineering thermoplastic, or one may simply mix all the polymers at the same time. There are many variants on the order of mixing that can be employed, resulting in the multi-component blends of the present invention. It is also clear that the order of mixing can be employed in order to better match the relative viscosities of the various polymers.
The block copolymer or block copolymer blend may be 8elected to essentially match the viscosity of the engineering thermoplastic resin and/or halogenated thermo-plastic. Optionally, the block copolymer may be mixed with a rubber compounding oil or supplemental resin as described hereinafter to change the viscosity charac- ;
teristics of the block copolymer. ~

19 ~f~98~

The particular physical properties of the block copolymers are important in forming co-continuous inter-locking networks. Specifically, the most preferred block copolymers when unblended do not melt in the ordinary sense with increasing temperature, since the viscosity of these polymers is highly non~Newtonian and tends to increase without limit as zero shear stress is approached.
Further, the viscosity of these block copolymers is also relatively insensitive to temperature. This rheological behaviou~t and inherent thermal stability of the block co~
polymer enhances its ability to retain its network -~
(domain) structure in the melt so that when the various blends are made, interlocking and continuous networks are formed.
The viscosity behaviour of the engineering thermoplastic resins, and halogenated thermoplastics on the other hand5 ;;
is more sensitive to temperature than that of the block co~
polymers. Aocordingly, it is often possible to;select a processing temperature Tp at which the viscosities of the ; ;b1ock copolymer and dlssimllar englneering resin and/or ~ -halogenated thermoplastic fall within the require~d range necessary to form interlocking networks. Optionally, a viscosity modifier, as hereinabove described, may first -.::, -:
be blended with the engineering thermoplastic resin or .
halogenated thermoplastic to achieve the necessary i :---viscosity matching. ~ ~

-50~ 8~

The blend of partial]y hydrogenated block copolymer, halogenated thermoplastic and dissimilar engineer:ing ther~oplastic resin may be compounded with an extending oil ordinarily used in the processing of rubber and plastics. Especially preferred are the types of oi] that are compatible with the elastomeric polymer blocks of the block copolymer. While oils of higher aromatics content are satisfactory, those petroleum-based white oils having low volatility and less than 50% aromatics content as determined by the clay gel method (tentative ASTM method D 2007) are particularly preferred. The oils ~ -preferably have an initial boiling point above 260C.
The amount of oil employed may vary from 0 to 100 phr (phr = parts by weight per hundred parts by weight of block copolymer), preferably from 5 to 30 phr.
The blend of partially hydrogenated block copolymer, halogenated thermoplastic and dissimilar engineerlng thermo-plastic resin may be further compounded with a resin. The additional resin may be a flow promoting resin~ such as an alpha-methylstyrene resin and an end-block plasticizing resin.

' ', ;'- ' 2~
:

Suitable end-block plasticizing resins include coumarone-indene resins, vinyl toluene alpha-methylstyrene co-polymers, polyindene resins and low molecular weight polystyrene resins. ^
The amount of additional resin may vary from 0 to ~;~
100 phr, preferably from 5 to 25 phr.
Further the composition may contain other polymers, fillers, reinforcements, anti-oxidants, stabilizers, fire retardants, anti-blocking agents and other rubber 10~ and plastic compounding ingredients.
Examples of fillers that can be employed are mentioned :: : : :
in the 1971-1972 Modern Plastics~Encyclopedia, pages 240-247.
:
Reinforcements are also useful in the present polymer blends. A reinforcement may be defined as the material that 15~ is added to a resinous matrix to improve the strength of the polymer. Most o~ these reinforcing materials are in~
organic or organic products Or high mo].ecular weight.
Examples of relnfor~ements are glass fibres, asbestos, -~
~, . . . .
boron fibres, carbon and gra;phite fibres, whiskers, quartz and silica fibres, ceramic fibres~ metal fibres, natural organic fibres, and synthetic organic fibres. Espeolal~y ;
preferred are rein~orced polymer blends containing 2 to 80 per cent by weight of glass fibres, based on the total weight of the resulting reinforced blend. ;~
The polymer blends of the invention can be employed as metal replacemerlts and :in those areas where h-igh performance is necessary.

.

-52- ~9~2~

In the illustrative Examples and the comparative Example ~iven be:Low, various polymer blends were prepared by mixing the polymers in a 3.125 cm Sterling Extruder having a ~enics Nozzle. The extruder has a 24:1 L/D
ratio and a 3.8:1 compression ratio screw.
The various materials employed in the blends are l,isted below:
1) Block copolymer - a selectively hydrogenated ~;
block copolymer according to the invention ~.
having a structure S-EB-S. ~;, B 2) Oil - TUFFLO 6056 rubber extending oil.
3) Nylon 6 - PLASKON ~ 8207 polyamide.
4) Nylon 6-12 - ZYTEL ~ 158 polyamide.

5) Polypropylene - an essentially isotactic poly-propylene having a melt flow index of 5 (230C/2.16 kg). ~ ;

6) Poly(butylene terephthalate) ("PBT") - VALOX
310 resin.

7) Polycarbonate - MERLON'~ M-40 polycarbonate.~: ~

8) Poly(ether sulphone) - 200 P. ~'

9) Polyurethane - PELLETHANE ~ CPR. ~:

10) Polyacetal - DELRIN ~ 500.
113 Poly(acrylonitrile-co-styrene) - BAREX ~ 210.
12) Fluoropolymer - TEFZEL ~ 200 poly(vinylidene fluoride) copolymer.

-5~ 9~Z~

In all blends containing an oi:l component, the block copolymer and oil were premixed prior to the addition o~
the other polymers.
Illustrative Example I
Various polymer blends were prepared according to the present invention. ~ blend Or two block copolymers o~ a higher and lower molecular weight was employed in the polymer blends in order to better match the viscosity with the fluoropolymer and/or other dissimilar engineer-ing thermoplastic resin. Comparative blends not containing a block copolymer were also prepared. However, these blends were not easily mixed. ~or example, blend 121 comprising the rluoropolymer and Nylon 6 su~fered ~rom extreme surging and a knobby gross pro~ile. In contrast, in each blend containing a block copolymer, the polymer blend was easily mixed, and the extrudate was homogeneous ;`~
in appearance. Further, in each blend containing a block copolymer, the resulting polyblend had the desired con-tinuous, interlocking networks as established by the ;~
crlteria hereinabove described.
The compositions, conditions and test results are presented below in Tables 1 and 2.
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The results of the above blends indicate the presence of unobvious properties for the blends. ~or example, by examining the ratio of the relative increase in Izod impact strength (at 23C) over the relative decrease in heat distortion temperature for polymer blends as the percerltage of block copolymer is increased frorn 0%
to 15% at a L:ixed 1:3 ratio Or fluoropolyrner to dis-similar engineering therrnoplastic, it can be seen that much larger than expected values are obtained. One skilled in the art would typically expect this value to be positive and less than 1. However, for blends con-taining Nylon 6 and polycarbonate, the ratios are 3.8 and minus 23 respectively. The minus value is partlcularly surprising since this indicates an increase in heat distortion temperature along with an increase in impact ~ ;
strength as the percentage of block copolymer is in-creased, which phenomeronis totally unexpected.

Claims (22)

C L A I M S

1. A composition containing a partially hydrogenated block copolymer comprising at least two terminal polymer blocks A of a monoalkenyl arene having an average molecular weight of from 5,000 to 125,000, and at least one inter-mediate polymer block B of a conjugated diene having an average molecular weight of from 10,000 to 300,000, in which the terminal polymer blocks A constitute from 8 to 55% by weight of the block copolymer and no more than 25% of the arene double bonds of the polymer blocks A
and at least 80% of the aliphatic double bonds of the polymer blocks B have been reduced by hydrogenation, characterized in that the composition comprises:
(a) 4 to 40 parts by weight of the partially hydrogen-ated block copolymer, (b) a halogenated thermoplastic polymer having a generally crystalline structure and a melting point over 120°C, (c) 5 to 48 parts by weight of at least one dissimilar engineering thermoplastic resin being selected from the group consisting of polyamides, polyolefins, thermoplastic polyesters, poly(aryl ethers), poly-(aryl sulphones), polycarbonates, acetal resins, thermoplastic polyurethanes, and nitrile resins, in which the weight ratio of the halogenated thermoplastic polymer to the dissimilar engineering thermoplastic resin is greater than 1:1 so as to form a polyblend wherein at least two of the polymers form at least partial continuous interlocked networds with each other.

2. A composition as claimed in claim 1, in which the polymer blocks A have a nwnber average molecular weight of from 7,000 to 60,000 and the polymer blocks B have a number average molecular weight of from 30,000 to 150,000.

3. A composition as claimed in claim 1 or 2, in which the terminal polymer blocks A constitute from 10 to 30% by weight of the block copolymer.

4. A composition as claimed in claim 1, in which less than 5% of the arene double bonds of the polymer blocks A and at least 99% of the aliphatic double bonds of the polymer blocks B have been reduced by hydrogenation.

5. A composition as claimed in claim 1, in which the halogenated thermoplastic polymer is a homopolymer or copolymer derived from tetra-fluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, vinylidene fluoride and vinylidene chloride.

6. A composition as claimed in claim 1, in which the dissimilar engineering thermoplastic resin has an apparent crystalline melting point in excess of 120°C.

7. A composition as claimed in claim 1, in which the dissimilar engineering thermoplastic resin is a thermoplastic polyester having a melting point in excess of 120°C.

8. A composition as claimed in claim 1, in which the dissimilar engineering thermoplastic resin is poly(ethylene terephthalate), poly (propylene terephthalate) or poly(butylene terephthalate).

9. A composition as claimed in claim 8, in which the dissimilar engineering thermoplastic resin is poly(butylene terephthalate) having an average molecular weight in the range of from 20,000 to 25,000.

10. A composition as claimed in claim 1, in which the engineering thermoplastic resin is a polycarbonate having the general formula:

I
or II

wherein Ar represents a phenylene or an alkyl, alkoxy, halogen or nitro-substituted phenylene group, A represents a carbon-to-carbon bond or an alkylidene, cycloalkylidene, alkylene, cycloalkylene, azo, imino, sulphur, oxygen, sulphoxide or sulphone group, and n is at least two.

11. A composition as claimed in claim 1, in which the engineering thermoplastic resin is a homopolymer of formaldehyde or trioxane.

12. A composition as claimed in claim 1, in which the engineering thermoplastic resin is a polyacetal copolymer.

13. A composition as claimed in claim l, in which the dissimilar engineering thermoplastic resin is a polyamide having a number average molecular weight in excess of 10,000.

14. A composition as claimed in claim 1, in which the engineering thermoplastic resin is a nitrile resin having an alpha, beta-olefinically unsaturated mononitrile content of greater than 50% by weight.

15. A composition as claimed in claim 14, in which the alpha, beta-olefinically unsaturatad mononitrile has the general formula:

wherein R represents hydrogen, an alkyl group having from 1 to 4 carbon atoms or a halogen.

16. A composition as claimed in claim 14 or 15 in which the nitrile resin is a homopolymer, a copolymer, a graft of a copolymer onto a rubbery substrate or a blend of homopolymers and/or copolymers.

17. A composition as claimed in claim 1, in which the composition contains the block copolymer and the dissimilar thermoplastic resin in an amount of from 8 to 20 parts by weight and from 10 to 35 parts by weight, respectively.

18. A composition as claimed in claim 1, in which the composition contains an extending oil in an amount of from 0 to 100 phr.

19. A composition as claimed in claim 18, in which the composition contains an extending oil in an amount of from 5 to 30 phr.

20. A composition as claimed in claim 1, in which the composition contains a flow-promoting resin as additional resin in an amount of from 0 to 100 phr.

21. A composition as claimed in claim 20, in which the composition contains a flow-promoting resin as additional resin in an amount of from 5 to 25 phr.

22. A composition as claimed in claim 20 or 21 in which the composition contains an additional resin selected from the group consisting of an alpha-methylstyrene resin, coumarone-indene resins, vinyl toluene-alpha-methyl-styrene copolymers, polyindene resins and low molecular weight polystyrene resins.