POLYMER BLENDS CONTAINING A POLYMER HAVING PENDANT OXAZOLINE GROUPS

Abstract: Thermoplastic polymer blends containing normally incompatible polymers are prepared by blending a first reactive polymer having repeating units containing pendant cyclic iminoether groups and a second reactive polymer having coreactive groups which are capable of reacting with the cyclic iminoether groups of said first reactive polymer to form linkages between the polymers. In one aspect, said blend is characterized by said first or second reactive polymer being blended or extended with miscible nonreactive polymer(s) to form a reactive blend thereof.

Description: POLYMER BLENDS CONTAINING A POLYMER HAVING PENDANT OXAZOLINE GROUPS This invention relates to a compatible blend of two or more normally incompatible polymers. More particularly, this invention relates to blends of a first reactive polymer or polymer blend containing pendant cyclic iminoether groups and another reactive polymer or polymer blend containing groups which react with cyclic iminoether groups to form linkages between the reactive polymers. At least one of the reactive polymers can. be extended with a miscible but nonreactive polymer or polymers to form a reactive blend thereof. It is often desirable to prepare blends of polymers which maximize the desirable properties but minimize the deficiencies of the component polymers. For example, monovinylidene aromatic polymers, such as polystyrene, have desirable properties such as the ability to be easily thermoformed and good mechanical characteristics. However, such monovinylidene aromatic polymers have certain undesirable properties such as poor environmental stress crack resistance (ESCR). On the other hand, polyolefins such as polyethylene or olypropylene have relatively good ESCR and low temper¬ ature properties but are not as readily thermoformed as desired. It would be highly desirable to provide a blend of a monovinylidene aromatic polymer and other polyolefins which exhibits the desirable properties but not the deficiencies, of the component polymers. Similarly, it is often desirable to blend other polymers in like manner. Unfortunately, however, such blends often do not exhibit these expected properties. Many such blends exhibit properties which are, in fact, far worse than those of the component polymers due to an incompat¬ ibility of the polymers. For example, monovinylidene aromatic polymers such as polystyrene and rubber modified -polystyrene are notably incompatible with many polymers -which would otherwise be advantageously blended therewith. Thus, most blends containing polystyrene and like polymers exhibit poorer properties than expected. Various methods have been proposed to prepare blends of normally incompatible polymers. Generally, these methods have focused on the use of grafting techniques or the use of a third component, a compati- blizing agent, in the blend. For example, in U.S. Patent Nos. 4 * 386,187 and 4,386,188 it is naught to prepare blends of polyole.fi.ns and a polystyrene using a styrene butadiene/styrene block copolymer. Compatibi- lizing agents which are ethylene/vinylacetate copolymers, ethylene/acrylic acid ester copolymers and ethylene/- methacrylic acid ester copolymers have also been taught for use in preparing blends of polystyrene and polyole¬ fins (see Japanesse Patent Announcement okai No. 48-43031/1973). Other such compatibilizing agents are taught in, for example, U.S. Patent Nos. 4,188,432; 4,020,025; British Patent No. 1,363,463 and German Patent No. 241,375. Unfortunately, these approaches to preparing compatible polymer blends often do not yield entirely satisfactory results. In many instances, the type and proportion of the component polymers which can be blended using these techniques is quite narrowly re¬ stricted. In addition, the inclusion of an additional component in the blend often has an adverse effect on the properties of the blend. Moreover, the blend achieved is still not as compatible as desired and accordingly the properties of the blend are sometimes not as good as expected. - Accordingly, it would be desirable to provide a blend of normally incompatible polymers in which improved compatibilization of the polymers and improved properties of the blend are achieved. It is further desirable to be able to maximize the type and proportion of the desirable component polymers in any particular blend. In one aspect, the invention is a thermoplastic polymer blend comprising a first reactive thermoplastic polymer containing a compatibil±zing amount of repeating units containing a pendant cyclic iminoether group and a second reactive thermoplastic polymer containing a compatibilizing amount of repeating units containing a coreactive group which is capable of reacting with said cyclic iminoether group to form a linkage between said first and second reactive polymers wherein said first and second reactive polymers are normally incompatible when said first and second polymers do not contain such cyclic iminoether and coreactive groups. In another aspect the invention is such a blend wherein said blend is characterized by said first and/or said second thermoplastic reactive polymer being extended with respective miscible nonreactive polymer(s). The blends of this invention are a compatible (or miscible) blend of the component polymers. Accord¬ ingly such a blend exhibits the desirable properties of each of the component polymers with no significant decrease in properties due to incompatibility. An additional significant advantage can be achieved in that the amounts of reactive polymers which are employed can be reduced by extending them with miscible non- reactive polymers without decreasing the compatibility of the normally incompatible polymers. In addition, the blends of this invention can be prepared using wide ranges of reactive polymer components as well as a variety of other types of miscible polymer components- By varying the proportions of cyclic iminoether and coreactive groups employed xn the reactive polymers and by varying the type and .amount of optional miscible nonreactive polymer blended with the respective reactive polymer, the properties of the xesultant "blend can be -engineered o many desired end uses. The term "blend" as employed herein refers to those solid mixtures of two or more polymers which are commonly referred to in the art as polymer blends or polymer alloys. The terms "compatible blend" or "mis¬ cible blend" and like terms, as employed herein, are not employed in the strict sense as meaning that the blend exhibits a single glass transition temperature, but instead are used to describe a blend which exhibits properties, especially physical properties, which are essentially intermediate to those of the component polymers, or better. By contrast, an "incompatible blend" or "immiscible blend" as used herein, refers to a blend which exhibits properties which are significantly poorer than those of the individual polymers. The subject blend or polymeric alloy generally comprises at least two "reactive polymers" which are not normally compatible. The "first reactive polymer" is functionalized with a cyclic iminoether group and the "second reactive polymer" is functionalized with a coreactive group that is capable of crosslinking with the cyclic iminoether group. In one aspect of the invention at least one or, optionally, both of the xeactive polymers are extended with miscible nonreactive polymer
 t.o form a reactive blend thereof, The miscible nonreactive polymer can comprise the base polymer of the respective reactive polymer or any otner polymer compatible with the reactive polymer. The reactive polymers and/or blends may then be blended to form a new blend or alloy. For example, the cyclic iminoether functionalized polymer can r>e extended witr. a miscible nonreactive polymer to render a reactive blend. Likewise, the coreactive second polymer can be extended with polymers to produce a coreactive polymer blend. Subsequently, the iminoether functionalized polymer or blend can be reacted with the coreactive functionalized polymer or blend. The blends of this invention contain a first reactive polymer or polymer blend having pendant cyclic iminoether groups. Said cyclic iminoether groups are present in a compatibilizing amount, i.e., an amount which is at least sufficient to render the first reactive polymer or polymer blend compatible with the other reactive polymer or polymer blend employed herein. Of course, the amount of cyclic iminoether group which is required to compatibilize the first reactive polymer blend depends somewhat on the particular polymers employed, the relative amount thereof present in the blend and the amount of coreactive groups on the second reactive polymer. However, in general, a compatibilizing amount of said cyclic iminoether group-is present when the repeating units containing said cyclic iminoether group comprise at least about 0.01 weight percent of the first reactive polymer. Since, as described more fully hereinafter, the cyclic iminoether group apparently forms a linkage with the coreactive group on said second reactive polymer, it is readily seen that the degree of cross- linking and the molecular weight of the polymers of the blend can also be controlled with the proportion cf cyclic iminoether and coreactive groups present m the blend. In fact, with control of the amounts of such groups m the blend, the blend of th s invention can be prepared as desired to form a very lightly crossiinke≤ thermoplastic ble d. However, it is only essential that i_he amount of cyclic iminoether group in said first reactive polymer and coreactive group on said second reactive polymer be sufficient to compatibilize themselves (with or without a miscible nonreactive polymer) in the blend. Most typically, the first reactive polymer contains from 0.01 to 10 weight percent of repeating units containing pendant cyclic iminoether groups. More preferably, the first reactive polymer contains from 0.1 to 5 weight percent of such repeating units. The cyclic iminoether groups are advantageously described by the general structure: wherein each R is independently hydrogen, or an inertly substituted hydrocarbon containing 18 or fewer carbon atoms; and n is a number from 1 to 5.- Said cyclic iminoether group can be attached to the polymer chains through any of the carbon atoms in the ring. Preferably, the cyclic iminoether is a 2-iminoether, i.e., is attached to the polymer chain through the 2-carbon atom to yield a structure as represented as K f^ \ r>r Ό wherein R and n are as defined hereinbefore. Pre- ferably, each R is hydrogen or lower alkyl and n is 1, 2 or 3. Most preferably, each R is hydrogen, n is 2 and the cyclic iminoether is a 2-oxazoline group. By "inertly substituted" it is meant that the referenced group contains no functional group which interferes * with the polymerization or curing of the oxazoline group. Polymers containing repeating units having 5 pendant cyclic iminoether groups are advantageously prepared by the polymerization of a monomer mixture comprising an ethylenically unsaturated monomer containing a cyclic iminoether group. Preferably, such monomer is a 2-alkenyl-2-oxazoline wherein said alkenyl 10 group contains from 2 to 8, preferably 2 to 4 carbon atoms. Most preferably, said monomer is 2-isopropenyl- -2-oxazoline. The first reactive polymer is a polymer of any monomer which (a) can be modified to contain pendant 15 cyclic iminoether groups, or (b) can be copolymerized with a monomer which contains or can be modified to contain pendant cyclic iminoether group. In the preferred embodiment, wherein an ethylenically unsaturated cyclic iminoether is employe as a monomer, the first 20 reactive polymer is advantageously a polymer of an addition polymerizable monomer copolymerizable therewith. Said first reactive polymer is advantageously a polymer of a lower alkene, particularly a C, - C_ alkene, more particularly, ethylene or propylene as 25 well as copolymers thereof; a connuσated diene εucr. as butadiene ox isopr ne as well as copolymers thereof; a vinylirSene hali-de such as vinylidene chloride or copolymers thereof; vinyl acetate; an ether of an or,β-ethylenically unsaturated carboxylic acid such as 30 alkyl esters of acrylic or methyl acrylic acid and copolymers thereof; a monovinylidene aromatic compound BAD ORIGINAL such as styrene, vinyltoluene, t-butyl styrene and vinylnaphtalene; as well as polymers of diverse other addition polymerizable monomers. Ethylenically unsaturated cyclic iminoethers, in particular 2-alkenyl- -2-oxazolines, generally resemble styrene in their polymerization reactions. Accordingly, as a rule of thumb, polymers of " monomers which are copolymerizable with styrene will generally be usefully employed herein. Due to the polymerization reactions of 2-alkenyl-2- oxazolines and the tendency for styrenic polymers to be incompatible with a wide range of other thermoplastic materials, it is preferred that the first polymer be a polymer of a 2-alkenyl-2-oxazoline and styrene, especially 2-isopropenyl-2-oxazoline and styrene.. The coreactive group is one which is capable of reacting with said cyclic iminoether group to form a linkage between said first and second reactive polymer. Such coreactive group is typically an electrophilic group containing an active hydrogen. Examples of such groups include carboxylic acid, amino or hydroxy! groups. The coreactive group may oe pendant on said second reactive polymer, may form terminal groups thereon or may be incorporated nto the polymer backbone thereof. Polymers containing coreactive groups along tne polymer backbone include, for example, poiyammes, such as the diverse polyalkylene amines. Polymers con¬ taining terminal coreactive -gxoups include, for example, diverse polysulfides (Thiokols), epoxy resins and poly- alkylene glycols. Most generally, said second reactive polymer contains pendant coreactive groups which are derived from an addition poly erizable monomer containing the desired coreactive group. Preferred are polymers 5 having repeating units derived from α,β-ethylenically unsaturated monomers containing said coreactive groups. Examples of such polymers are polymers of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid and unsaturated 10 amines such as vinylamine. In addition, polymers of other monomers which can be chemically modified to form pendant coreactive groups in the polymers, such as acrylonitrile, are usefully employed herein. The second reactive polymer contains at least 15 a sufficient amount of said coreactive groups to com¬ patibilize itself with said first reactive polymer. As stated hereinbefore, a compatibilizing amount of said coreactive group will depend on the particular polymers employed in the blend as well as the relative propor- 20 ions of said polymers in the blend and the amount of the iminoether groups present on said, fixst xeactive polymer. However, as with the iminoether group, a compatibilizing amount of the coreactive group is typically present when at least 0.01 weight percent of 25 the repeating units of the second reactive polymer contain coreactive groups. When said coreactive group is an integral part of the structure of the polymer oackoone, as many as 100 weignt percent of sucn repeating units n the second polymer may 30 contain coreactive groups. Typically, when said coreactive group is a pendant group incorporated into said second reactive polymer for the primary purpose of BADORIGINAL compatibilizing 'the blends of this invention, it is preferred that the repeating units containing said coreactive groups comprise from 0.01 to 10, more preferably, from 0.1 to 5 weight percent of said second reactive polymer. The second reactive polymer can be one of any thermoplastic polymer which contains or can be modified to contain a coreactive group as described hereinbefore. Addition polymers such as polymers of olefins, vinyl halides, vinylidiene halides, acrylic esters, mono¬ vinylidene aromatics and the like as described herein¬ before in conjunction with a description of said first reactive polymer are useful with said second reactive polymer. The second reactive polymer is generally a copolymer of an addition polymerizable monomer which contains said coreactive group or which can be modified subsequent to polymerization to impart said coreactive group thereto. For example, any of the aforementioned addition polymers can be copolymerized with an addition polymerizable carboxylic acid to .impart carboxyl groups to the polymer. .Amino -groups, amide groups and like coreactive groups can -be imparted to the second reactive polymer in similar manner by cop.oiymerizing a monomer mixture containing the desired proportion of an addition polymerizable monomer containing such group. Also, graft or block copolymers wherein at least one of the grafted segments or blocks contain a reactive group can be employed nerem. Polymers of certain monomers such as vinyl or vinylidene halide or acrylonitrile can be modified after the polymerization thereof to impart coreactive moieties thereto. For example', vinyl chloride can be reacted with ammonia or a primary amine to place pendant amine groups on the polymer. Similarly, acrylonitrile can be hydrogenated after its polymerization to form 5 pendant amine groups. Certain other polymers which normally contain coreactive groups may be employed as the second reactive polymer. For example, polymers containing repeating amine linkages, such poly(ethyleneimine) or a partially 10 hydrolyzed poly(2-alkyl-2-oxazoline) are suitable as the other polymer herein. Other suitable polymers include those which contain amine, carboxylic acid, hydroxyl, epoxy, mercaptan, anhydrate and like groups in the polymer chain or as end groups therein. 15 When the second reactive polymer does not normally contain coreactive groups it is generally desirable to prepare the polymer with relatively small amounts of said coreactive groups. This is because it is usually desirable to minimize the effect of the 20 coreactive group or monomers containing said coreactive group on the physical properties of the polymer. The presence of large amounts of certain reactive groups, such as acid groups, can cause the blend to have certain undesirable properties such as water-sensitivity, 25 adhesion to molds and corrosion of molds. The blends of th s invention are advantageous1; pxepared fxo the component poiyaers and/or blends thereof by conventional melt blending or solution blending techniques. Melt blending is advantageously 30 performed by heating each polymer to a temperature about its softening point and thoroughly mixing the BADORIGIN " softened polymers. ' Solution blending is performed by dissolving each component polymer into a common solvent and precipitating the dissolved polymers therefrom. Melt blending is the preferred method of preparing the blends of this invention. Generally, the reactive polymers (and the miscible nonreactive polymers if used) can be simul¬ taneously blended to form the subject blend. However, where it is desirable to first form a preblend of the reactive polymers, only miscible nonreactive polymer which corresponds to the continuous phase of the pre¬ blend can be post-blended. This characteristic is the result of the reactive polymer which makes up the discontinuous phase not being able to compatibilize its respective miscible nonreactive polymer due to the surrounding continuous phase which is composed of a noncompatible polymer which prevents the incorporation of the miscible polymer. On the contrary, the dis¬ continuous phase does not prevent the extension of the continuous phase reactive polymer with its corresponding miscible nonreactive polymer. Preferably, "the reactive polymers are either blended simultaneously with the miscible nonreactive polymers or preblended with their respective miscible nonreactive polymer. Preferably, when a miscible nonreactive polymer is contained in the blends according to the invention, the reactive polymer is extended w th miscible nonreactive polymer m a five to one weig t ratio or less of nonreactive polymer to reactive polymer. Higher levels of nonreactive polymer can progressively deteriorate the blend properties. βADORIGINAL Nonreactive polymers that can be blended with the reactive polymers are those which are normally miscible (compatible) with either of the reactive polymers. For instance, reactive polystyrene (cyclic iminoether functionalized polystyrene) can be blended with polyphenylene oxide or a polystyrene; and a coreactive polymer such as ethylene acrylic acid can be pre-blended with a polyethylene. One preferred blend consists of reactive polystyrene and high impact polystyrene with ethylene acrylic acid and low density polyethylene. Although it is not intended to limit the invention to any theory, it is believed that the compati¬ bility of the blends of this invention.is due to the reaction of said coreactive and iminoether groups present therein. Said coreactive and iminoether groups are believed to react to form linkages between said first and second reactive polymer, thereby overcoming the normal tendency of these polymers to resist the formation of a compatible blend. Since crosslinkages between the polymers are present in the blends of this invention, it is apparent that presence of linking groups on each polymer can also be used as a control on the rheological and thermo¬ plastic properties of the blends. Since the presence of such linking groups increase the molecular weight of the polymers in the blends, increasing the amounts of such linkages enables the practitioner to prepare more viscous, stronger materials by further increasing the amount of linkage in the blends. Typically the formation of said linkages is achieved by the application of a moderate amount of heat to the blends. The amount of heat required is typically dependent on the particular coreactive group employed. In general, carboxylic acid groups are more reactive than amide, amine or hydroxyl groups and therefore require lower temperatures to form such crosslinkages. Usually, when a hot blending technique is employed to form the blends, the temperature at which the melt blending is performed is generally sufficient to cause the formation of linkages therein. Generally, and especially when the coreactive group is a carboxylic acid, such linkages are formed in one minute or less at the temperatures used to melt blend the polymers. It may be desirable to incorporate into the blend a catalyst which increases the rate of the reaction between the iminoether and coreactive group. . Lewis acids such as zinc chloride or iron chloride are suitable as such catalysts. In addition, it may be desirable to include a plasticizer or lubricant in the blends in order to facilitate the iminoether and coreactive groups contacting each other in the blending process. However, the inclusion of either a catalyst, plasticizer or lubricant is optional herein. An impor¬ tant advantage of the present invention is that the formation of links in the blends of this invention is accomplished without the formation of any by-products and without the formation of ionic links. Unlike most curable systems, in which water, ammonia, or alcohol or other condensation product is formed in the curing reaction, the formation of links in this invention does not create such by-products. Accordingly, the links are formed in these blends without the undesirable formation of vaporous condensation products and without introducing such condensation products as impurities in the blends. The use of ionic crosslinks is also unde- sirable because such ionic crosslinks are often sensitive to pH, water and electrolytes and render the blends somewhat hydrophilic. In one aspect, the properties of the blends can be adjusted by the amount and type of miscible nonreactive polymer blended with either of the reactive polymers. The cyclic iminoether functionalized polymer or coreactive polymer can be effectively diluted to a desired level which will control the amount of potential crosslinking. " This will also allow the use of non¬ reactive polymers which are less expensive with reactive polymers to design more economic blends. The physical and chemical characteristics of the blends prepared with both reactive and nonreactive polymers are generally proportional to the amount of polymers employed in the blends. The process of extending the reactive polymers with compatible polymers can therefore be employed to improve the properties of the final blend. For example, where blending the reactive polymers resulted in a blend having a low melt flow rate either of the reactive polymers could be first extended with an appropriate polymer having a high melt flow rate such that the final blend had an acceptable flow rate. Therefore, the pxocess of extending the reactive polymexs allows the skilled artisan an opportunity to selectively engineer the final blend properties. The blends of this invention may be employed in most applications for which the component polymers are suitable. Said blends may be employed to form shaped articles of all types as well as for films for packaging and like usages. ' The following examples are provided to illus¬ trate the invention but not to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated. Experiment 1 In a Brabender mixer heated to about 220°C were softened 25 grams (g) of an ethylene acrylic acid (EAA) copolymer (9 percent by weight repeating acrylic acid units). To the softened EAA polymer was added 25 g of a styrene/2-isopropenyl-2-oxazoline (SIPO) copolymer containing 1 percent by weight repeating isopropenyl oxazoline (IPO) units. Mixing is continued until a homogeneous appearing blend is obtained. The heat distortion temperature, heat distor¬ tion temperature under load, tensile strength, tensile modulus, elongation at break, notch impact strength and melt flow of the resulting blend were determined in conventional manner and are reported as Sample .No- 1 in Table I following. For co par g corresponding valu s a commercially available polystyrene, an EAA copolymer used in preparing the blend and a commercially available high-impact polystyrene wer obtained and xeporten xn Table I following. For these and other samples, the heat distor¬ tion temperature was determined according to ASTM D1525 and is given in °C and °F. The heat distortion tempera¬ ture under load was determined at 1.82 MPa (264 pounds ° 'GJ per square inch) according to ASTM D648 and is given in °C and °F. The tensile strength, tensile modulus and percent elongation were determined according to ASTM D638, the tensile strength and modulus being given in Mega Pascals (MPa) and pounds per square inch (psi). The impact strength is determined according to ASTM D256 and is given in Joules per meter of notch (J/m) and foot pounds per inch notch (ft.lb/in). The melt flow rate was determined according to ASTM D1238 and is given in grams per 10 minutes (g/10 min). TABLE I Sample Sample No. 1 PS 1 * EAA 2 * HIPS 3 * Heat Distortion Temperature in °C and (°F) 88 (190) 104 (220) 77 (170) 100 (212 Heat Distortion Under Load in °C and (°F) 52 (126) 99 (210) ND 92 (197) Tensile Strength in MPa and (psi) 20 (2,900) 36 (5,200) 7.6 (1,100) 18 (2,600 Tensile Modulus in MPa 414 2900 <69 1600 and (psi) (60,000) (420,000) (<10,000) (230,000 Elongation (%) 50 > 150 40 Impact Strength in J/m and (ft.-lb./in. ) 534 (10) 10.7 (0.2) NB 80.1 (1.5 Melt flow in g/ 0 min. 1.7 iSD 3.0 * - Not an example of the present invention . ND - Not Determined . NB *- .sample does not break, there fare no szaiβae is lObtaiaaed. ^Polystyrene, :κ n ~ 200, QVO . % fey!ene/A'cr lic acid cof^olywex- 3 High Impact Polystyrene. BAD ORlQJJ It is readily seen from the data presented in Table I that a compatible blend of the SIPO and EAA polymer was achieved. Excellent tensile and heat distor¬ tion properties were obtained with the blend of this 5 invention in contrast to non-compatible blends of styrenic and olefin polymers which exhibit notably poor tensile properties. In order to monitor the formation of linkages between the SIPO and EAA polymers, torque measurements 10 were made while mixing varying EAA and SIPO polymers in a Brabender.as described hereinbefore. As a control, a torque measurement was made on a 50/50 blend of poly¬ styrene and an EAA (3 percent acrylic acid) polymer. Upon adding the polystyrene to the softened EAA polymer, 15 the torque exerted by the blend abruptly increased due to the presence of unsoftened polystyrene in the system. As the polystyrene softens and is blended with the EAA polymer, the torque steadily decreases until a constant value of about 120 meter*grams was xeached. This blend 20 was incompatible as exhibitied by poor physical properties. In like manner, the torque exerted by a 50/5C blend of the same EAA polymer and a SIPO polymer contain¬ ing 0.2 percent repeating IPO units was determined. The torque exerted m preparing the olend was essentially 25 the same as that of the contol, indicating tnat the crosslmkages formed between the SIPO and EAA polymers did not sis ai ie- sly affect t&e saasr&l rheol©ξ^ sf 3ae blenaL Bos?®s*e , ensile tttBtέat if i ated Saat the blend had significantly im rov d physical properties as 30 compared to the control indicating that sufficient linkages between the EAA and SIPO polymers were formed to compatibilize the blend. ^BADORIGINAL A third evaluation was run, this time employing a 1 percent IPO SIPO polymer. This time, the blended polymers exhibited a torque of 160 meter*grams indicating that significant crosslinkages between the EAA and SIPO polymers occurred. A fourth evaluation was run, this time employ¬ ing a 50/50 blend of an EAA polymer containing 6.5 percent acrylic acid units and a 1 percent IPO SIPO polymer. After the SIPO polymer was melted and blended with the EAA, the torque exerted by the blend exhibited a constant value of about 180 meter*grams, indicating that a still greater amount of linkages were formed between the component polymers. A fifth evaluation was run employing 25 g of the same EAA polymer as used in the fourth evaluation, 16 g of a 5 percent IPO SIPO polymer and 9 g of a 10 percent IPO SIPO polymer. The torque exhibited by the blend reached a constant value of about 230 meter*grams. A sixth evaluation was run employing a 50/50 blend of a 9 percent acrylic acid ethylene acrylic acid polymer and a 10 percent IPO SIPO polymer. This time the torque exerted by the blend reached a maximum as the SIPO was added, fell to a minimum value of about 300 7 ιneter•grams as the SIPO softens and then gradually rose to about 400 -meter-grams as linkages between the EAA and the SIPO polymers formed. o further vary the formation of linkages between the SIPO and the EAA polymers, a. blend of a 2.5 percent IPO SIPO polymer and a 10 percent acrylic acid EAA polymer was prepared by melt-blending. This blend [BAD ^GINAL was studied by infrared variable temperature techniques by heating the blend from ambient temperature to about 200°C in hot orthodichlorobenzene while periodically taking infrared scans of the heated blend. The initial 5 cool system exhibited infrared peaks corresponding to the presence of dimerized (C00H) 2 groups and oxazoline rings as well as a small proportion of amide ester groups. As the blend was heated, the dimerized (C00H) 2 and oxazoline peaks diminished while the amide ester 10 peaks increased in intensity indicating that the carboxyl and oxazoline groups were reacting to form amide ester groups. Upon heating the sample, the amide ester peak did not significantly decrease in intensity indicating that the amide ester linkages were permanent and stable. 15 " Experiment 2 In a Brabender mixer equipped with a torque measuring apparatus 75 parts of high density polyethylene/maleic anhydride graft copolymer (HDPE MA) containing 1 pexcent by weight maleic anhydride units 20 were softened at 220'°C. To the softened HDPE/MA polymer was added 25 parts SIPO polymer containing 1 percent IPO units. Upon adding the SIPO polymer, the torque exerted by the blend increased. Tne torque then decreased as the SIPO was softened and blended. The 25 torque slightly increased again as crosslinkages between the SIPO and HPDE/MA polymers formed and then reached a constant value .of about 270 meter-grams. A sample of the resulting blend was compression molded at 160°C and •δδ.9 && (10,00© psi) for 3 aπisEaSaes. The notch impact 30 strength of the molded sample was measured and found to be 46.7 J/m (0.874 ft.-lb./in). BADORIGINAL The foregoing experiment was repeated, this time using 30 parts SIPO and 70 parts HPDE/MA. The torque exerted by the blend followed a pattern similar to that of the previous sample reaching a constant value of about 280 meter*grams. The notched impact strength of this blend was 28.5 J/m (0.532 ft.-lb./in). The experiment was again repeated, this time using 35 parts SIPO polymer and 65 parts HDPE/MA polymer. Again a similar torque pattern is seen with the torque reaching a final constant value of about 280 me'ter*grams. The notched impact strength of this sample was 26.0 J/m (0.487 ft.-lb./in). Another blend containing 70 percent HDPE/MA polymer and 30 percent SIPO polymer was prepared in like manner except 0.2 percent zinc chloride was added to the blend to promote the formation of crosslinks between the polymers. Mechanical testing of molded samples of this blend was conducted with results as reported in Table II following. ^SADORIGIN TABLE I I Sample HDPE/MA//SIP0 1 PS 2 HDPE 3 Heat Distortion in °C and Temperature ( °F) 121 (250) 104 (220) 127 (260) Heat Distortion Under Load in °C and (°F) 65 (149) 99 (210) 53 (127) Tensile Strength in MPa and (psi) 29 (4,200) 36 (5,200) 30 (4,400) Tensile Modulus in MPa 1700 • 2900 1000 and (psi) (240,000) (420,000) (150,000) Elongation in % 70 >150 Impact Strength in J/m and (ft.-lb./in. ) 139 (2.6) 10.7 (0.2) 139 (2.6) Melt Flow in g/10 min. 0.6 7 o.ε " " 70 percent high density polyethylene grafted with 1 percent maleic anhydride polymer : 30 percent styrene/isopropenyl oxazoline copolymer containing 1 percent isopropenyl oxazoline units. "Polystyrene, Mn = 200,CC1. "High density polyetnyiene As can be seen from the data presented in Table II, excellent mechanical properties were exhibited by this blend. By comparing the properties of the blend with those of polystyrene and high density poly- ethylene, it is seen that the blend exhibited properties which are generally intermediate to those of the poly¬ styrene and HDPE. Experiment 3 Four blends of a 75 percent styrene/24 percent acrylonitrile/1 percent IPO terpolymer (SANIPO) and a 94 percent propylene/6 percent acrylic acid copolymer (PAA) were prepared in a Brabender mixer at the propor¬ tions indicated in Table III following.. Two of the blends also contained 0.6 percent zinc chloride. As a control, a blend of polystyrene and the PAA polymer was also prepared. Torque measurements of the blend were made as a measure of the compatibility of the blends. TABLE III Sample /o T /a Torque No. SANIPO x PAA^ %PS 3 %ZnCl 4 meter•grams III-A 80 20 0 410 III-B 70 30 — 0 290 III-C 70 30 — 0.6 290 III-D 60 40 — 0.6 270 III-E* «... 30 70 0 150 * Not an example of this invention. 10 Percent by weight Styrene/acrylonitrile/IPO (75/24/1) terpolymer. 2 Percent by weight propylene acrylic acid (94/6) copolymer. 3Percent by weight polystyrene. 4 15 Percent by weight zinc chloride catalyst. " "Measured on a Brabender Honaratus. In the control (Sample No. III-E) the poly¬ styrene and PAA polymers resisted blending due to the mutual incompatibility thereof. The resulting blend was 20 a stringy mixture exhibiting poor plastic properties. By contrast, each of Sample Nos. III-A through III-Z exhibited good plastic properties evidencing a compatibili- zation of "the port onaen slysβe .. Ttee increased toxque measurement for Sample Nos. III-A - III-D as compared 25 with Sample No. III-E indicated increased compatibility between the compared polymers. BADORIGINA Experiment 4 In a Brabender mixer 75 parts of a SIPO (1 percent IPO) copolymer was softened at 220°C. To the softened SIPO was added 25 parts of a carboxylated polyester resin, sold as Vitel VPE6434. The blending was continued until the blend assumed a homogeneous appearance. Torque measurements made during the blending indicated that crosslinkages are formed between the component polymers during blending. The torque exerted by the blend reached a final constant value of about 170 meter*grams. For comparison, this experiment was repeated this time substituting 75 parts polystyrene for the SIPO polymer. Torque measurements showed no formation of linkages between the polymers. The final torque reading was only 90 meter*grams. Experiment 5 In this example, blends of a vinylidene chloxide/ ethacrylic acid copolymer (1 percent etha- crylic acid) were prepared with diverse other polymers. 35 parts polystyrene were softened on a Brabender mixer at 220°C. To the softened polymer 55 parts of vinylidene chlor de/methacryiic acid copolymer were added. Torque measurements indicated the formation of no crosslinkages between the polymers. Substitution of a 1 percent IPO SIPO copolymer for tne polystyrene resulted in the formation of sibstantial amounts of linkages between the component polymers. Similarly, substitution of 15 percent chlorinated polyethylene and 20 percent of a 1 percent IPO SIPO copolymer for the polystyrene again provided a blend in which linkages between the component polymers were formed. ^BAD ORIGINAL The foregoing experiment was again repeated, this time employing in place of the polystyrene a coagulated methyl methacrylate/ethylaerylate latex which had been coagulated to powdered form. Viscosity 5 measurements made during blending indicated no formation of crosslinks between these polymers. However, when a methyl methacrylate/ethylacrylate/acrylic acid/IPO polymer was employed, viscosity measurements during the blending clearly indicated the formation of linkages 10 between the polymers and the resulting blend was a compatible blend exhibiting good physical properties. Experiment 6 In a Brabender mixer heated to 280°C at 50 rpm the polymer blends listed in Table IV were melt 15 blended . The subject reactive blends exemplary of the invention were prepared by mixing the polyphenylene oxide (PPO) and polystyrene/2-isopropenyl-2-oxazoline (SIPO) copolymer containing 1 percent by weight repeating 2-isopropenyl-2-oxazoline (IPO) units for approximately 20 3 minutes until a homogeneous blend was obtained. Similarly, a control blend w prepared by first blending the polyphenylene oxide nd polystyrene until a homogeneous blend was obtained. To the first blends were tnen added ethylene acrylic acid copolymer (EAA) and tne 25 blends were allowed to mix for an additional 5 minutes. The torque measurements for blending the components were recorded and both blends were then compress or. molded and tested for melt flow rate, impact, c elongation. These measuremen s axe recorded in Table IV, 30 Sample 1 being an example of iae invention and Sample 2 being the control blend. [BADORIGINAL Experiment 7 Various polymeric alloys were prepared as in Experiment 6 and are also shown in Table IV. A com¬ parison was made between blends of unreactive polymers (Sample 3), the corr sponding blend of reactive polymers (Sample 4) and the blend of the miscible base polymer with the corresponding reactive polymer blends (Samples 5 and 6). The samples were prepared, compression molded and measured for melt flow rate, impact, elongation and tensile (Samples 3-6 only). The results are shown in Table IV. Torque Notched After Polymer Blend Izod Tensile in 8 min A (Percent Flow in in J/m and MP and Elongation in Sample Weight Polymer) g/10 min (ft. lbs/in) (psi) in percent Meter*Gra 1 35 PPO/35 SIPO 06 68.4 7.8 300 (1^ IPO) (1.28) 30 EAA 2 35 PPO/35 polystyrene 24 29.4 2.0 130 30 EΛA (.55) 3 50 polystyrene 11.93 32.6 7.8 (1131) 1.7 50 LLDPE (.61) w I 4 50 SIPO (1% IPO) 1.03 66.8 24 (3425) 8.8 o I 50 LLDPE ( .44% MAH) (1.25) 5 50 SIPO (1% IPO) 1.10 82.2 27 (3866) 8.0 25 LLDPE ( .88% MAH)/ (1.54) 25 LLDPE 6 20 SIPO (2.5% IPO)/ 1.05 75.8 25 (3638) 13.2 30 Polystyrene (1.42) 25 U.ϋPE ( .08% MΛH) 25 LLUFE Not an example: of the invention. PPO - polypheny1 ne oxide; SIPO - polystyrene/2-isopropenyl-2-oxazoline; IPO - 2-isopropenyl-2-oxa oline; EΛA-ethylene acrylic acid; LLDPE - linear low density polyethylene; MΛII - maleiα anhydride. It is readily seen from the data presented in Table IV that a compatible blend can be prepared from a miscible nonreactive polymer blended with either or both reactive polymers (Samples 1, 5 and 6). Excellent physical properties are obtained with the blend of this invention in contrast to non-compatible blends of Samples 2 and 3 which generally exhibit poorer properties. In order to monitor the formation of linkages between the SIPO and EAA polymers, torque measurements were made in Experiment 6 while mixing the EAA and SIPO polymer in a Brabender as described hereinbefore. As a control, a torque measurement was made on a 35 PPO/- 35 Styrene/30 EAA blend (Sample 2). Upon adding the PPO/polystyrene blend to the softened EAA polymer, the torque exerted by the blend steadily decreased until a constant value of about 130 meter*grams was reached. The low torque value indicates that crosslinking did not occur between the PPO/styrene and EAA polymer. In like manner, the torque exerted by the 35 PPO/35 SIPO/30 EAA blend (Sample 1), was determined. The final torque exerted in preparing the blend was higher than that of the control (Sample 2), indicating the presence of crosslinking between the PPO/SIPO reactive blend and the EAA polymer. With respect to the results for Experiment 7, it is .seen that the physical pxoperties of the reactive blends (Samples 5 and f>) are better than the comparative nonreactive blend (Sample 3). In addition, it is seen that Samples 5 and 6 which contained the. miscible polymers preblended with the reactive polymers were not /f l βfi tøH adversely affected from the inclusion of the miscible polymers in view of Sample 4 which only contained reactive polymers.

Claims: 1. A thermoplastic polymer blend comprising a first reactive thermoplastic polymer containing a compatib*Llizihg amount of repeating units containing a pendant cyclic iminoether group and a second reactive thermoplastic polymer containing a compatibilizing amount of repeating units containing a coreactive group which is capable of reacting with said cyclic iminoether • group to form a linkage between said first and second reactive polymers wherein said first and second reactive polymers are normally incompatible when said first and second polymers do not contain such cyclic iminoether and coreactive groups. 2. The blend of Claim 1 wherein repeating units of said first reactive polymer which contain a pendant cyclic iminoether group comprise from 0.01 to 10 percent by weight of said first reactive polymer and the repeating units of said second reactive polymer vhich contain said coxeactive gxoup comprise from 0.01 to 10 percent by weight of said second reactive polymer. 3. The blend of Claim 1 wherein the cyclic amino, ether group is a 2-oxazoline group. BADORIGINAL 4. The blend of Claim 3 wherein said first reactive polymer is a polymer of styrene and said second reactive polymer is a polvmer of an olefin having from 2 to 8 carbon atoms. 5. The blend of Claim 4 wherein said first reactive polymer is a copolymer of styrene and a 2-alkenyl-2-oxazoline and said second reactive polymer is a polymer comprising ethylene and an α,β-ethylenically unsaturated carboxylic acid. 6. The blend of Claim 3 wherein said first reactive polymer is a polymer of styrene and said second reactive polymer is a polymer of a vinyl halide. 7. The blend of Claim 1 wherein said blend - is characterized by said first and/or said second thermoplastic reactive polymer being extended with respective miscible nonreactive polymer(s). 8. The blend of Claim 7 wherein said miscible nonreactive polymer(s) is blended with the xespective xeactive polymer in a five to one weight ratio or less of nonreactive polymex(s) to reactive polymer. 9. The blend of Claim 8 wherein said miscible polymer(s) is the base polymer of the respective reactive polymer with which said miscible polymer(s) is blended. It). The blend of Claim 7 wherein said first reactive polymer is a polymer of styrene and a 2-alkenyl- -2-oxazoline which is extended with polyphenylene oxide. SADORI "

Inventors: HOHLFELD RONALD WILLIAM, MERIDITH BRENDA CHRISTINE, SCHUETZ JAMES EDWIN, HOHLFELD, RONALD, WILLIAM, MERIDITH, BRENDA, CHRISTINE, SCHUETZ, JAMES, EDWIN
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1984
Main classification: C08L39
IPC codes: C08F12, C08F212, C08G85, C08L25, C08L33, C08L39, C08L51, C08L57, C08L71, C08L101