CA1292827C - Polyphenylene compositions having improved melt behavior - Google Patents

Abstract

POLYPHENYLENE COMPOSITIONS
HAVING IMPROVED MELT BEHAVIOR
Abstract of the Disclosure Polyphenylene ether resin compositions exhibiting improved melt behavior without degradation of other thermal properties are provided by combining a polyphenylene ether polymer and an alkyl or aralkyl sulfonate of an alkali metal, where the alkyl or aralkyl radical has 5 to 25 carbon atoms.

Description

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POLYPHENYLENE COMPOSITIONS
HAVING IMPROVED MELT BEHAVIOR
Field of the Invention The melt behavior of polyphenylene ether compositions can be improved or controlled without reducing the inherent thermal properties of such compositions. The improvement is achieved by a combination of polyphenylene ether resin and an alkyl or aralkyl sulfonate compound.
Background of the Invention Polyphenylene ether resin compositions have long been utilized as thermoplastics because they exhibit a variety of beneficial physical and chemical properties which are useful in many applications. E`xcellent electrical properties, high DTUL as well as inherent flame retardance are three of the prime advan-tages of polyphenylene ether resins. Despite these advantages, polyphenylene ether resins are not necessarily suitable as molding compositions or many applications without further modification. One of the primary reasons for this is -the relatively high melt viscosity of polyphenylene ether resins. A result of this property is relatively poor flow channel exhibited in a typical molding process. Poor flow results in difficulties in molding, losses in manufacturing efficiency as well as poor material performance. For example, in a typical molding process, polyphenylene ethers might have a flow channel of less than twelve inches even at very high temperatures. A glass transition temperature ~Z~Z8~7 of 210C for polyphenylene ethers also indicates that these polymers have characteristically superior thermal properties which may require an element of control in order to provide certain useful products.
A very successful fami]y of thermoplastic products are the modified-polyphenylene ether products wherein the polyphenylene ether base resin is modified or plasticized with another compound in order to provide useful plastic compositions. Typically, modified poly-phenylene ethers are comprised of PPE and an alkenyl aromatic compound such as high impact polystyrene. These materials are alloyable in all proportions and provide a variety of products exhibiting advantages of both classes of compounds while minimizing the disadvantages of each.
Other plasticization methods are also useful for poly-phenylene ether compounds and many conventional plasticizers have been tried. One successful category of such plasticizers has been the triaryl phosphates which are low molecular weight materials which not only tend to plasticize the polyphenylene ethers but also impart an additional degree of flame retardance for these compounds.
Such plasticized modi~ied polyphenylene ether compositions have provided use~ul products whi.ch, however, do not necessarily exhibit the extraordinary thermal properties oE unmodlfied polyphenylene ether.
Additionally, some plasticized modiEied-polyphenylene ether compositions tend to experience environmental stress cracking under certain conditions when exposed to stress cracking agents.
In U.S. Patent 4,529,761, which issued July 16, 1985, Lohmeijer described polyphenylene ether resin compositions which exhibited improved environmental stress crack resistance and which were comprised of polyphenylene ether resins or such resins modified with alkenyl aromatic resins and effective amounts an ~Z9Z~2~

- 3 - 8CN ~245 environmental stress crack resistance agent which was an alkyl or aralkyl sulfonate compound. Lohmeijer did not recognize, however, that such environmental stress crack resistance agents could be utilized in unmodified polyphenylene ether resin compositions (i.e. those which do not contain alkenyl aromatic compounds) and which would thereby provide extraordinarily beneficial thermal properties not otherwise available in modified-PPE systems.
It has now been discovered that the melt behavior of polyphenylene ether resin compositions can be controlled or improved without significantly reducing the inherent thermal properties of such materials and without having to incorporate conventional plasticizers in the compositions.
Although conventional plasticizers can improve the melt behavior of polyphenylene ether resins as, for instance, by making them easier to flow in a molding process, they traditionally degrade the other thermal properties of the base resin due to their plasticizing effect. For example, when plasticizers are added to polyphenylene ethers, the flow channel of the resin may increase but the heat distortion temperature of the plastic wll]
generally decrease.
The present invention improves the melt behavior of the polyphenylene ether without conventional plasticizer~, thereore, while the Elow channel in a molding process will be improved, the heat distortion temperature and thermal stability will not be degraded.
The polyphenylene ether resin compositions of the present invention will thereby exhibit good low temperature and high temperature ductility, as well as, excellent hydrolytic stability and the aforementioned excellent electrical properties.
Unmodified polyphenylene ether resin compositions were former non-processable or difficult to process materials. The compositions of the present invention, which exhibit improved flow and melt ~2~Z1~32~7 characteristics while not tending plasticizing the base resin can form the basis of new resin systems which take advantage of these properties.
It is therefore an object of the present invention to provide polyphenylene ether resin compositions which exhibit improved or at least controlled melt characteristics while no generally degrading the inherent advantageous thermal properties of the base resin.
It is a further object of the present invention to provide a process for advantageously controlling the melt behavior of the otherwise difficult to process polyphenylene ether resin compositions.
Summary of the Invention There is provided a thermoplastic resin composition exhibiting controlled melt behavior without degradation of the inherent thermal properties of the base resin, which consists essentially of:
a) a polyphenylene ether resin or copolymers thereof, and which typically will be poly(2,6-dimethyl-1,4-phenylene ether), and b) a property improving amount of a compound of the formula ~-SO3X wherein R represents an alkyl or aralkyl radical having S to 25 carbon atoms and X represents an alkali metal ion.
Typically radical ~ will have approximately 12 to 20 carbon atoms and is preferably an alkyl radical, X is preferably a sodium ion. The polyphenylene ether base resin will generally have an intrinsic viscosity less than, approximately, 0.42 and preferably between 0.38 to 0.42 deciliters per gram as measured in chloroform at 25C. Conventional polyphenylene ether resins have intrinsic typically in excess of 0.~5 deciliters per gram and often in excess of 0.50 deciliters per gram and this is felt to substantially contribute to the poor melt lZ9ZB27 behavior of such conventiona, unmodified polyphenylene ether resins. On the other hand, there is a practical limit as to how low the intrinsic viscosity of such polyphenylene ether resins can be and those acquainted with polymer physics will recognize that intrinsic viscosities for PPE much lower than the 0.38 deciliters per gram required by compositions of the present invention will yield polymer products having poor physical properties. When the intrinsic viscosity of the PPE utilized in compositions of the present invention rises much above the 0.42 deciliters per gram mentioned above, the compositions begin to behave more like relatively unprocessable conventional poly-phenylene ether resin compositions despite the addition of the melt behavior improving agents utilized by the present invention.
Polyphenylene ethers are a well known class of compounds cometimes referred to as polyphenylene oxides.
Examples of suitable polyphenylene ethers and processes for their peparation can be found in U.S. Patent Nos. 3,306,874, issued February 28, lg67 to llay;
3,306,875, issued February 28, 1967 to Hay; 3,257,357, is~ued June 21, 1966 to Stamato~f; and 3,257,358, issued June 21, l9h6 to Stamatoff. Compositions of the present invention will encompass homopolymers, copolymers and graft copolymers obtained by the oxidative coupling of phenolic compounds. The preferred polyphenylene ethers used as base resins in compositions of the present invention will be comprised of units derived from 2,6-dimethyl phenol. Also contemplated are PPE copolymers comprised of units derived from 2,6-dimethyl phenol and 2,3,6-trimethyl phenol.
The polymer compositions of the present invention will consists essentially of 0.5 to 10 parts 129Z~3Z7 by weight of the melt behavior improving compound based upon 100 parts of the polyphenylene ether base resin.
Preferably about 1 to 5 parts by weight of the additive will be used per 100 parts of the PPE base resin. When less than about 0.5 parts additive are utilized, insufficient beneficial effect will be achieved for typical applications. When greater than approximately 5 to 10 parts of additives are utilized, little additional benefit is achieved while other advantageous properties of PPE may be diminished. This additive compound is an alkyl or aralkyl sulfonate having a formula R-SO3X in which R represents an alkyl or aralkyl radical with 5-25 carbon atoms and preferably and 12 to 20 carbon atoms and X represents an alkali metal ion which is preferably a sodium ion. It is also possible to utilize a mixture of such SUlfOllateS.
Suitable sulfonates include the following products which may be obtained commercially.
Cl~ 20H25 40SO3Na are compounds sold uner the trademark HOSl'ASTAT. Compounds sold uner the -trademar]c ATMER 190 have the general Eormula Cx~2x~lSO3Na. Others are sold under the trademarlc MARANIL A and have the C12H25 C6H4-SO3Na. It will be recogni~ed by those skilled in the art that these formulas represent sulonate salts o hydrocarbon compounds having varying chain lengths.
The improved composi-tions of the present invention are provded by combining the polyphenylene ether based resin and the property improving melt behavior additive by conventional means as will be demonstrated in the examples below. Blended or extruded compositions may be molded and tested by conventional means.
The following examples illustrate the invention without limitation.
Examples 1-3 Compositions of the present invention exhibiting 129Z~27 improved melt behavior were provided in the following manner. The four experimental blends described in Table 1 were compounded using a 28 mm Werner & Pfleiderer twin screw extruder having this temperature profile through several stages (set temperatures)~ 500F (Feed Section), 550F, 590F, 590F, 590F, 600F (die Temperature).
During compounding, a vacuum of 5 inches were maintained for all four samples, while the screw RPM's were a constant 272. Table 1 also describes the extrusion conditions which were observed to change among the materials due to the compositional differences and which demonstrate some of the advantages of the present invention. The polyphenylene ether resin, having the intrinsic viscosity indicated in Table 1, was the oxidative coupling product of 2,6-dimethyl phenol.
Table 1 Composition (parts by weight) A*1 2 3 poly(2,6-dimethyl-1,4-phenylene ether)(a) 100 100 100 100 Extrusion Conditions A 1 2 3 Torque (in-lbs) 780 640 600 500 Power/Current (amp) 15 13 12,5 10 Melt ~emp. (E) 705 598 690 680 25 Extrusion Rate (g/hr) 2400 3400 4000 4000 Observations -Very Smooth -Very Smooth -Smooth -Rough Strand Strand StrandStrand -Uniform -Uniform -Uniform-Gassy, Extrusion Extrusion Extrusion Surging Extrudate * Comparative Example (a) polyphenylene ether having as intrinsic viscosity of 0.40 dl/g as measured in chloroform at 25C.
(b) HOSTASTAT HS-l sodium salt of lauryl sulfonate (A.G. Hoechst Co.) 2~27 Table 1 demonstrates that the sodium salt additive clearly improved the compounding process for a polyphenylene ether polymer. The reduction of extruder torque and power requirements (amperes) are noteworthy improvements in the processability of polyphenylene ether.
Furthermore, the lowering of the melt temperatures while extrusion rates were increased are two additional benefits achieved in compositions of the present invention. Lower melt temperatures save energy and are less abusive to the polymer. Increased extrusion rates are a productivity improvement indicative of the efficiencies gained by the present invention.
Pellets of each of the aforementioned composi-tions were molded into ASTM test specimens using a 4 ounce Newbury injection molding machine. Prior to molding the pellets were dried for four hours at 115C.
The followin~ molding conditions were present and remained constant during the molding process of all four samples:
Barrel Temperature (F) 630 Mold Temperature (F) 220 Cycle Time, Total (Sec) 40 Back Pressure (Psi) 50 Injection Speed Slow As observed during the compounding process, certain conditions changed during the molding process for each of the four sample materials. Table 2 describes these changes in molding conditions which are attributable to the inherent advantages of the present invention.

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lZ9Z8'~7 It is apparent that the sulfonate salt additive lowers the melt temperature of the polyphenylene ether required to mold parts. Furthermore there is a concurrent lowering of the pressure required to fill the cavities of the AST~ test speclmen mold. The channel flow increased even though the molding temperature decreased.
It is evident from the foregoing that the sulfonate salt additive for polyphenylene ether improves not only the extrusion and compounding process for such materials but also is beneficial for the polyphenylene ether molding process.
The foregoing experimental materials were tested to compare important physical properties of the resultant thermoplastic products. The me]t viscosities of the materials were tested using an Instron melt rheometer at 600F and 1500 sec l shear rate. Table 3 describes the other physical properties which were tested hy ASTM test methods and other accepted test practices.
Table 3 COM~OSITION NO. A* 1 2 _ 3 Tenslle (psi) 12,700 10,700 10,500 10,100 Elongation ~percent) 27 31 30 13 Flexur~l Str. tpsi) 15,200 15,200 15,200 14,700 Flexural Mod. (p8i) 344,000 356,000 349,000 343,000 rmpact Resistance Notch. I~od @ 73P (ft-lb/in.ll) 1.4 1.7 1.9 2.0 Notch. I~od @ -40F (ft-lb/in.n) 1.2 1.7 1.9 l.S
Dynaptup Imp. St. ~ 73F (in-lbs) 63 156 205 61 Dynatup Imp. St. @ -40F (in-lbs) 32 55 64 39 Melt Viscosity ~ 600F (poise) 3168 2761 2440 2105 and 1500 sec D~L @ 264 psi (F) 368F 368F 367F

*Comparative Example 1'~9ZE~Z7 The sulfonate salt modified polyphenylene ether especially at the 2 or 3 weight percent level has greatly improved physical properties except for lower tensile strength values. The most beneficial increase are those of impact resistance and melt flow. The latter benefit is achieved with a very slight sacrifices in deflection temperature under load.

Claims (8)

1. A thermoplastic composition having improved melt behavior consisting essentially of:
(a) a polyphenylene ether resin having an intrinsic viscosity less than approximately, 0.42 dl/g as measured in chloroform at 25°C; and (b) a compound of the formula R-SO3X wherein R
represents an alkyl or aralkyl radical having 5 to 25 carbon atoms and X represents an alkali metal ion, in an amount effective for improving the melt behavior of said polyphenylene ether resin.

2. A composition as in claim 1 wherein said compound of formula R-SO3X is present in an amount of, approximately, 0.5 to 5.0 parts per 100 parts of the polyphenylene ether resin.

3. A composition as in claim 1 wherein said compound of formula R-SO3X is a mixture of compounds having said formula and R represents alkyl radicals independently having 12 to 20 carbon atoms.

4. A composition as in claim 1 wherein the formula R-SO3X, X represents a sodium ion.

5. A composition as in claim 1 wherein said polyphenylene ether is a homopolymer or a copolymer.

6. A composition as in claim 5 wherein said polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene)-ether.

7. A composition as in claim 1 wherein said polyphenylene ether has an intrinsic viscosity of approximately, 0.38 to 0.42 dl/g.

8. A molded article comprised of the thermoplastic composition of claim 1.