HIGHEST HEAT AMORPHOUS THERMOPLASTIC POLYIMIDE BLENDS

Kapil C. Sheth, SABIC Innovative Plastics, Mt.Vernon, IN, USA Abstract

Novel thermoplastic polyimide blends have been designed with capability to tailor glass transition temperatures exceeding 300C. These highest heat amorphous thermoplastic blends offer high temperature load bearing capability and dimensional stability. These compositions also demonstrate excellent flame resistance. A series of amorphous TPI blends using the new TPI polymer has been commercialized as EXTEM** UH products6-7. These EXTEM UH TPI blends offer good dimensional stability, high temperature strength, creep resistance and best-in-class flame resistance. Another class of high temperature semi-crystalline blends has also been introduced by alloying polyetheretherketone resin with the new TPI polymer8.

Introduction
Aromatic polyimides represent a distinctive class of materials that are widely used in electronics, aerospace and many other demanding applications. Aromatic polyimides have a unique combination of properties including high glass transition temperatures (Tg), mechanical property retention at high temperatures, high thermal stability, good electrical properties and solvent resistance. However, many such polyimides are infusible, rendering them impossible to process by conventional techniques. Lack of melt processability is a big drawback. Significant efforts have been devoted to the development of melt processable polyimides, commonly referred to as thermoplastic polyimides (TPI)1-3. Evaluation of new monomer combinations has led to the introduction of new materials such as amorphous LARCTPI resin (Tg~250C) and semi-crystalline AURUM* resin (Tg~250C, Tm~388C). A related class of melt processable materials known as polyetherimides (e.g., ULTEM** 1000 resin, Tg~217C) were also developed. Another approach to improve melt processablity of aromatic polyimides is to blend with other easier to process high temperature crystalline and amorphous resins. For example, many blends of polyimides with polyetherimides have been reported4-5. Recently a genuine new TPI polymer has been introduced by SABIC Innovative Plastics. It is the highest glass transition temperature, amorphous thermoplastic resin available (Tg ~ 311C). Its high Tg and viscosity limit injection molding applications. However, other processing techniques such as extrusion and compression molding can process high viscosity materials such as the new TPI polymer. In order to improve its injection moldability, many new TPI blends with good melt processability have been developed by alloying the new TPI polymer with other amorphous thermoplastic polyimides, polyetherimides or semi-crystalline resins.

Experimental
The new TPI polymer from SABIC Innovative Plastics was blended with other thermoplastic polyimides and/or polyetherimides in varying proportions across the composition space. Blend compositions can be varied to tailor mechanical, thermal, flow and end-use properties for a wide-array of applications. Two such TPI blends have recently been commercialized as EXTEM UH1006 and UH1016 grades. These TPI blends are melt processable on existing standard processing equipment. All blends were compounded on a WP30 twin-screw extruder. Barrel temperatures varied from 350C to 400C depending on blend composition. All ASTM test parts were molded on a standard 170-ton injection molding machine equipped with a general purpose screw according to guidelines recommended in Table 1. Prior to molding, pellets were dried at 175C for 6 hours in a dehumidifying dryer to a moisture content of 0.02 wt% or lower. All molded part data were generated according to ASTM guidelines.

Discussion
Figure 1 shows capillary rheology (melt viscosity vs. shear rates) for the TPI blends in their typical processing range. The two commercial grades have significantly different viscosities to enable a variety of end use applications and part designs. The viscosity can be further tweaked as needed with the addition of processing aids. Typical flow lengths for the EXTEM UH1006 grade are shown in Figure 2. These data were generated using a spiral flow tool on a 170-ton injection molding machine. Injection pressure was fixed at 1,378 bar (20,000 psi). The actual mold temperature was ~165-170C. Flow lengths were measured at three different thickness and three melt temperatures. Since the UH1016 grade has a lower viscosity, it demonstrates longer flow lengths under comparable processing conditions.

Datasheet properties of one of the new TPI blends (EXTEM UH1006 grade) are compared in Table 2 to a polyetherimide (ULTEM 1000 resin) and a semicrystalline TPI (AURUM PL450C resin). The new TPI blend shows improved tensile and flexural properties (modulus and strength) at 23C as well as at 150C. Compressive strength is also higher for the new TPI blend. The new TPI blend has a lower coefficient of thermal expansion and hence better dimensional stability. Flammability performance in terms of UL-V0 rating and limiting oxygen index are equivalent for the new TPI blend and the semi-crystalline TPI. UL rating of V0 at a thickness of 0.4 mm without addition of any other additives demonstrates that the flame-retardant performance of the TPI blend is significantly superior to the polyetherimide and other high performance materials. The semi-crystalline TPI AURUM has a Tg~250C and Tm~388C, but it is a slow crystallizing polymer. It is amorphous and transparent as molded, and the use temperature is limited to 240C9. It requires a secondary annealing step (>10 hours at 220-280C) to develop crystallinity and improve heat resistance for use above 240C. Exposure of molded amorphous parts to temperatures above 240C without any annealing can cause dimensional stability issues. Annealing of a semicrystalline resin can also lead to dimensional changes. The new TPI blends, however, do not require any annealing since these are amorphous blends. Molded parts maintain good dimensional stability even at high temperatures. High temperature performance of a commercial TPI blend (EXTEM UH1006 grade) is highlighted in Figures 3 and 4. The blend shows superior tensile and flexural strength retention even at 200C (Figure 3). Modulus retention at higher temperatures for the blend also leads to excellent creep resistance at 150C and 200C (Figure 4). Another distinguishing feature of the new amorphous TPI blends is that the heat resistance (Tg or heat distortion temperature) is tailorable over a wide range by varying blend components and composition. The new TPI polymer can be blended with other thermoplastic polyimides and/or polyetherimides. Since the new TPI polymer has a Tg ~ 311C, blends with a Tg greater than 300C are feasible. The commercial TPI blends (EXTEM UH1006 and UH1016 grades) represent only two of a wide-range of products which are possible by blending with the new TPI polymer. Figure 5 shows an example of a binary blend of the new TPI polymer and a polyetherimide. The blend composition was varied by changing the new TPI polymer

content in the 60% to 100% range. The Tg of a miscible blend can be usually be predicted using the well known Fox equation10. The actual Fox equation is shown in Figure 5. The blend Tg was experimentally measured using a Perkin-Elmer Differential Scanning Calorimeter at a heating rate of 20C/min under a nitrogen purge. The predicted and measured Tg for this binary TPI blend are in very good agreement. Thus, for this particular blend Tg can be designed to any target by varying the composition i.e. the content of the new TPI resin.

Conclusions
Two new high heat thermoplastic polyimide blends with good melt processability have been designed. These TPI blends offer good dimensional stability, high temperature strength, creep resistance and excellent flame resistance. By leveraging the new TPI polymer, it is possible to design a wide-range of blends with other amorphous thermoplastic polyimides, polyetherimides or semi-crystalline resins to target glass transition temperatures exceeding 300C.

References
S. Tamai, A. Yamaguchi and M. Ohta, Polymer, 37(16), 3683 (1996). 2. J. de Abajo and J.G. de la Campa, Advances in Polymer Science, 140, 23 (1999). 3. V.L. Bell, U.S. Patent 4,094,862 (1978). 4. K. Blizard and M. Druy, ANTEC, 53(2), 3124 (1995). 5. S.P. Ma and T. Takahashi, Polymer, 37(25), 5589 (1996). 6. S. Lee, Plastics Technology Magazine, January 2007. (http://www.ptonline.com/articles/200701fa6.html) 7. EXTEM Resins from SABIC Innovative Plastics. (http://www.geplastics.com/gep/Plastics/en/ProductsA ndServices/ProductLine/extem.html) 8. MAX-Series (http://www.victrex.com/en/peek_poly/ victrex_max-series.php) at Victrex plc website. 9. AURUM Product literature from Mitsui Chemicals. (http://www.aurumtpi.com) 10. L.A. Utracki, Polymer Blends Handbook, 187 (2002). 1.

Key Words: TPI, thermoplastic polyimide, TPI blend

* trademark of Mitsui Chemicals **trademark of SABIC Innovative Plastics IP BV

Table 1. Typical Injection Molding Conditions for the TPI Blends EXTEM UH1006 / UH1016 Grades Maximum Moisture Content % 0.02 Drying Temperature C 175 Drying Time hr 6 Melt Temperature C 400 - 415 Nozzle Temperature C 395-415 Front - Zone 3 Temperature C 395-415 Middle - Zone 2 Temperature C 390 - 405 Rear - Zone 1 Temperature C 380 - 390 Mold Temperature C 150 - 175 Back Pressure bar 3-5 Screw Speed rpm 40-70 Shot to Cylinder Size % 40 - 70

Table 2.
ASTM Testing PROPERTY Tensile Modulus - 23C Tensile Strength - 23C - 150C Flexural Modulus - 23C - 150C Flexural Strength - 23C - 150C Compressive Strength - 23C Izod Impact, notched - 23C

Property Comparison of EXTEM UH1006 Grade

Amorphous TPI Blend EXTEM UH1006 3,800 120 68 3,520 2,500 175 109 160 75 46 240 1.37 0.4 47 Amorphous Polyetherimide ULTEM 1000 3,200 105 50 3,300 160 130 53 50 190 1.27 0.8 to 1.6 45 Semi-crystalline TPI AURUM PL450C 2,760 92 58 2940 2550 137 88 120 90 55 238 1.33 0.4 47

Unit MPa MPa MPa MPa MPa MPa MPa MPa J/m

Coefficient of Thermal Expansion ppm/C HDT, 1.8 MPa, 3.2mm (as-molded) C Density UL-V0 Flammability Rating Limiting Oxygen Index g/cc mm %

Figure 1. Rheology of EXTEM UH Blends

10000

Figure 2. Spiral Flow of EXTEM UH1006 Grade

400 Flow Length (mm) 300 200 100 1.5 mm 0 390 400 410 420 430
1,378 bar (20,000 psi) Injection Pressure

415C

UH1006 UH1016

Viscosity (Pa-s)

3.0 mm

1000

2.3 mm

100 100

1000

10000

Shear Rate (1/s)

Melt Temperature (C)

Figure 3. High Temperature Strength of EXTEM UH1006 Grade

100% Property Retention (%) 80% 60% 40% 20% 0% 0 50 100 150 200 Temperature (C) Flexural Strength Tensile Strength

Figure 4. Creep Resistance of EXTEM UH1006 Grade

10 23C 150C 200C 20MPa Load

Strain (%)

0.1 1.0E-02

1.0E-01

1.0E+00

1.0E+01

1.0E+02

Time (Hours)

Figure 5. Tailoring Tg of the TPI Blends

1
Blend Tg (C)

(Tg )blend

w1 (Tg )1

w2 (Tg ) 2

311C

>200C 0.0 0.2 0.4 0.6

Predicted Actual
0.8 1.0

New TPI Polymer (wt fraction)