6.3 6.3.

PV( -Nitrile Rubber Blends Chemistry

PVC has been added to compounds of baled thermoset NBR to improve ozone and s o h e n t resistance since
the 1960s. In 1983. the first powdered non-crosslinkcd NBR. developed specifically as a modifier for PVC. became available. Since thai time a number of others NBRs. including food and improved processing grades, have been commercialized. These are true plasticizers that provide the PVC' with desired rubberlike properties. Thermoplastic blends are created when the predominant polymer is PVC. compounded with NBR. plasticizers such as dioctyl phthalate <IX)P), fillers, and stabilizers. A typical formulation is:

Ingredients
PVC NBR DOP CaCO, Ba-Zn stabilizer Epoxidizcd soy oil

Pan.\ 100 33 75 20 2 2.5

Such blends with non-crosslinked NBR feel and act more rubbery than conventional liquid plasticized flexible PVC (FPVC). but they arc not very clastomeric. Rapid recover)' or rubber-like snap is poor. Properly formulated PVCNBR blends are flexible at low temperatures

and have good tear strength. They show good resistance to abrasion and compression set and low swelling when immersed in oils or fuels. However, any liquid plastici/crs used are subject to extraction on immersion resulting in shrinkage and hardening. Important formulation variables, besides the ratio of PVC to NBR. are the acrylonitrile (AN) content and the Mooney viscosity of the NBR. and the molecular weight of the PVC. In general. NBR with an optimum AN content of MY', is needed to obtain single-phase homogeneous blends. Reports of a single 7^, as measured by differential thermal analysis 113 1, intermediate between the T^s of the two polymers, and the absence of two phases by electron photomicroscopy 114]. support a single-phase morphology. There are also reports of two glass transitions [15] and micro-domains, rich in one or the other of the components 116]. indicating the morphology of these blends is complex. The NBR may be cither non-crosslinkcd or prc-crosslinkcd to varying degrees. Use of non-crosslinkcd NBR results in the lowest viscosity FPVC blends, analogous to making thermoplastic olefins (TPOs) by adding un-crosslinked EPDM to polypropylene. Their lower viscosity makes these flexible plastics suitable for injection molding operations. However, only crosslinkcd NBRs provide the FPVC with enough resistance to compression set and other measurements of rubber character to be considered true TPEs. The use of precrosslinked NBR increases melt viscosity, making these blends more suitable for calendering or extrusion operations. Resistance to compression set improves with the level of NBR added and its crosslink density.

6.3.2

Melt Compounding and Processing

The NBR additives arc supplied as free-flowing powders for easy incorporation in ihc standard PVC dry blending operation. They have an average particle size of about 0.5 mm and contain about 10% of a PVC. calcium carbonate, or silica partitioning agent 117J. They are free flowing, air conveyable. resistant to separation from PVC blends, and resistant to agglomeration during long-term storage. The NBR powders can be added to the PVC dry blending cycle after the PVC lias absorbed all of the liquid plasticizers. Tlie temperature of die PVC dry-blend should be no higher than 40 C to avoid rubber agglomeration [IS]. The P\C-NBR powder-blends can be processed in conventional thermoplastic mixing equipment, including low- and high-intensity mixers, single and twin-screw exuuders. continuous mixers, and kneaders. The PVC-NBR blend can be either melt compounded and pelletized prior to further processing or it can be immediately fabricated into finished shapes id-bouse. Conventional PVC melt processing equipment is recommended for fabrication. In recent years, fully compounded blends of PVC-NBR in pellet form have become available to rubber and flexible plastics fabricators. They have been marketed as alternatives to FPVC, mid-performance rubbers,

and to "in-house" PVC-NBR compound development. The rtieology curve for a typical commercially available PVC-NBR compound (70 Shore A) is shown in Figure 6.4 1 19]. It shows lower viscosity than either the MPRs in Fig. 6.3 or typical "in-house" compounded PVC-NBR blends.

10OO

oI

------------------J_____________I_____________________I__________I
lOO 1000 Slieai Rate, l/sec 10000

10

Figure 6.4 Commercial PV ( -mlrilc rubher compound (Sarlink I 170), capillary riwotegy at ISO C

6.3.3

Mechanical Properties

The physical properties of these compounds are typical for those found in mid-performance TSRs. The stress-strain curves for three compounds |20| arc shown in Fig 6.5. With increasing crosslinking and viscosity the stiffness of the compound increases slightly and the elongation decreases. Other properties are show n in Table 6.6. Resistance to both high-temperature and low-temperature compression set is somewhat improved by use of more highly crosslinked rubber. As for the remaining properties shown in this table, rubber selection docs not appear to greatly affect hardness, tear resistance, or brittle point. Some drop-off in abrasion resistance, however, is evident at the highest crosslinking level.

In another study 114|. using a higher level of NBR. a lower level of liquid plasticizer and no filler, greater differences in physical properties were evident when comparing formulations containing crosslinked versus un-crovslmked NBR. The formulation containing the cross-linked NBR showed significantly superior tensile strength, compression set resistance, abrasion resistance, and llexural properties. The molecular weight of the PVC also has a strong influence on the compound's physical properties; as it was increased, the tensile, modulus, and hardness values of the blends also increased. Compression set also unproved writh increasing PVC molecular weight. Very soft compositions with Shore A hardnesses

6.4.4

Melt Compounding

The plasticized PVC dry-blend portion of these blends is prepared from suspension grade PVC", either in a high intensity mixer or in a heated ribbon blender. Ester type plasticizers such as DOP are most commonly used. Plasticizer levels between 10 and so parts per 100 of polymer <php) arc recommended tor the PVC-

i a

3O0

Elongation, % Figure 6.5 pnipcrtics PVC-nitrile rubber compounds, slrcs-s-strain

COPE blends. This is less than the 1 : 1 level often used in plasticized PVC. Plasticizer levels below lOphpmay give poor impact resistance and proccssibilitv- Polymeric ester plasticizers combined with trimcllitate plasticizer should offer improved heat and oil resistance over DOP. Ground limestone and whiting are the most common fillers for these systems. China clay is also used for electrical insulation compounds. Filler levels of 10 to 20 php are typical, although up to 50 php have been used. It is impartial 10 use neutral pH grade (i.e., ph 7-8) filler to avoid degradation of the COPE. Although stearic acid and other free fatty acids are used for both internal and external lubrication of plasticized PVC compounds, they are not recommended for use in these COPE-PVC blends, since they promote degradation of the COPE Instead, fatty acid amides (used at the I % level) arc rccommcnded.The copolycstcr can be mixed into the plasticized PVC dry-blend before melt compounding, or the PVC and COPE can be metered independently to the melt compounding device. Melt compounding can be carried out in conventional compounding machines including Banbury batch mixers, kneaders. and single- or twin-screw extruders with sufficient mixing sections. Maximum melt temperature should he less than 190 CC. The product must be dried to less than 0.10** moisture, and packaged in moisture-barrier containers.

6.4.5

Processing

PVC-COPE blends can be processed on conventional injection molding and extrusion equipment.
Gradual transition screws, such as those used for polyethylene, ate preferred to avoid overworking the material. Compression ratios of 3.0 : 1 to 3.5 : I arc recommended, as well as L/D's of at least 1 8 : 1 for molding and 24 : I for extrusion. Relatively deep metering zone flights, from 2.5 to 3.0 mm for a 6.35 cm (2.5 in.) screw, are also re-commended.Since COPHs are subject to hydrolysis at processing temperatures, il is absolutely essentia] that the PVC -COPE compound be dry for processing. PVC is inherently thermally unstable and total heat history during processing should be kept to a minimum. Temperatures at the feed zone in the region of 130 to 155 C arc suggested w ith a gradual rise in temperature toward the nozzle to approx. 150 to 170C. The preferred melt temperature range for a 50 : 50 PVC -COPE blend is 160 to 170 nC. Increased melt temperature, particularly for injection molding, may be required at higher levels of COPE or if the plasticizer level is lower than 30 php. In any event, maximum melt temperature should never exceed 190 C. As w ith all PVC -bascd blends, corrosion resistant matcnals of construction arc recommended to maximize equipment life.

6.4.6

Applications

PVC-COPE blends are a lower cost alternative to TPUs in protective covers tor hose and tubing. They also offer an extended operating temperature range over HKI'r PVC cover stocks. In automotive primary wiring, PVC-COPE blends can withstand higher under-the-hood temperatures than 100'* PVC systems, lor sport shoe soling, PVC-COPE blends cost less than TPUs, but have equivalent low-temperature properties and abrasion resistance. They do not suffer from plasticizer loss, avoiding the cracking problems

associated with 100rr PVC soling. PVC-COPE blends are

also used as protective jackets in retractile cords for telephones and domestic electrical appliance because of their better memory characteristics compared to FPVC. They do not lose their retractile characteristics because of tension | temperature. Although material costs are higher than tor plasticized PV ( , PVC-COPE blends offer a lower-cost finished product. The better memory characteristics of the blends allow cord covers to be reduced in thickness. This also permits the use of fewer strands of larger diameter copper conductors in place of multiple tw ist constructions for thinner conductors, which offers additional savings,