Elastomer polarity

Polado Polarcor Polar elastomers Polar imetry Polarite... 

Surface Activity - A filler can offer high siuface area and high structure, but still provide relatively poor reinforcement if it has low specific surface activity. The specific activity of the filler siuface per cm of filler-elastomer interface is determined by the physical and chemical nature of the filler surface in relation to that of the elastomer. Nonpolar fillers are best suited to nonplar elastomers polar fillers work best in polar elastomers. Beyond this... 

Two gas chromatograms showing the effect of polarity of the stationary phase on the separation efficiency for three substances of increasing polarity toluene, pyridine, and benzaldehyde. (a) Separation on silicone SE-30, a nonpolar phase, and (b) separation on elastomer OV-351, a more polar phase. Note the greatly changed absolute and relative retention times the more polar pyridine and benzaldehyde are affected most by the move to a more polar stationary phase. 

Rubbers. Plasticizers have been used in mbber processing and formulations for many years (8), although phthaHc and adipic esters have found Htde use since cheaper alternatives, eg, heavy petroleum oils, coal tars, and other predominandy hydrocarbon products, are available for many types of mbber. Esters, eg, DOA, DOP, and DOS, can be used with latex mbber to produce large reductions in T. It has been noted (9) that the more polar elastomers such as nitrile mbber and chloroprene are insufficiendy compatible with hydrocarbons and requite a more specialized type of plasticizer, eg, a phthalate or adipate ester. Approximately 50% of nitrile mbber used in Western Europe is plasticized at 10—15 phr (a total of 5000—6000 t/yr), and 25% of chloroprene at ca 10 phr (ca 2000 t/yr) is plasticized. Usage in other elastomers is very low although may increase due to toxicological concerns over polynuclear aromatic compounds (9). 

Nitrile mbber compounds have good abrasion and water resistance. They can have compression set properties as low as 25% with the selection of a proper cure system. The temperature range for the elastomers is from —30 to 125°C. The compounds are also plasticized using polar ester plasticizers. The main dilemma is the selection of a heat-stable, nonfugitive plasticizer that also gives good low temperature properties. 

Epichlorohydrin. Commercial polyester elastomers include both the homopolymer and the copolymer of epichl orohydrin with ethylene oxide. The very polar chloromethyl groups create basic resistance to oil for these polymers, and they have been extensively used in fuel lines however, the desire for lower fuel permeation is causing a search to be made for other polymers (10) (see Elastomers, synthetic-polyethers). 

Fluoroelastomers excel compared to aU other elastomers in heat, chemical, flame, weathering, fuel, and o2one resistance. In addition oU, oxygen, and water resistance ate very good. The fluoroelastomers, however, ate attacked by amines and some highly polar solvents. The abrasion resistance and low temperature properties ate adequate for most appHcations. 

SiHcone elastomers possess outstanding resistance to heat aging. The Si—O—Si backbone imparts resistance to oxygen, o2one, uv, and to some polar fluids. However, the strength of these elastomers is usually just adequate. They have low abrasion resistance and tear strength (see Silicon compounds, silicones). 

Ester plasticizers are used mainly in very polar elastomers, such as neoprene and nitrile mbber, to improve low or high temperature performance or impart particular oil or solvent resistance to a compound 5—40 parts are commonly used (see Plasticizers). Resins and tars are added to impart tack, soften the compound, improve flow, and in some cases improve filler wetting out, as is the case with organic resins in mineral-filled SBR. Resinous substances are also used as processing agents for homogenizing elastomer blends. 

To improve the performance of acryUc elastomers, side chains are required where the 5 value is higher than with alkyl groups. Thus the use of polar groups, for instance heteroatoms, is suggested. The general formula for these acrylate monomers may be portrayed as follows ... 

The process yields a random, completely soluble polymer that shows no evidence of crystallinity of the polyethylene type down to —60°C. The polymer backbone is fully saturated, making it highly resistant to ozone attack even in the absence of antiozonant additives. The fluid resistance and low temperature properties of ethylene—acryUc elastomers are largely a function of the methyl acrylate to ethylene ratio. At higher methyl acrylate levels, the increased polarity augments resistance to hydrocarbon oils. However, the decreased chain mobiUty associated with this change results in less fiexibihty at low temperatures. 

FZ elastomers have excellent resistance to hydrocarbons and inorganic acids as expected for a fluoriaated elastomer. They are strongly affected by polar solvents, but are more resistant to amines than most other fluoriaated elastomers as showa ia Table 2. 

All these elastomers, especially poly(ethylene- (9-butylene) and poly(ethylene- (9-propylene), are nonpolar. The corresponding block copolymers can thus be compounded with hydrocarbon-based extending oils, but do not have much oil resistance. Conversely, block copolymers with polar polyester or polyether elastomer segments have Htde affinity for such hydrocarbon oils and so have better oil resistance. 

In the hard polymer/elastomer combinations, the elastomer is often chosen to be a polar mbber or it is cross-linked in some cases it is both. Either of these features improves the resistance to oils and solvents (44). 

In thermoplastic polyurethanes, polyesters, and polyamides, the crystalline end segments, together with the polar center segments, impart good oil resistance and high upper service temperatures. The hard component in most hard polymer/elastomer combinations is crystalline and imparts resistance to solvents and oils, as well as providing the products with relatively high upper service temperatures. 

Commercially, anionic polymerization is limited to three monomers styrene, butadiene, and isoprene [78-79-5], therefore only two useful A—B—A block copolymers, S—B—S and S—I—S, can be produced direcdy. In both cases, the elastomer segments contain double bonds which are reactive and limit the stabhity of the product. To improve stabhity, the polybutadiene mid-segment can be polymerized as a random mixture of two stmctural forms, the 1,4 and 1,2 isomers, by addition of an inert polar material to the polymerization solvent ethers and amines have been suggested for this purpose (46). Upon hydrogenation, these isomers give a copolymer of ethylene and butylene. 

Table 15. Properties of Hard Polymer/Elastomer Combinations Based on Polar Elastomers...

Oil resistance demands polar (non-hydrocarbon) polymers, particularly in the hard phase. If the soft phase is non-polar but the haid phase polar, then swelling but not dissolution will occur (rather akin to that occurring with vulcanised natural rubber or SBR). If, however, the hard phase is not resistant to a particular solvent or oil, then the useful physical properties of a thermoplastic elastomer will be lost. As with all plastics and rubbers, the chemical resistant will depend on the chemical groups present, as discussed in Section 5.4. 

Class and Chu demonstrated that if a tackifier is chosen that is largely incompatible with the elastomer, a modulus increase due to the filler effect is observed and little change in Ta results, and once again a PSA would not be obtained. This was observed for mixtures of low molecular weight polystyrene resin and natural rubber. The same polystyrene resin did tackify SBR, a more polar elastomer that is compatible with the resin. Hydrogenating the polystyrene to the cycloaliphatic polyvinylcyclohexane changed the resin to one now compatible with the less polar natural rubber and no longer compatible with SBR. These authors also provide... 

Chlorobutyl rubber is prepared by chlorination of butyl rubber (chlorine content is about 1 wt%). This is a substitution reaction produced at the allylic position, so little carbon-carbon double unsaturation is lost. Therefore, chlorobutyl rubber has enhanced reactivity of the carbon-carbon double bonds and supplies additional reactive sites for cross-linking. Furthermore, enhanced adhesion is obtained to polar substrates and it can be blended with other, more unsaturated elastomers. 

For rosins and rosin esters, the produets having high aeid numbers are the most susceptible to oxidation and have inferior viscosity stability and colour stability in adhesive formulations. Thus, when stability properties are essential in adhesives, rosin esters rather than high aeid number rosins are used. However, the high acid number resins are polar and display better adhesion to polar elastomers and polymeric surfaces. 

A more quantitative estimation of compatibility can be obtained with the solvent cloud point test. The solvent cloud point is based on the idea that resins will be compatible with elastomers of similar chemical nature. Thus aliphatic resins will be effective tackifiers for aliphatic elastomers, such as natural rubber, while aromatic solvents are needed for aromatic elastomers, such as SBR. Solvent cloud point tests are carried out in three solvent systems which represent aliphatic, aromatic, or polar systems [16j ... 

Tackifying resins enhance the adhesion of non-polar elastomers by improving wettability, increasing polarity and altering the viscoelastic properties. Dahlquist [31 ] established the first evidence of the modification of the viscoelastic properties of an elastomer by adding resins, and demonstrated that the performance of pressure-sensitive adhesives was related to the creep compliance. Later, Aubrey and Sherriff [32] demonstrated that a relationship between peel strength and viscoelasticity in natural rubber-low molecular resins blends existed. Class and Chu [33] used the dynamic mechanical measurements to demonstrate that compatible resins with an elastomer produced a decrease in the elastic modulus at room temperature and an increase in the tan <5 peak (which indicated the glass transition temperature of the resin-elastomer blend). Resins which are incompatible with an elastomer caused an increase in the elastic modulus at room temperature and showed two distinct maxima in the tan <5 curve. 

The chemical nature of the tackifier also affects the compatibility of resin-elastomer blends. For polychloroprene (a polar elastomer) higher tack is obtained with a polar resin (PF blend in Fig. 27) than with a non-polar resin (PA blend in Fig. 27). Further, the adhesion of resin-elastomer blends also decreases by increasing the aromatic content of the resin [29]. Fig. 28 shows a decrease in T-peel strength of styrene-butadiene rubber/polychloroprene-hydrocarbon resin blends by increasing the MMAP cloud point. Because the higher the MMAP... 

Superior resistance to oils. NBR has the highest resistance of any of the general elastomers. NBR resists most greases and non-polar solvents. 

NBR is a polar polymer and shows superior compatibility with resins as compared to other elastomers. The major ingredients, in addition to the elastomer, for the NBR adhesives are given below. 

Both the dipolymers and terpolymers have excellent resistance to hydrocarbons found m petroleum-based fuels and lubricants The 69 5% F terpolymer resists swellmg m blended fuels that contain metlianol and can be used in contact with certain phosphate ester-based hydraulic fluids Terpolymers are preferred for contact with aromatic solvents, although either type performs well in higher alcohols VDF-based elastomers dissolve m polar aprotic solvents such as ketones, esters, amides, and certam ethers These elastomers are therefore not suitable for contact with fluids that contain substantial amounts of these solvents because of excessive swell and consequent loss of mechanical properties... 

Replacement of a vinylidene fluonde unit by an e ylene or propylene unit in a locally perfluonnated cham environment greatly reduces the acidity ot the methylene hydrogens Copolymers of TFE and propylene are therefore considerably more resistant to bases and polar solvents than VDF-based elastomers TFE and propylene form a highly altematmg structure... 

Zinc salt of maleated EPDM rubber in the presence of stearic acid and zinc stearate behaves as a thermoplastic elastomer, which can be reinforced by the incorporation of precipitated silica filler. It is believed that besides the dispersive type of forces operative in the interaction between the backbone chains and the filler particles, the ionic domains in the polymer interact strongly with the polar sites on the filler surface through formation of hydrogen bonded structures. 

Figure 11 Polarized microscope photographs ( x 800) (A) PBT-TLCP-elastomer blend (60 25 15 wt ratio). Dark phase is the TLCP phase. (B) Nylon 6-TLCP-elastomer blend (60 25 15 wt ratio). Dark phase is the TLCP phase and large white one is the elastomer phase. Source Ref. 56.

As shown in Fig. IIB, dispersion morphology for the nylon 6/Vectra B/SA-g-EPDM blend was totally different from that of the PBT-Vectra A-SA-g-EPDM blend. TLCP phases were very uniformly and finely dispersed in the nylon 6-Vectra B-SA-g-EPDM blend and a large fibril shape observed in the PBT-Vectra A-SA-g-EPDM blend could not be seen under polarized microscope. It should be noted that the size of the dispersed TLCP phase is very small (submicron size). This small size of the TLCP phase in the nylon 6/elastomer matrix was not observed by any others [4,54,55,58]. A closer look by SEM more clearly revealed the dispersion of Vectra B in the matrix (Fig. 12B). TLCP phases are very... 

---