Low temperature rubbers

Bis(nitrile oxides) obtained from dialkylbenzenes have been claimed as low-temperature rubber vulcanization agents (517). Curing of poly(butadiene-co-acrylonitrile) with 2,4,6-trimethylisophthalodinitrile N-oxide produces rubbery material of good quality, however, curing of (polybutadiene) was unsuccessful (518). The solubility of dinitrile oxides and stability of their ketone solutions has been studied for their application as vulcanizing agents in the production of mbberized materials (519). 

Borodachev IV, Volkhonskaya EV, Guk YuV, Zhukov AYu, Tsypin GI, Chernysheva SYu, Antipova VF, Panova NV. Bis(nitrile oxides) of dialkylbenzenes as low-temperature rubber vulcanization agents with low unsaturation and their manufacture from dialkylbenzenes, RU Patent No. 2042664 1995 [Chem. Abstr. 1996 124 263170],... 

The rubber addition results, as expected, in the presence of a low temperature rubber loss maximum. The DMA measurements also show, however, that a part of the added rubber phase influences the intensity of both PP relaxation effects. Such an effect might be important for the toughening efficiency of the used type of rubber. 

The Vistalon 404 and 4608 are amorphous C2C3 rubbers, while Vistalon 5600 contains a crystalline fraction of 4 %wt. The Nordel 1500 and 3391 are typical semi-crystalline C2C3 rubbers with crystalline fractions of respectively 15 %wt. and 12 %wt. Bach of these rubbers was added to the PP in three different concentrations i.e. 10, 15 and 20 %wt. Only the amorphous fraction of these C2C3 rubbers is assumed to contribute to the measured low temperature rubber loss maximum. 

Whether rubber, in the light of the foregoing discussion, would be better described as a liquid or a solid is one which would no doubt have appealed to the scholastic philosophers. What is reaUy more significant is that rubber provides another example of the way in which certain combinations of the variables defining configurations cease to be fixed while others remain subject to control. At low temperatures rubber-hke substances freeze, in the sense that the molecular motions characteristic of the condition cease to be possible. 

Nitrile mbber finds broad application in industry because of its excellent resistance to oil and chemicals, its good flexibility at low temperatures, high abrasion and heat resistance (up to 120°C), and good mechanical properties. Nitrile mbber consists of butadiene—acrylonitrile copolymers with an acrylonitrile content ranging from 15 to 45% (see Elastomers, SYNTHETIC, NITRILE RUBBER). In addition to the traditional applications of nitrile mbber for hoses, gaskets, seals, and oil well equipment, new applications have emerged with the development of nitrile mbber blends with poly(vinyl chloride) (PVC). These blends combine the chemical resistance and low temperature flexibility characteristics of nitrile mbber with the stability and ozone resistance of PVC. This has greatly expanded the use of nitrile mbber in outdoor applications for hoses, belts, and cable jackets, where ozone resistance is necessary. 

Dry chlorine has a great affinity for absorbing moisture, and wet chlorine is extremely corrosive, attacking most common materials except HasteUoy C, titanium, and tantalum. These metals are protected from attack by the acids formed by chlorine hydrolysis because of surface oxide films on the metal. Tantalum is the preferred constmction material for service with wet and dry chlorine. Wet chlorine gas is handled under pressure using fiberglass-reinforced plastics. Rubber-lined steel is suitable for wet chlorine gas handling up to 100°C. At low pressures and low temperatures PVC, chlorinated PVC, and reinforced polyester resins are also used. Polytetrafluoroethylene (PTFE), poly(vinyhdene fluoride) (PVDE), and... 

Butyl mbber, a copolymer of isobutjiene with 0.5—2.5% isoprene to make vulcanization possible, is the most important commercial polymer made by cationic polymerization (see Elastomers, synthetic-butyl rubber). The polymerization is initiated by water in conjunction with AlCl and carried out at low temperature (—90 to —100° C) to prevent chain transfer that limits the molecular weight (1). Another important commercial appHcation of cationic polymerization is the manufacture of polybutenes, low molecular weight copolymers of isobutylene and a smaller amount of other butenes (1) used in adhesives, sealants, lubricants, viscosity improvers, etc. 

Polypropylene polymers are typically modified with ethylene to obtain desirable properties for specific applications. Specifically, ethylene—propylene mbbers are introduced as a discrete phase in heterophasic copolymers to improve toughness and low temperature impact resistance (see Elastomers, ETHYLENE-PROPYLENE rubber). This is done by sequential polymerisation of homopolymer polypropylene and ethylene—propylene mbber in a multistage reactor process or by the extmsion compounding of ethylene—propylene mbber with a homopolymer. Addition of high density polyethylene, by polymerisation or compounding, is sometimes used to reduce stress whitening. In all cases, a superior balance of properties is obtained when the sise of the discrete mbber phase is approximately one micrometer. Examples of these polymers and their properties are shown in Table 2. Mineral fillers, such as talc or calcium carbonate, can be added to polypropylene to increase stiffness and high temperature properties, as shown in Table 3. 

Nitrile Rubber. Nitrile mbbers are made by the emulsion copolymerization of acrylonitrile (9—50%) and butadiene (6) and designated NBR. The ratio of acrylonitrile (ACN) to butadiene has a direct effect on the properties on the nature of the polymers. As the ACN content increases, the oil resistance of the polymer increases (7). As the butadiene content increases, the low temperature properties of the polymer are improved (see Elastomers, SYNTHETIC-NITRILE RUBBER). 

Fast, low temperature curing mbber compounds can be prepared by initial heat prevulcanisation of the Hquid latex and are marketed commercially (Revultex, Doverstrand Corporation). Rubber deposited from these often needs tittle more heat than that required to dry the deposit, to achieve optimum tensile strength and elongation. Such compounds are often used by small companies manufacturing thin-wall dipped medical latex products, such as examination gloves, as few compound preparation facilities are needed by the dipping company. 

Citric acid esters are used as plasticizers ia plastics such as poly(viayl chloride), poly(vinhdene chloride), poly(viQyl acetate), poly(viQyl butyral), polypropylene, chlorinated rubber, ethylceUulose, and cellulose nitrate. Most citrate esters are nontoxic and are acceptable by the FDA for use in food-contact packaging and for flavor in certain foods. As a plasticizer, citrate esters provide good heat and light stabiUty and excellent flexibiUty at low temperatures. Triethyl citrate, tri- -butyl citrate, isopropyl citrate, and stearyl citrate are considered GRAS for use as food ingredients (224—228). 

The polymerization system is of the cationic type, usiag coinitiators such as AlCl and water at very low temperatures (—100° C) and leading to an almost instantaneous polymeriza tion (see Elastomers, SYNTHETIC-BUTYL RUBBER). 

S. Hayashi, M. Oyama, K. Hashimoto, and T. Nakagawa, "New Improved Low Temperature Hydrogenated Nitrile Rubber (HNBR)," paper presented at theH.CA. Racbber Division Meeting, Detroit, Mich., Oct. 8—11,1991. 

Well, that is the case at the low temperature, when the rubber has a proper modulus of a few GPa. As the rubber warms up to room temperature, the Van der Waals bonds melt. (In fact, the stiffness of the bond is proportional to its melting point that is why diamond, which has the highest melting point of any material, also has the highest modulus.) The rubber remains solid because of the cross-links which form a sort of skeleton but when you load it, the chains now slide over each other in places where there are no cross-linking bonds. This, of course, gives extra strain, and the modulus goes down (remember, E = [Pg.61]

The metal film is then electroplated with copper, and the metal part brazed to the copper plating. Adhesives, usually epoxy resins, are used to join parts at low temperatures. Finally, ceramic parts can be clamped together, provided the clamps avoid stress concentrations, and are provided with soft (e.g. rubber) packing to avoid contact stresses. 

Although the nitrile rubbers employed normally contain about 35% acrylonitrile the inclusion of nitrile rubber with a higher butadiene content will increase the toughness at low temperatures. For example, whereas the typical blend cited above has an impact strength of only 0.9 ft Ibf in notch at 0°F, a blend of 70 parts styrene-acrylonitrile, 30 parts of nitrile rubber (35% acrylonitrile) and 10 parts nitrile rubber (26% acrylonitrile) will have an impact value of 4.5 ftlbfin notch at that temperature. ... 

Whilst exhibiting the excellent low-temperature flexibility (with a Tg of about -80°C) and very good heat resistance (up to 200°C) typical of a silicone rubber, the fluorosilicones also exhibit good aliphatic oil resistance and excellent aging resistance. However, for some applications they have recently encountered a challenge from the polyphosphazenes (see Section 13.10). 

The important properties of the rubbers are their temperature stability, retention of elasticity at low temperatures and good electrical properties. They are much more expensive than the conventional rubbers (e.g. natural rubber and SBR) and have inferior mechanical properties at room temperature. 

If polypropylene is too hard for the purpose envisaged, then the user should consider, progressively, polyethylene, ethylene-vinyl acetate and plasticised PVC. If more rubberiness is required, then a vulcanising rubber such as natural rubber or SBR or a thermoplastic polyolefin elastomer may be considered. If the material requires to be rubbery and oil and/or heat resistant, vulcanising rubbers such as the polychloroprenes, nitrile rubbers, acrylic rubbers or hydrin rubbers or a thermoplastic elastomer such as a thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer may be considered. Where it is important that the elastomer remain rubbery at very low temperatures, then NR, SBR, BR or TPO rubbers may be considered where oil resistance is not a consideration. If, however, oil resistance is important, a polypropylene oxide or hydrin rubber may be preferred. Where a wide temperature service range is paramount, a silicone rubber may be indicated. The selection of rubbery materials has been dealt with by the author elsewhere. ... 

Hybrids of block copolymer rubbers and acrylics have also been used to increase the low-temperature impact resistance of the adhesive used for body-side molding attachment [127]. To further enhance performance, a new type of hybrid adhesive has been developed, which combines an adhesive polymer, like an... 

Both side groups and carbon-carbon double bonds can be incorporated into the polymer structure to produce highly resilient rubbers. Two typical examples are polyisoprene and polychloroprene rubbers. On the other hand, the incorporation of polar side groups into the rubber structure imparts a dipolar nature which provides oil resistance to these rubbers. Oil resistance is not found in rubber containing only carbon and hydrogen atoms (e.g. natural rubber). Increasing the number of polar substituents in the rubber usually increases density, reduces gas permeability, increases oil resistance and gives poorer low-temperature properties. 

When the temperamre is lowered, rubbers become stiff and brittle. All rubbers eventually stiffen to a rigid, amorphous glass at the glass transition temperature (Tg). This temperature also indicates the low-temperature service limit of the rubber. Tg values are dependent on the structure, degree of cross-linking (vulcanization) and isomeric composition of the rubber. 

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