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Nitrile rubber

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Nitrile rubber
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Nitrile rubber, also known as Buna-N, Perbunan, acrylonitrile butadiene rubber, and NBR, is a synthetic rubber copolymer of acrylonitrile (ACN) and butadiene. Trade names include Nipol, Krynac and Europrene.

Nitrile butadiene rubber (NBR) is a family of unsaturated copolymers of 2-propenenitrile and various butadiene monomers (1,2-butadiene and 1,3-butadiene). Although its physical and chemical properties vary depending on the polymer’s composition of nitrile, this form of synthetic rubber is unusual in being generally resistant to oil, fuel, and other chemicals (the more nitrile within the polymer, the higher the resistance to oils but the lower the flexibility of the material).

It is used in the automotive and aeronautical industry to make fuel and oil handling hoses, seals, grommets, and self-sealing fuel tanks, since ordinary rubbers cannot be used.[1] It is used in the nuclear industry to make protective gloves. NBR's ability to withstand a range of temperatures from −40 to 108 °C (−40 to 226 °F) makes it an ideal material for aeronautical applications. Nitrile butadiene is also used to create moulded goods, footwear, adhesives, sealants, sponges, expanded foams, and floor mats.

Its resilience makes NBR a useful material for disposable lab, cleaning, and examination gloves. Nitrile rubber is more resistant than natural rubber to oils and acids, and has superior strength, but has inferior flexibility. Nitrile gloves are therefore more puncture-resistant than natural rubber gloves, especially if the latter are degraded by exposure to chemicals or ozone.[citation needed] Nitrile rubber is less likely to cause an allergic reaction than natural rubber.

Nitrile rubber is generally resistant to aliphatic hydrocarbons. Nitrile, like natural rubber, can be attacked by ozone, ketones, esters and aldehydes. [citation needed]

Production

Krynac 33110 F nitrile rubber bales

Emulsifier (soap), 2-propenenitrile, various butadiene monomers (including 1,3-butadiene, 1,2-butadiene), radical generating activators, and a catalyst are added to polymerization vessels in the production of hot NBR. Water serves as the reaction medium within the vessel. The tanks are heated to 30–40 °C to facilitate the polymerization reaction and to promote branch formation in the polymer. Because several monomers capable of propagating the reaction are involved in the production of nitrile rubber the composition of each polymer can vary (depending on the concentrations of each monomer added to the polymerization tank and the conditions within the tank). One repeating unit found throughout the entire polymer may not exist. For this reason there is also no IUPAC name for the general polymer. The reaction for one possible portion of the polymer is shown below:

1,3-butadiene + 1,3-butadiene + 2-propenenitrile + 1,3-butadiene + 1,2-butadiene → nitrile butadiene rubber

Monomers are usually permitted to react for 5 to 12 hours. Polymerization is allowed to proceed to ~70% conversion before a “shortstop” agent (such as dimethyldithiocarbamate and diethyl hydroxylamine) is added to react with the remaining free radicals. Once the resultant latex has “shortstopped”, the unreacted monomers are removed through a steam in a slurry stripper. Recovery of unreacted monomers is close to 100%. After monomer recovery, latex is sent through a series of filters to remove unwanted solids and then sent to the blending tanks where it is stabilized with an antioxidant. The yielded polymer latex is coagulated using calcium nitrate, aluminium sulfate, and other coagulating agents in an aluminium tank. The coagulated substance is then washed and dried into crumb rubber.

The process for the production of cold NBR is very similar to that of hot NBR. Polymerization tanks are heated to 5–15 °C instead of 30–40 °C. Under lower temperature conditions, less branching will form on polymers (the amount of branching distinguishes cold NBR from hot NBR).

Properties

The raw material is yellow in color, though it can be orange or red tinted, depending on the manufacturer. Its elongation at break is ≥ 300% and possesses a tensile strength of ≥ 10 N/mm2. NBR has good resistance to mineral oils, vegetable oils, benzene/petrol, ordinary diluted acids and alkalines.

An important factor in the properties of NBR is the ratio of acrylonitrile groups to butadiene groups in the polymer backbone, referred to as the ACN content. The lower the ACN content, the lower the glass transition temperature; however, the higher the ACN content, the better resistance the polymer will have to nonpolar solvents as mentioned above.[2] Most applications requiring both solvent resistance and low temperature flexibility require an ACN content of 33%.

Applications

A disposable nitrile rubber glove.

The uses of nitrile rubber include disposable non-latex gloves, automotive transmission belts, hoses, O-rings, gaskets, oil seals, V belts, synthetic leather, printer's form rollers, and as cable jacketing; NBR latex can also be used in the preparation of adhesives and as a pigment binder.

Unlike polymers meant for ingestion, where small inconsistencies in chemical composition/structure can have a pronounced effect on the body, the general properties of NBR are not altered by minor structural/compositional differences. The production process itself is not overly complex; the polymerization, monomer recovery, and coagulation processes require some additives and equipment, but they are typical of the production of most rubbers. The necessary apparatus is simple and easy to obtain. For these reasons, the substance is widely produced in poorer countries where labor is relatively cheap. Among the highest producers of NBR are mainland China and Taiwan.

A hydrogenated version of nitrile rubber, HNBR, also known as HSN (highly saturated nitrile) is commonly used to manufacture O-rings for automotive air-conditioning systems.[3]

In January 2008 the European Commission imposed fines totaling €34,230,000 on the Bayer and Zeon groups for fixing prices for nitrile butadiene rubber, in violation of the EU ban on cartels and restrictive business practices (Article 81 of the EC Treaty and Article 53 of the EEA Agreement).[4]

Dangers

Use of these gloves when working with nitric acid or other strong oxidizers can be hazardous; the sample may spontaneously oxidize the gloves on contact, resulting in thermal and chemical burns from both the heat of oxidation and the caustic sample.[citation needed]

HNBR

Hydrogenated nitrile butadiene rubber (HNBR) is widely known for its physical strength and retention of properties after long-term exposure to heat, oil and chemicals. Trade names include Zhanber (Lianda Corporation), Therban (Arlanxeo [5]) and Zetpol (Zeon Chemical).

Depending on filler selection and loading, HNBR compounds typically have tensile strengths of 20–31 MPa when measured at 23 °C. Compounding techniques allow for HNBR to be used over a broad temperature range, -40 °C to 165 °C, with minimal degradation over long periods of time. For low-temperature performance, low ACN grades should be used; high-temperature performance can be obtained by using highly saturated HNBR grades with white fillers. As a group, HNBR elastomers have excellent resistance to common automotive fluids (e.g., engine oil, coolant, fuel, etc.) and many industrial chemicals. Like NBR, fluid and chemical resistance improves as the ACN content is increased.[citation needed]

The unique properties and higher temperature rating attributed to HNBR when compared to NBR has resulted in wide adoption of HNBR in automotive, industrial, and assorted, performance-demanding applications. On a volume basis, the automotive market is the largest consumer, using HNBR for a host of dynamic and static seals, hoses, and belts. HNBR has also been widely employed in industrial sealing for oil field exploration and processing, as well as rolls for steel and paper mills.

XNBR

An improved version of nitrile butadiene rubber (NBR) is carboxylated nitrile butadiene rubber (XNBR). In this execution there are beside the sulfur bridges also carboxyl groups R-COO- on the double bond of the butadiene part. These groups will make ionic cross links with zinc (Zn2+) to give improved physical properties as compared to a non-carboxylated nitrile rubber. These ionic crosslinks are formed along with sulfur links. The carboxyl groups which are needed for these extra links are distributed randomly and are present at levels of 10% or less.

XNBR structure XNBR extended structure

See also

References

  1. ^ Market Study Synthetic Rubber, published by Ceresana, June 2013
  2. ^ http://www.iisrp.com/webpolymers/07nbr-18feb2002.pdf
  3. ^ http://orings.com/tech_compound.php
  4. ^ Simon Zekaria (23 January 2008). "Bayer, Zeon fined 34.2 mln eur for synthetic rubber cartel activity". Forbes. AFX News.
  5. ^ http://www.therban.com/
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