industrial manufacturing of nitrile rubber

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    Industrial manufacturing of Nitrile Rubber

    INTRODUCTION

    Acrylonitrile Butadiene copolymers are commonly known as

    Nitrile rubbers. India has consuming this rubber for over four decades,

    however, the consumption remained small and restricted to mainly the

    products requiring oil resistance properties. The picture changed rapidly since

    1970 as the combined properties of abrasion resistance even at high

    temperatures was used for making products like rice dehusking rolls. Today

    over 2500 MT of NBR is used in this single application the growth of

    automotive industries, oil companies have further spurred the demand of

    Nitrile rubbers in India.

    The first rubber is to be commercialized is Natural rubber. Since

    that time two attempts have been made by scientists world over to study the

    structure of natural rubber, elasticity of natural rubber and then try to synthesis

    a rubber that can do the job of natural rubber. During the World War II(1941),

    these attempts got the boost, when allies realized that natural rubber comes

    from East Asia was under the threat of Japanese aggressiveness and that wars

    cannot be fought without rubber i.e. rubber tyres etc. Synthetic rubber

    manufacturing programs got stabilized and expanded due to improvements

    like cold polymerization, oil extensions etc. Synthetic rubbers which can fully

    C.O.E.& T.,Akola 1

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    or partially replace the natural rubbers are generally termed as general purpose

    synthetic rubbers. Today we have an array of synthetic rubbers.

    The second type of development involved considerations to have

    those properties deficient in the natural rubber such as resistance to oil, heat,

    ozone etc. to be eliminated. Thus developments of special purpose rubbers like

    Nitrile rubber came on scene and has grown substantially.

    C.O.E.& T.,Akola 2

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    SYNTHETIC RUBBER POSITION IN INDIA

    At present consumption of all synthetic rubbers together is

    approximately 22% of the total rubber consumed in India it is expected that

    the synthetic rubber consumption in India can be as much as 40% provided

    indigenous availability improves and import duties on rationalized for highly

    specialized rubber which are not produced in India. Presently the synthetic

    rubber scenario can be as under. Availability of monomers like butadiene,

    styrene in the country will play significant role in promoting production of

    general purpose rubbers like SBR, PBR in country. Though the SBR

    production came in India 1963 by Synthetics and Chemicals Ltd it did not

    grow with demand on natural rubber with its sustained growth supported the

    growth of rubber industry.

    Company Name Type PresentCapacity(MTA) Trade Name

    Synthetics & ChemicalsLtd. SBR 40,000 Synaprene

    APAR Industries ltd. NBR 10,000 Aparene

    APAR Industries ltd. HSR 9000 Powerene

    Unimers India ltd EPDM 6000 Herlene

    NOCIL EVA 50000 Powerene

    C.O.E.& T.,Akola 3

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    MONOMER SYNTHESIS

    Nitrile Rubbers are co-polymers of Butadiene and Acrylonitrile.

    A. Butadiene

    Butadiene is a major monomer in production of NBR. Butadiene can

    be manufactured by various routes. In past routes from acetylene (Berthelot,

    REPPE process) ethylalcohol (Ostronislenksy, Lebdev process) has been used

    in West. Even today in our country we are using alcohol as starting material

    for the production of Butadiene. This can be shown as under :

    CH 3 CH 2 OH CH3 CHO + H 2

    2CH 3 CHO CH 3 CHOH CH CHO CH 3 CH==CH-CHO

    CH 3 CH== CHCHO + CH 3 CH 2 OH CH3 CH==CHCH 2OH+CH 3 CHO

    CH 3 CH == CH CH 2OH CH 2==CHCH==CH 2+H 2O

    (Approx. 250 parts of Ethylalcohol gives 100 parts of Butadiene)

    B. Acrylonitrile

    B.1. Acrylonitrile synthesis from acytelyene and hydrogen cyanide Hydrogen

    cyanide manufactured by Andrussor reaction as :

    Feed ratio NH 3 : Natural gas : air is 11.2:12.0:76.8

    2CH 2 + NH 3 +3O 2 HCN + 6H 2O

    Addition of hydrogen cyanide to acetylene in presence of an aqueous

    catalyst HCN

    C.O.E.& T.,Akola 4

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    Catalyst (HCN)

    Ammonium Chloride 21.1%

    Cuprous Chloride 54.3%

    37% HCL 1.4%

    Water 23.2%

    pH

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    Acrylonitrile monomer can also be synthesized from acetaldehyde and

    hydrogen cyanide (KNAPSACK PROCESS). In Distillers process

    acrylonitrile is synthesized from acrolein. First acrolein is produced from

    propylene, by catalytically oxidized to acrolein. Acrolein in presence of

    ammonia and air is converted to acrylonitrile as :

    CH 2=CHCHO+NH 3+1/2 O 2 CH 2 = CHCN+2H 2O

    This process which operates at elevated temperatures in presence of an

    oxidation catalyst (Molybdic Oxide)

    There are many other routes for synthesis of Acrylonitrile monomer,

    but the above process is used in India by the only producer, i.e. IPCL.

    The most popular route today use predominantly hydrogen-rich

    straight-chain C4 units which results from petroleum (naphtha) cracking

    which is shown below.

    1. Butadiene Oil Naphtha Butadiene

    2. Acrylonitrile Oil Naphtha Propylene + Ammonia & air Acrylonitrile

    MONOMER SUPPLIERS

    Gujrat Apar Polymer Limited.

    National Organic Chemical Industries Limited.

    Indian Petrochemical Corporation Limited.

    Reliance Petrochemicals; Surat.

    C.O.E.& T.,Akola 6

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    CHEMICAL STRUCTURE OF NBR

    Chemical structure of NBR is generalized as copolymer of butadiene

    and acrylonitrile as shown below

    -----(CH 2-CH=CH-CH 2)x---(CH-CH 2)y-------|

    CNToday the commercial grades are available with 16 50% of the

    acrylonitrile (ACN) content. The chemical structure of NBR is very similar to

    SBR. The replacement of benzene group by cinogen group introduces the

    polarity in the molecule. The influence of this group enhances the properties

    like oil, heat, air permeability resistance, electrical conductivity properties of

    vulcanizates. However low temperature (Tg value) properties are affected with

    increase in ACN content.

    Like SBR, NBR can be vulcanized by conventional cure system based

    on sulphur and accelerator or with organic peroxides. Polarity in the molecules

    decreases electrical resistance of the polymer and bring it in antistatic range,

    so that NBR can be compounded for products where dissipation of electrical

    charges are essential e.g. textile cots and aprons.

    NBR is amorphous in nature and needs reinforcing fillers like carbon

    black, precipitated silica to develop physical properties such as tensile

    strength, modulus, resistance to abrasion etc.

    C.O.E.& T.,Akola 7

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    METHODS OF MANUFACTURING OF NBR

    Nitrile rubbers are manufactured by Emulsion co-polymerization of

    butadiene and acrylonitrile together. The stainless steel reactors are mirror

    finished to exercise excellent temperature controls and entire latex production

    is through the digital control system. Thus the addition of all ingredients and

    reactions are automatically controlled. This ensures the excellent quality with

    high consistency in properties of polymer manufactured. At present the

    emulsion polymerization is carried out at 5 oC compaired to 50 o C in the earlier

    days.

    Nitrile rubbers are produced by

    I ) Emulsion process :

    a) hot polymerization -------------------- 50 o C

    b) cold polymerization-------------------- 05 o C

    II) Solution process--- this process has found limited applications so far

    REACTION MECHANISM OF FREE RADIAL EMULSION

    POLYMERISATION

    Following are the three steps involved in this process :

    1) Initiation 2) Propagation and 3) Termination

    C.O.E.& T.,Akola 8

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    1. Initiation

    ROOH + Fe 2+ ----------------------------------> RO* + Fe 3+ + OH -

    Fe 3 + Sodium Sulfoxilate ---------------------> Fe 2+

    RO* + CH 2 = CH - CH = CH 2 --------------> RO- CH 2-CH=CH-CH 2*

    2. Propagation

    RO - CH 2 - CH = CH - CH 2 * + CH 2= CH - CH = CH 2

    ----> RO - CH 2 - CH = CH - CH 2 - CH 2- CH = CH - CH 2* + CH 2 =CH|

    CN

    RO - CH 2 - CH = CH - CH 2 - CH 2- CH = CH - CH 2 - CH 2 -CH*|

    CN

    There is a random arrangement of monomer in the polymer, can be

    represented as

    ------B-B-B-A-A-B-B-A-A-A------ A for AcrylonitrileB for Butadiene

    3. Termination

    S R R - || | |

    RO* + S -C - N + H 2O ----------------> ROOH + CS 2 + NH| |

    (From Hydroperoxides ) R R

    Polymerization Reaction

    CH 2 = CH - CH= CH 2+ CH 2=CH -----(-CH 2 - CH = CH- CH 2) x -----CH 2-CH-----------| |

    CN CN y n

    C.O.E.& T.,Akola 9

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    C.O.E.& T.,Akola 10

    Emulsifier Initiator Activator Modifier

    Refrigerant

    Flow

    DiagramofNitrileRubberManufacturing

    Butadienerecycle

    ACNrecycle

    Coagulation

    Water

    SerumRecycle

    WashWaterRecycle

    Steam

    Vent

    FinishedProduct

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    Figure Index

    1. Butadine Storage .

    2. ACN storage .

    3. Reactor .

    4. Flash Tank .

    5. Stripper .

    6. Latex storage tank.

    7. Coagulation tank .

    8. Conversion tank .

    9. & 9A Dewatering screens .

    10.Wash Tank .

    11. Dewatering Press.12.Shredder .

    13.Dryer .

    14.Baler .

    15. Magnetic detector .

    16.Film wrapping .

    17. Bagging and stitching.

    C.O.E.& T.,Akola 11

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    EMULSION POLYMERIZATION

    The basic polymer recipe in addition to the monomers contains water,

    stabilizers, emulsifiers, catalysts, activators, electrolytes and terminating

    agents. The basic steps involved in the manufacture are polymerization,

    coagulation, washing and drying.

    In polymerization, the monomers are emulsified in water, a free radical

    generating catalyst is added and the mixture is agitated while a constant

    temperature is maintained. Following the polymerization cycle, the material is

    transferred to a blow down tank in which the terminating agent is added to

    control the molecular weight of the polymer according to the grade, the

    residual monomers are removed. Then the latex is stabilized and coagulated

    into fine crumbs by the addition of various coagulating agents like alum,acids, and salts. This is then washed, dewatered, and finally dried crumbs are

    compacted to form the bales. Nitrile rubbers are available in several forms

    such as sheets, crumbs, powers and liquids as per requirement.

    POLYMERIZATION

    NBR is produced from the emulsion polymerization of butadiene and

    acrylonitrile at 5 0c for cold and 50 0c for hot process. Redox system of initiator

    is used for cold while for hot process K 2 SO 8 is used. The monomer or is used

    C.O.E.& T.,Akola 12

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    for cold while for hot process K 2 SO 8 is used. The monomer ratio and the

    temperature at which polymerization are carried out are important features of

    NBR manufacturing. The properties of product may also be influenced by

    other things like amount and nature of modifiers and emulsifiers. The

    conversion of monomer to copolymer is not carried out to completion for

    quality reasons. The reaction is stopped at predetermined stage when desired

    properties are obtained in the product. The unreacted monomers are stripped

    from latex and recovered for the reuse in the stripper column. Following

    parameters affects the polymer properties during polymerization.

    1. polymerization temperature

    2. emulsifier

    3. modifier

    1. Polymerization temperature

    Polymerization temperature influences the branching, cross-linking, the

    stereoregular configuration of the enchained butadiene units and the molecular

    weight distribution of the polymer. In general the lower polymerization

    temperature, the less branched and crosslinked is the rubber and lower will be

    the gel content. In microstructure the proportion of vinyl groups in the

    polymer varies little over the rang of polymerization temperature from -200c

    to 1000c. By contrast, the balance between cis-1,4, and trans- 1,4 structure is

    C.O.E.& T.,Akola 13

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    markedly affected by polymerization temperature, the ratio of cis and trans

    falls as the polymerization temperature is decreased. The presence of

    acrylonirtile unit has little effect upon the microstructure of the enchained

    butadiene butadiene units. The improved mechanical properties of NBR

    vulcanizate from cold process have been attributed to the greater structural

    regularity caused by increased trans- 1,4 content as well as to the formation of

    less branched and crosslinked structure in polymer.

    2. Effect of emulsifier

    Emulsion polymerization is a heterogeneous system. The

    polymerization is carried out using water as a liquid or solvent but in

    emulsion. The emulsifying agents are used for this purpose. It has two

    portions, first is hydrophobic due to long hydrocarbon chain of emulsifier and

    second is the hydrophilic due to the polar end (e.g. sodium or potassium

    sulphonate) attached to the emulsifier carbon chain. Emulsifiers are hardly

    soluble in water. There lies a critical concentration of the emulsifier called as

    CMC. above which they are insoluble and forms insoluble spherical structures

    called as micelle. Increase in emulsifier causes the formation of smaller

    particles. The synthetic emulsifier having a low temperature water solubility

    shows no tendency to gel even down to 5 0C due to their branched structure

    their calcium and magnesium salts are more soluble. Therefore they shows

    C.O.E.& T.,Akola 14

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    less tendency to be precipitated from hard water. For synthetic soap, rate of

    polymerization increases linearly with the square root of the soap level.

    3. Modifier

    These are mercaptans, which are used to control molecular weight and

    acts as a reaction transferring agent in the free radical reaction. It does not

    effects the rate of polymerization. On increasing the modifier amount in

    polymerization recipe, both polymer plasticity and gel content falls sharply.

    C.O.E.& T.,Akola 15

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    VULCANIZATION

    The vulcanizing agents are usually sulfur compounds, which react with

    the polymer to produce a cross-linked material in which the linkages are -C-S x

    -C-. The cross links may be mono-, di-, or polysulfidic. The type of linkage

    is determined by the concentrations of sulfur, accelerators, and retardants, and

    temperature. Most of the conditions to produce a given products are

    empirical, but some advances in knowledge are beginning to allow a scientific

    basis for vulcanizing conditions.

    The accelerators reduce the time required for the vulcanization of

    rubber from several hours to a few minutes. In addition, less sulfur is needed

    and a more uniform product is obtained. The mechanism of accelerator action

    is not well understood, in spite of much research, but presumably involves the

    formation of an activated form of sulfur, which forms a "sulfur bridge" at

    reactive sites within the rubber molecule, linking the large molecules into a

    tight network structure. Most accelerators contain nitrogen and sulfur. Two-

    thirds of all the accelerators made, consist of mercaptobenzothiozole (MBT)

    and its derivatives.

    Nitrile rubbers are some what similar to SBR's in comparison, however,

    Sulphur is less soluble in NBR. Thus early addition of sulphur or sulphur

    donor systems are more appropriate. Semi-EV and EV cure systems play a

    C.O.E.& T.,Akola 16

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    special role in NBR vulcanization and provide high heat resistance & low

    compression set. Like other diene rubber, Nitrile rubber is vulcanized by

    sulphur cure system (S+Accelerator+ZnO). This can be depicted as below.

    1. CH 2-CH=CH- CH 2 - CH 2 -CH -------->| -H -

    CN

    2. CH 2-CH=CH- CH 2 - CH 2 -C* + S n + Accelerator * -------->|

    CNCN|

    CH 2-CH=CH- CH 2 - C|

    Sx|

    CH 2-CH=CH- CH 2 - C|

    CNThus cross-linking continues.

    Conventional accelerator system such as MBTS, Sulfenamides, Dithio-

    Carbamates, Guanidins have given best results. A good heat resistance is

    easily obtained by using TMTD with low or no sulphur or a sulphur donor

    (0.5phr). Cadmium oxide (0.25phr.) provides very high heat resistant

    however very toxic in nature. Carboxylated NBR needs multifunctional

    reagents such as ZnO or Zinc Peroxides. Curing of NBR is also common for

    achieving better heat resistant properties with additional use of co-activators

    C.O.E.& T.,Akola 17

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    such as EDMA(Ethylene Diamine Methacrylate) high hardness grades can be

    produced.

    However peroxide cures give lower tensile, tear, swell resistance &

    poorer dynamic properties. They restrict flexibility in compound development.

    Vulcanization can be achieved with Sulphur, Dioxide or peroxide system. As

    with NR, SBR, ZnO at 3-5 phr. level & stearic acid at a 1-2 phr. level are

    added for proper activation.

    C.O.E.& T.,Akola 18

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    COMPOUNDING

    Pure rubber (natural or synthetic) is usually not suitable for use. The

    desirable properties of plasticity, elasticity, toughness, hardness or softness,

    abrasion resistance, impermeability and the myriad combinations possible are

    achieved by the art of the rubber compounder.

    A broad range of properties can be obtained from properly

    compounded Nitrile rubber. In general, NBR is compounded along lines

    similar to those practiced with NR and SBR.

    As mentioned earlier, selection of grade of rubber is very important

    criteria depending on the oil and fuel resistance is required. Higher

    acrylonitrile NBR rubber is chosen when high resistance is required. Lower

    acrylonitrile rubbers are used when low temperature and dynamic properties

    are important. Activation system generally used contains 3-5 phr of zinc oxide

    with 1-2 phr of stearic acid. This system is used along with sulphur donor

    vulcanization system. With peroxide curing system cynurate (Tac) can be used

    as activator.

    Unlike natural and polychloroprene rubbers, NItrile rubbers does not

    crystallize on stretching (self reinforcement) and therefore is a balanced

    reinforcing system. When used alone, low reinforcing carbon blacks are

    preferred as the highly reinforcing blacks which tend to stiffen the uncured

    C.O.E.& T.,Akola 19

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    stock as vulcanizate and pose problems during processing. Consequently high

    reinforcing carbon blacks are used mainly at low loadings or in conjunction

    with the less reinforcing fillers. Non-black application will require the use of

    reinforcing silicas of various types of calcium carbonates hard clays, talc and

    other pigments. Silicas are capable of imparting properties as good as carbon

    black barring compression set and resilience. Nitrile rubbers needs proper

    choice of antioxidants to perform under heat, air and ozone. Ozone resistance

    can be improved by blending it with PVC, EPDM and Epichlorohydrine.

    In summarizing Nitrile rubbers can be compounded with :

    a) filler types: carbon blacks, silica, silicates, alumina

    b) plasticizers: esters, polymeric esters, aromatic oils and resins

    c) cure systems: ebonite conventional sulphur and peroxidesADDITIONAL DATA ON COMPOUNDING

    Pure rubber (natural or synthetic) is usually not suitable for use. The

    desirable properties of plasticity, elasticity, toughness, hardness or softness,

    abrasion resistance, impermeability, and the myriad combinations possible are

    achieved by the art of the rubber compounder. A typical rubber compound is

    shown in Table .

    C.O.E.& T.,Akola 20

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    Table - Typical Rubber Compound

    Ingredient PartsRubber

    Sulfur

    Zinc oxide

    Stearic acid

    Accelerator

    Loading or filling pigment

    Reclaim, softeners, extenders, colors, blowingagents, antioxidants, antiozonants, odorants,

    etc.

    100.0

    2.0

    5.0

    3.0

    1.5

    50

    As required

    1. Selection of NBR Grade : In formulating compound, one of the important

    step is to select correct grade of rubber, to meet and product

    specifications/requirements.

    The major variables which permit various grades are :

    a) Type of Soap Fatty Acids, FattyAcids/Rosin Acids, Synthetic

    b) Mooney value 20 ML - 80 ML

    c) ACN Percentage 18% - 50%

    d) Types of stabilizer Staining, Non-staining

    e) X-linked polymers

    2. Selection of Reinforcing Filters :

    C.O.E.& T.,Akola 21

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    NBRs are like SBR in amorphous character, and being unable to

    crystallize on stretching requires presence of reinforcing fillers to attain good

    physicals. Carbon blacks and silica fillers are major fillers used for improving

    physicals. In carbon black one can use right from SAF. ISAF mix , down

    upto MT blacks. Fine particle blacks are difficult to disperse and gives tough

    compounds to process. Thus softer and medium blacks like FEF, GPF, SRF,

    MTS are used. FEF is selected as the name indicates for Fast Extrusions.

    The effect of SRF-HM is given below to give guidance of physicals it imparts

    LoadingCB

    Plasticizer T.S.(psi)

    Elongation.@Break

    Hard-ness

    300% Mod(psi)

    Angle Tear lbs/In.

    25 phr 10

    20

    2200

    2000

    550

    600

    55

    50

    650

    500

    250

    210

    3. Curatives :

    Normal accelerator, sulphur combination is NBR 100, MBTS or CBS

    1.5, Sulphur 1.5. For improved compression set, heat resistance EV systems

    are used. EV cures affect tear and flex properties of the vulcanizate.

    Vulcanizates, which have been made with TMTD with little or no

    sulphur, tend to 'bloom' because of the high dosage, but this can be reduced or

    even eliminated by simultaneous use of MBT, MBTS or CBS. Then too, the

    blooming can be suppressed by the partial replacement of the TMTD with

    another thiuram disulphide. NBR can be cured with peroxides giving better

    C.O.E.& T.,Akola 22

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    heat and compression set properties. The following characteristics are attained

    with nitrile rubber compounds optimally prepared with dicymyl peroxide.

    a) Good tensile strength at room temperature but relatively lower values at

    elevated temperatures,

    b) Low elongation at break,

    c) High modulus

    d) Low permanent set at break,

    e) Moderate tear resistance at room temperature and very low values at higher

    temperatures,

    f) Excellent performance under dynamic loading with the Goodrich flexometer

    and in ball fatigue testing,

    g) Low compression set especially in hot air at high temperatures and in hotoils.

    h) Very good aging in hot air,

    i) Good aging in steam and hot oils, and

    j) Relatively strong swelling when kept in boiling water.

    4. Selection of Plasticizers :

    Nitrile Rubbers are polar (due to ACN) and hence only aromatic/highly

    a aromatic oils/plasticizers are compatible. The most common plasticizers are

    C.O.E.& T.,Akola 23

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    DBP/DOP types. Adipates/sebacate ester plasticizers are used when low

    temperatures flexibility is desirable. Paraffinic and Naphthanic oils should be

    avoided as it would tend to 'exdue' from the vulcanizate. The recent trend is

    supply DBP/silicate blend (e.g. E-2 Mix DBP from C.P. Hall) to facilitate easy

    addition. When flame retardance is required Triaryl/Trieresyl phosphate is

    added.

    NBR is a polar rubber and hence for better compatibility only aromatic

    plasticizers and its compounds (with high polarity) are used. The plasticizers

    have far reaching effect on NBR vulcanizate. The mol. wt. also has an

    important effect on its plasticizing action. Thus, the viscosity of the

    compound the physical properties of the vulcanizates are largely dependent on

    the type and the amount of the plasticizer.Plasticizers are added to improve processing, impart tackiness, improve

    low-temperature performance and to lower hardness of the vulcanizate.

    Plasticizers also assist in filler dispersions during mixing. Esters of carboxylic

    acid or phosphoric acid are most suitable in compounding NBR. These can be

    either monomeric or polymeric in nature. Monomeric plasticizers get easily

    extracted, when in contact with oils.

    All plasticizers decrease the viscosity and the elastic recovery forces of

    unvulcanized NBR and these increase with increasing easing amounts. The

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    degree of reduction is especially variable in magnitude. Plasticizers can be

    classified in two different groups, depending on whether they have a strong or

    weak effect on the elastic, restoring forces.

    Fats, waxes, resins, and polymeric plasticizers belong to one group. In

    general, they strongly reduce the resilience of the vulcanized compounds and

    thus exert a most favorable effect on processibility; that is to say, they

    improve the calendar ability, extrudability and building tack.

    Stearic acid, wool fat and some others of this group are relatively

    poorly compatible and, therefore, may readily sweat out if sued in too high

    concentrations and cause trouble in building operations. This same thing

    holds, as has been said, for petroleum plasticizers which are high in aliphatics.

    The molecular weight of the plasticizer is significant for compatibility.Easter and ether plasticizers are typical representatives of the other

    group. They work by solvation, in the previously given sense, swelling the

    NBR compounds strongly and causing pronounced softening. Actually they

    lower the elasto-recovery forces relatively little. Because of their ability to

    increase the elasticity of the vulcanisates, they are usually referred to an

    "elastomers".

    Certain viscous xylene-formaldehyde resins, alkyd resins, aldol resins

    as well as rosin, Koresin, coumarone resins and swell-resistant and liquid

    C.O.E.& T.,Akola 25

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    factices, have found value as processing aids for improving calendarability

    and extrudability as well as the building tack. Viscous butadiene/acrylonitrile

    copolymers (10,000-300,000 cp) also serve very well. Being the same type of

    material, they do not tend to sweat out when used in large amounts and thus

    are oil resistant and non-volatile at higher temperatures.

    PROCESSING

    Nitrile rubber compounds are fabricated into a wide variety of articles

    requiring many different types of processing involving milling, internal

    mixing, extrusion, calendaring and vulcanizing in many different ways. All of

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    commercially available Nitrile rubber can be mixed either on a two rollmill is

    of no exception. The only care taken during mixing is the addition of sulphur

    immediately after rubber has formed smooth band on the roll.

    Compounds can be designed to be easily extruded, calendared or

    molded with injection, compression, or transfer techniques. Optimum

    breakdown and dispersion are required for both calendaring and extrusion,

    sometimes requiring remilling operation, at least 16 hrs after original mixing.

    In extrusion the screw and barrel should be at about 60-70 0c with head at

    about 90 0c and die in the region of 120 oc. While for calendaring conditions,

    for unsupported sheet, coating or plying are generally as follows:

    Top roll ------ 75-85 o c Middle roll------ 60-70 o c Bottom roll----- 75-85 o c

    For excellent extrusion, high Mooney viscosity rubber is chosen particularly when high green strength is required. Low or medium Mooney

    viscosity polymers will lend excellent calendaring characteristics molding of

    Nitrile rubber can be carried out conventional way and at conventional

    operating conditions.

    VERSATILITY IN NBR GRADESWide range of ACN content (16-50%).

    16%, 20%, 23% ACN, for Very Low Temperature Service.

    26%, ACN, with Carboxylation, for improved abrasion.

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    27%, 29% ACN ,for Low Temperature Service.

    33% ACN ,For General purpose use.

    39% ACN ,For Fuel ,Oil, High Temp and Oil Drilling application .

    40% ACN, For Fuel ,Oil, High Temp and Freon resistance application.

    45% ACN, For Fuel, Freon and High Temp. Service products.

    INCREASE IN ACN CONTENT LEAD TO THE FOLLOWING

    1. Improves resistance to fuels and oils.

    2. Increases abrasion resistance and hardness.

    3. Improves tensile strength and modulus.

    4. Improves processing behaviour.

    5. Increases permeability resistance to gas diffusion.

    6. Decreases Low temperature flexibility.

    7. Reduces Resilience and Elasticity.

    8. Improves heat resistance.

    9. Decreases electrical insulation resistance.

    10. Increases compatibility with polar plastics.

    PROPERTIES OF NBR

    1. Excellent resistance to Oils & Fuels.

    2. Excellent resistance to Abrasion & wear.

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    3. Good heat and chemical resistance.

    4. Low permeability to air & gases.

    5. Excellent overall physical properties when compounded with

    reinforcing filler.

    6. Low electrical insulation resistance, hence excellent Anti-static

    properties.

    7. Excellent compatibility with PVC; NBR/PVC fluxed properly displays

    excellent resistance to ozone and weather.

    8. Blends with PVC permits developments of TPEs. suitable for many

    applications including footwear soling, gas tubing, garden hoses etc.

    9. Excellent compatibility with Phenol-formaldehyde resins. Such blends

    are useful for adhesives, high hardness products, leather like products etc.

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    APPLICATIONS OF NBR

    NBR is one of the most widely consumed rubber worldwide. It's

    applications in different fields are discussed below.

    1) In Military applications : Increase in ACN content of NBR improves

    resistance to fuels and oils with increased abrasion resistance. Hence it is used

    for manufacturing fuel, hydraulic, pneumatic hoses, diaphragms, oil seals,

    valves, abrasion resistance soles, combat boots and engine mounts.

    2) Automotive applications : NBR is prone to have excellent resistance to

    fuels and oils, so it is used advantageously used for manufacturing of fuel

    hose, oil seals, ('O' rings), 'V' packings, crash pads, hydraulic hoses, power

    stearing hose and pressure bellows.

    3) Industrial applications : Variety of grades of NBR can be obtained with

    varying heat resistance depending on ACN contents, so NBR is used for

    manufacturing water pipe insulations, cots & aprons, gaskets & friction material.

    NBR is having low electrical insulation resistance hence excellent

    antistatic properties and liable to be used for conveyor beltings.

    4) Commercial applications : Commercial applications include food and

    solvent handling hoses and Belts, Rice Rolls, Printing Rolls, Adhesive, Shoe

    Soles, Milking Inflations, Floorings, Astro-turf underlays, Hawai Chappals,

    Printing blankets and Blocks.

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    CONCLUSION

    So our country has been using the NBR and it should gather higher uses

    as there is increase in availability in NBR indigenously. Some latest

    advancements in the field and NBR technology are also taking place like

    1) Emergence of carboxylated NBR

    2) Halogenated NBR

    3) Nitrile rubbers containing based antioxidants

    4) NBR-Polyolefin blends (NBR+PVC)

    5) NBR in powder form.

    Importantly NBR can be efficiently used for the manufacture of various

    molded products due to its excellent processibility & easy of availability. It

    should replace the applications of some inferior rubbers, also new applications

    should be bourn for nitrile rubber.

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    BIBLIOGRAPHY

    C.M. Blow & C. Hepburn : " Rubber Technology and Manufacture "

    (2nd Edition) Butterworths P.N. 130-137

    Maurice Morton : " Rubber Technology "

    (3rd Edition ) Van Nostrand Reinhold Newyork P.N. 322-338

    Harry Barron : " Modern Rubber Chemistry"

    D Van Nostrand Company.inc Newyork P.N. 303-318

    J.Y. Brydson : " Plastic Materials "

    (6th Edition) Butterworth Heinemann Publication P.N. 267-268

    Industrial Manual of APAR INDUSTRIES LIMITED, Mumbai.

    WEBSITES

    www.aparindustries.com

    www.azon.com