Department Process Engineering

Rubber & Plastics Technology

- Translation of the german lecture

Chapter 0.1 Table of contents

Rubber

TABLE OF CONTENTS 1. General Natural rubber, synthetic rubbers Rubber compound; rubber - viscoelastisc behavior Rubber chemicals: Fillers, plasticizers, crosslinking agents, inhibitors, special chemicals 2. Compound manufacturing Mixing hall concepts Manufacturing systems, rolling mills, breakers, internal mixers, processing plants, continuous mixing systems, technology of powdered caoutchouc 3. Semifinished products and green manufacturing Extruders, calender, fabric coating; Reinforcing textiles Machining and manual manufacturing Latex - technology 4. Vulcanization Press vulcanization: compression - moulding, transfer - moulding, injection moulding Boiler vulcanization: steam, air, water Continuous vulcanization:"AUMA"-vulcanization, hot air, UHF, salt bath, glycol, fluidized bed, shear extrusion, lead coating, radiation vulcanisation, cold cure 5. Finishing 6. Recipe structure 7. Rubber testing methods 8. Rubber products (selection): Tires, belts, conveyor belts, tubing, cable, moulded goods, latex goods

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Rubber Chapter 0.2

Introduction

Viscoelastic Behavior depending on Temperature G = elastic part of the moduli in torsion from the torsion experiment Tg = glass temperature range Tm = melting temperature range

Prof. Dr. M. Hberlein

10/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 0.3 Introduction

Rubber

For Comparison: Viscoelastic behavior of thermoplastics depending on temperature: G = elastic part of the modulus of torsion from torsion experiment Tg = glass-melting temperature range Tm = melting temperature range

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.1 Caoutchouces

Rubber

CAOUTCHOUCES structure - production - properties 1. Dialkene rubbers: general structure: 1.1. Natural Rubber World consumption NR 1998: 6.178 Mio t 36 % of cautchouces Symbol: NR Chemical name: cis-1.4-Polyisopren rubber (variant "Gutta Percha: tras -1.4- polyisoprene) Structure: R = CH3; Z =.-/Production: Natural product of Hevea brasiliensis; Plantation in Malaysia, Indonesia, Kenya and Brazil - latex tapping - coagulation - washing - drying Properties: High tensile strength, unfilled as para rubber, high elasticity, masticatable; good tear growth strength; application temperature: -50 to +80C Main application: Tires, conveyor belts, economical, high elastic goods Manufacturer: Large plantations, small caoutchouc farmers Commercial products: Pale crepe dehydrated on ribbed rollers Air dried sheets air-dried Smoked sheets smoked SMR 10, 20, 50, L standardized NR of MalaySIR dito of Indonesia sia SMR-CV 50,SMR-CV 60 NR of constant Mooney viscosity SP PA 80 pre cross linked caoutchouc brown crepes, flat bark contaminated NR types Crusoe powdered rubber
( CH2 C CH CH2 ) ( Z ) x y n R

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.2 Caoutchouces

Rubber

CAOUTCHOUCES 1.2 production of natural rubber Tap latex off the bark - filter the latex Coagulate the caoutchouc with acetic acid, Soak and wash Roll out to sheet, wash again Dry sheet (in air or smoke) Air drying: Pale crepe or ADS (air-dried sheet) Smoke drying: Smoked sheets (RSS 1 to RSS 3) Press sheest to bales Shipment "Caoutchouc tree" : Hevea brasiliensis

Latex Caoutchouc droplets (2 - 4 m) stabilized in water by proteins (emulsifying)

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.3 Caoutchouces

Rubber

CAOUTCHOUCES 1.3 Polyisoprene Rubber World consumption synthetic caoutchoucs 1998: 10.827 Mio t (ca. 64 %) Symbol: IR Chemical name: cis-1.4-polyisoprene-rubber Structure: R = CH3; Z = / Production: Solvent polymerization with Ziegler catalyst and/or ferrocenes (96% cis-structure) lithium catalyst (92% cis-structure) Form of delivery: bales on palettes Properties: similar to natural rubber, more expensive, more uniformly and more brightly than NR, however; transparent Main application: High performance tires, food use goods, alternative to NR Manufacturer: Goodyear, Shell Commercial products: Natsyn Cariflex IR

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.4 Caoutchouces

Rubber

CAOUTCHOUCES 1. 4 Butadiene rubber Worldwide tonnage of BR c. f. SR 1998: 18.2 % Symbol: BR Chemical name: cis-1.4-polybutadien-rubber (variant: trans-1.4- polybutadiene, no caoutchouc; putty or cement) Structure: R = H; Z = / Production: Solvent polymerization, Ziegler catalysis Ti catalyst (92% cis) Co - catalyst and/or ferrocenes (98% cis) (ionically in emulsion polym. yields trans isomers) Properties: high elasticity, abrasion resistant, low temperature flexible -80 to +90 C Main application: Tire, conveyor belts, dynamically high loaded goods Form of delivery: bales on palettes Manufacturer: Firestone, Shell, Bayer AG Commercial products:Buna CB 11 titanum type Buna CB 10 cobalt type Buna CB 30 titanum type, oil extended BR alone is badly processable. It is mostly blended with NR or SBR (see below). An addition of about 10 pphr BR to CR decrease stickiness to processing machines.

The compounding components in the caoutchouc recipe are specified in pphr (part per hundred rubber). Reference quantity is caoutchouc with 100 mass-%.

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.5 Caoutchouces

Rubber

CAOUTCHOUCES 1.5 Styrene-butadien-rubber

Worldwide tonnage of SBR cf. SR 1998: 31.4 %; Latex 22.0 % Symbol: SBR Chemical name: Poly-(styrene-butadiene)-rubber Structure: Production: R = H; Z =
CH CH2

Emulsion polymerization, by radical ca. 5C - cold-, ca. 50C - hot polymerizate styrene content: 9 to 45%, normally 23.5%; aging protection in polymer; Solvent polymerization (25% styrene) Properties: low price, aging resistance is better than NR, general purpose rubber of great variety of types Main application: tires, belts, commercial rubber goods Form of delivery: bales on palettes, also available as powder rubber Manufacturer: Bayer AG, Firestone, Shell, Goodrich, etc. Commercial products:Buna EM, Krylene, Cariflex S etc. Type designation according to numeric code: 10xx hot polymer without filler 12xx solution - SBR 15xx cold polymer without filler 16xx cold polymer, carbon black masterbatch 17xx hot polymer, oil extended 18xx cold polymer, carbon black/oil master batch 19xx emulsion- resin- master batch 'xx' indicates viskosity, coagulant, content of styrene

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.6 Caoutchouces

Rubber

CAOUTCHOUCES 1.6 Butyl rubber Worldwide tonnage of IIR + IR and others cf. SR 1998: 14.2 % Symbol: IIR Chemical name: Poly-(isobutylene-isoprene)-rubber Structure: R = CH3 (0.5 to 3.0%); Z = -C(CH3)2-CH2Production: Ionic polymerization in solution at -80C with AlCl3 as initiator Properties: Application temperature to approx. 130C, small gas diffusion, high attenuation Main application: Tire tubing, tire inside liners, bumper (shock absorber) Form of delivery: bale on palettes Manufacturer: ESSO, Polysar (Bayer AG) Commercial products: Specific numeric codes according to viscosity and isoprene content (vulcanization velocity) Halogen butyl rubber Symbol: CIIR (chloric butyl); BIIR (bromine butyl) Chemical Name : Poly-(isobutylene 2-halogen butadiene) Structure: R = Cl, Br, CH3; Z see IIR Production: see IIR Properties: as IIR, faster vulcanization Main application: as IIR Form of delivery: as IIR Manufacturers: as IIR Commercial products: see IIR

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.7/1 Caoutchouces

Rubber

CAOUTCHOUCES 1.7 Polychloroprene rubber Worldwide tonnage of CR cf. SR 1998: 2.7 % Symbol: CR Chemical name: Poly-(2-chlorobutadien), mainly trans isomers Structure: R = -Cl; Z = / Production: Emulsion polymerization, by radical at 20 to 50C Modifiers: Thiuram - types Mercaptane - not peptizabale types Properties: Application temperature -40 to +110 C, small oil swelling, dynamically capable, hardly flammable Main application: Conveyor belts, belting, cable Form of delivery: Chips in bags Manufacturer: Bayer, Du Pont Commercial products: Baypren, Neoprene Baypren: Digit code (Neoprene: Alphabetic characters) Type Crystallinity Viscosity Modifier 110 very small 40-50 ML-4 mercaptane 210 medium strong 35-50 -220 medium strong 70-80 -320 very strong 80-95 - (adhesives) 130 very small 100-120 -230 medium strong 95-125 -330 very strong 95-105 - - (adhesives) 510/610/611 small 35-55 thiurame 710 medium 35-55 thiurame pre cross linked types: 115 very small 45-55 mercaptane 214 medium 50-60 -215 medium strong 45-55 -124 very small 70-80 -235 medium strong 90-110 -Further specialities are in use, see www.rubber.bayer.de.

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.7/2 Caoutchouces

Rubber

1.7 CR Family Characteristics of Dow Du Pont Neoprene:

G Types
Limited Storage Stability Peptizable to Varying Degrees No Accelerators necessary

W Types

T Types

A Types

Latex

Raw Polymers

Excellent Excellent Storage Stability Storage Non Peptizable Stability Least Nerve Accelerator Required Cure Accelerator Flexibility Required Cure Flexibility Solid polymers Best Extrusion, Fast Curing, for solventCalendering but safe based adhesives Performance Processing Best Tear Best Properties Strength Compression Set similar to W Resistance Types Best Flex Best Resilience Best Heat Aging Excellent contactability

Solid AquaStik and Polymers for Latex types for solvent based waterbased Adhesives adhesives and other applications Formulating Formulating Latitude Latitude

Excellent contactability Bond durability

Excellent contactability Bond durability High-temperature resistance Long-term

Product Performance

Highperformance temperature Chemical resistance resistance

Selection Guide to help select the appropriate type of Neoprene in developing a compound for a particular application:

Further specialities are in use, see http://www.dupont-dow.com/.

Prof. Dr. M. Hberlein 10/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.8 Caoutchouces

Rubber

CAOUTCHOUCES 1.8 Acrylic nitrile butadiene rubber

Worldwide tonnage of NBR cf. SR 1998: 3.2 %; Latex 0.4 % Symbol: NBR Chemical name: Poly-(Acrylnitril-butadien)-rubber Structure: R = -H; Z = -CH(C=N)-CH2Production: Radicalic emulsion polymerization at 5C (cold polymerizate) or 25-50C (hot polymerizate) Properties: Application temperature to approx. 110C; low swelling in oil and gasoline, small gas diffusion rate Main application: Motor vehicle parts, gasoline- and oil tubes, seals, also for food as milk Form of delivery: bale on palettes Manufacturer: Bayer AG, Polysar, Goodyear Commercial products:Special manufacturer numeric codes, distinguished according to viscosity and acrylic nitrile content. Example: Perbunan N (Bayer AG) type acrylic nitrile content viscosity polym. temperature 1807 NS 18% 45 ML-4 cold 2802 NS 28% 35 cold 2807 NS 28% 45 cold 2810 28% 65 warm 2818 NS 28% 95 warm 3302 NS 33% 30 cold 3307 NS 33% 45 cold 3310 33% 65 warm 3312 NS 33% 80 cold 3807 NS 38% 45 cold 3810 38% 65 warm 4807 NS 48% 45 ? Goodyear products up to 45% of acrylic nitrile (Chemigum N 206)

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.9 Caoutchouces

Rubber

CAOUTCHOUCES Schematic Production of NBR

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.1.10 Caoutchouces

Rubber

CAOUTCHOUCES Reactions for Synthesis of Poly(acrylic nitrile butadiene) rubber NBR:

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.2.1 Caoutchouces

Rubber

CAOUTCHOUCES 2. Saturated Polymers general structure: [-Xx-YY-ZZ-]n

2.1 Ethylene Propene Rubber Worldwide tonnage of EPDM cf. SR 1998: 7.8 % Symbol: EPM (copolymer); EPDM (terpolymer) Chemical Name : Poly-[ethylene-propene] Structure: X = -CH2-CH2-; Y = -CH(CH3)-CH2- (copolymer) terpolymer: Z = ethyl norbornene (max.10%) or hexadiene and/or dicyclopentadiene Production: Solvent polymerization with Ziegler catalysts ethylene content 45 to 70% molar mass Mn = 25 000 to approx. 200 000g/mol Properties: Application temperature to approx. 130C, waterand steam resistant; EPDM is vulcanizable with sulfur; EPM: peroxide cross-linking Main application: vehicle profiles, radiator hoses, steam tubing, window seals, building profiles Form of delivery: bale on palettes Manufacturers: Bayer AG / Huels, Du Pont, DSM, ESSO and other Commercial products:Special manufacturer designations, distinguished in terms of viscosity, molar mass, ethylene- and diene Example: type 241 251 341 451 541 content Buna AP (Bayer-Huels) viscosity ENB content ethylene 45 ML-4 "v.-fast ca.50 % 45 8.9 % 49 % 70 5.1 % 48 % 90 8.6 % 51 % 110 4.6 % 53 %

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.2.2 Caoutchouces

Rubber

CAOUTCHOUCES 2.2 Hydrogenated nitrile butadiene rubber Symbol: Chemical name: Structure: HNBR partly hydrogenated polyacrylonitril butadiene X = -CH2-C(C N)H-; Y = -CH2-CH2-CH2-CH2-; Z = -CH2-CH=CH-CH2Production: Catalytic hydrogenation of NBR Properties: Oil- and gasoline swelling as NBR, application temperature up to 150C, high tensile strength, weather resistant Main application: vehicle tubing, seals, cables and profiles Form of delivery: bales on palettes Manufacturers: Bayer AG Commercial product: Therban Type double bond ratio acrylic nitrile content ML-4 viscosity a) Peroxide-vulcanisable 1706 <1% 33 % 75 1707 <1% 32 % 68 1907 <1% 37 % 85 2207 <1% 43 % 85 b) Sulfur-vulcanisable 1706 S 4-6% 33 % 63 1707 S 4-6% 32 % 72 2207 S 4-6% 43 % 85

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.2.3 Caoutchouces

Rubber

CAOUTCHOUCES 2.3 Epichlorhydrine rubber

Symbol: Chemical name:

CO (homopolymer); ECO (copolymer) Poly-(epichlorohydrine) (CO) Poly-(epichlorhydrine ethylenoxid) (ECO) Structure: X = -CH2-CH(CH2Cl)-O(CO) Y = CH2-CH2-O(ECO); Z = / Production: ionically initiated solvent polymerization Properties: Amine cross-linking, heat-resistant to 135C, cold flexibly CO only to -15C, small oil- and gasoline swelling rate, climate resistant Main application: Oil and fuel tubing to 135C, esp. for automotive; rolls Form of delivery: slabs in boxes Manufacturer: Hercules, Goodrich Commercial products CO: Herclor H; ECO Hydrin 100: Herclor C; Terpolymer Hydrin 200, Terpolymers, vucanizable with sulfur: Herclor T, Hydrin 400

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.2.4 Caoutchouces

Rubber

CAOUTCHOUCES 2.4 Acrylate rubber

Symbol: Chemical name: Structure:

ACM e. g. Poly ethylene acrylate X = -CH2-CH(COOC2H5)Y = -CH2-CH(OC2H4Cl)- (copolymer) Z = -CH2-CH2(terpolymer) Production: Emulsion polymerization radically initiated Properties: small oil swelling, heat resistant to 180C, resistant against heavy oils (sulfur, amine and/or soap cross-linking) Main application: Oil tubing, seals Form of delivery: Powders, pastes, bales, batches Manufacturer: Goodrich, Cyanamid, Du Pont Commercial products: Hycar, Cyanacryl, VAMAC, differentiated according to application temperature, cold flexibility

Prof. Dr. M. Hberlein

09/99

Department Rubber & Plastics Technology Process - Translation of the german lecture Engineering

Chapter 1.2.5 Caoutchouces

Rubber

CAOUTCHOUCES 2.5 Silicone rubber

Symbol: Chemical name: Structure:

SI, Q Polysiloxanes X = Si(R2)-O; Y = /; Z = / R = -CH3, -C2H5 u.a. Production: Condensation chain-growth polymerization Properties: heat-resistant to 200C, cold flexible to approx. -100C, high electrical resistance Main application: Cable, tubing, foils, seals Form of delivery: Batches, peroxide accelerated Manufacturer: Bayer AG, Wacker Commercial products: Silopren HV, HTV silicone rubber

2.6 Fluoroelastomers Symbol: Chemical name: Structure: Production: FKM e.g. Polyvinylidene fluoride hexa fluoro propene X = -CF2-CH2-; Y = -CF(CF3)-CF2-; Z = / Radicalically initiated copolymerization; also terpolymers cureable by perfluornitroso-system (amine-) Properties: High temperature-resistant up to 250C and more, chemical resistant, solvent resistant, flexible in cold Main application: Aviation, turbo charger tubing, diaphragms Form of delivery: batches Manufacturer: MMM, Du Pont Commercial products: Fluorel, Viton

Prof. Dr. M. Hberlein

09/99