PKL - Cray Valley

Product Guide

Liquid Polybutadienes 6

SMA Resins 10

Crosslinking Monomers

Thermoplastic Urethanes

Reference Guide

12

14

16

Hydrocarbon Resins 8

Product Guide

Profile

Cray Valley Hydrocarbon Specialty Chemicals (HSC) is a global organization dedicated to supplying specialty materials. As part of the Total Group, Cray Valley HSC can leverage key petroleum feedstock positions to deliver high-quality products. The various product lines are marked by a diversity of chemistries, which enables a broad spectrum of end-use opportunities.

Cray Valley HSC manufactures and supplies diene-based liquid homopolymers and copolymers, C5 and C9 hydrocarbon tackifying resins, styrene-maleic anhydride copolymers and derivatives, metallic monomer salts of acrylic and methacrylic acid, and specialty monomer products.

Cray Valley HSC sells these products under the Ricon®, Ricobond®, Krasol™, Poly bd®, Wingtack®, Norsolene®, and SMA® brand names.

The Hydrocarbon Specialty Chemicals organization focuses on two main markets, Rubber and Adhesives, while also supporting other traditional markets and new opportunities in the electronics, coatings, and plastics modification areas.

The many applications of Cray Valley HSC products include: plasticizing polymeric systems; crosslinking saturated and unsaturated polymers or other resins systems; adhesion aids or components of adhesives and sealants; chemical intermediates including polyols for polyurethane synthesis; additives to improve the dispersion of fillers, pigments, or other materials; and additives used in the compounding of thermoplastic resins.

The HSC Business Unit continues to create synergies between the core product lines and provide increased value to the market, building on a strong technology and manufacturing base, which enables Cray Valley HSC to grow together with our customers.

Main Trademarks

•Ricon®

•Ricobond®

•Krasol™

•Polybd®

•Wingtack®

•Norsolene®

•SMA®

•Dymalink®

• Headquarters

Exton, Pa., USA Paris, France Guangzhou, China

• Laboratories

Exton, Pa., USA Verneuil, France Kralupy, Czech Republic

• Sales Offices

Exton, Pa., USA Paris, France Yokohama, Japan São Paolo, Brazil Guangzhou, China

• Manufacturing Sites

Grand Junction, Colo., USA Channelview, Texas, USA Beaumont, Texas, USA Chatom, Ala., USA Stratford, Conn., USA Carling, France Kralupy, Czech Republic Ravenna, Italy

Americas

Cray Valley USA, LLC Oaklands Corporate Center 468 Thomas Jones Way, Suite 100 Exton, PA 19341 USA

Tel: 877-US1-CRAY (877-871-2729) Fax: 610-363-4198 E-mail: [email protected]

Europe & Africa

Cray Valley 16-32 rue Henri Regnault La Défense 6 92902 Paris La Défense Cedex France

Tel: +01 47 96 99 08 Fax: +01 47 96 99 86

Asia

Cray Valley (Guangzhou) Chemical Co., Ltd. Room 2507-09, The South Securities Building No. 140-148, Tiyu Dong Rd. Tianhe District Guangzhou 510620 P.R. China

Tel: +86 20 38879156 Fax: +86 20 28878495

Contacts Around the World

Global Presence

2 3

Rubber Market

Cray Valley HSC has a long history serving the rubber marketplace with functional additive products.

Beginning with classic peroxide-cure coagent technologies, Cray Valley HSC is a trusted provider of metallic monomers to belt, hose, seal, and wire and cable manufacturers. Cray Valley HSC metallic monomer products are employed to improve rubber adhesion and dynamic properties in a variety of applications. Cured-in-place rubber to metal adhesion is enabled through the use of metallic monomer coagents and Ricobond resins. Other diene polymers can be used as functional additives for treating reinforcing textiles.

More recently, Cray Valley HSC has developed a portfolio of products for the tire industry. Ricon liquid polybutadiene resins are established as performance-enhancing additives for tire applications. Ricon resins are employed to modify the viscoelastic response of the tread compound, enabling improvements to the traction/fuel economy/wear property balance. Cray Valley HSC has developed specialty monomer products to improve key aspects of accelerated sulfur vulcanization, including cure efficiency and reversion.

Cray Valley HSC is committed to supplying value-added specialty materials to the rubber market, and will work with customers to develop custom materials to meet their performance needs.

Adhesives and Sealant Market

Cray Valley HSC is a well-known supplier of hydrocarbon resins to the adhesives marketplace. Wingtack and Norsolene grades tackifying resins are specified in a variety of adhesive applications, including hot melt adhesives, pressure sensitive tape and label adhesives, and formulated mastics.

Expansion into new adhesive technologies is made possible by leveraging other product lines. Reactive urethane and epoxy-based adhesives may benefit through the use of maleic-anhydride functional resins, polybutadiene diols, and metallic monomers.

In addition, Cray Valley HSC supplies Poly bd polyols to a variety of urethane-based sealant applications, including the insulated glass sealant market. Adhesive tie layers can be formed from our unique thermoplastic urethane products.

Rubber Adhesives & Sealants Thermoplastics Specialty Markets

Ricon®Packaging, Coatings,

Electronics

Poly bd®Fuel Binders, Urethanes,

Electronics

Krasol™Urethanes, Coatings,

Electronics

Wingtack®Waxes, Casting,

Coatings

Norsolene® Coatings

SMA®Electronics, Leather,

Inks, Sizing, Dispersions


Coatings, Sporting Goods

Main Markets

4 5

Specialty Markets

The Cray Valley HSC product lines are utilized in a number of other market segments which take advantage of the unique structure/property relationships inherent in the specialty grades.

Most notably, many of the reactive polymer products have found utility in the thermoplastic modification market. The high Tg resins can impart increased heat distortion resistance to many commodity plastic grades, SMA resins are used to improve the properties of virgin and recycled polyaramids, and metallic monomers are capable of improving the physical properties of standard polyolefins. The diene-based polymer products are also finding utility as additives to thermoplastics packaging, improving the oxygen barrier properties of films. Ricon MA and other functional grades are used to improve the dispersion of organic and inorganic fillers in many thermoplastic compound formulations.

There are many other markets that have taken advantage of the diversity of chemistry and material properties including electronics, industrial coatings, and polyurethanes. Our goal is to work with every customer to provide value-added specialty materials that increase the performance of their products.

Market Breakdown

Cray Valley HSC offers a diverse selection of specialty liquid polybutadiene grades including low and high vinyl polybutadiene homopolymers and poly(styrene-butadiene) copolymers. Ricon grades offer a complete selection of microstructures, which translates to a wide spectrum of glass transition temperatures. In addition to the base product line, functional derivatives are available. The Ricon MA and Ricobond series include maleic anhydride grafted grades. Poly bd hydroxyl-terminated polyb-utadienes are available, and our unique Krasol product line consists of both unsaturated and fully hydrogenated telechelic polybutadiene diols.

The products are used in an equally broad spectrum of markets and applications. Low-viscosity liquid polybutadienes are used as processing aids, and the wide Tg range allows for modification of tire performance properties. In addition, high vinyl grades are useful as coagents for the peroxide cure of rubber. Functional grades expand the utility of the polybutadiene res-ins to many other applications, including polyurethanes, hydrophobic sealants and coatings, and thermoplastic modification.

Liquid Polybutadienes

*Krasol and Poly bd products require a license for export.

Product Description Typical Properties Availability

Molecular Weight (Mn, g/mol) 1,2 Vinyl (%) Viscosity (cps) Tg (°C) Specific Gravity MA (/chain) -OH (/chain) Epoxy

(eq. wt.)

Ricon Low Vinyl Content

Ricon 130 Homopolymer of Butadiene 2,500 28 750 @ 25 °C -86 0.89 -- -- -- US, EU, Asia


Ricon 134 Homopolymer of Butadiene 8,000 28 15,000 @ 25 °C -81 0.89 -- -- -- US, EU, Asia

High Vinyl Content

Ricon 150 (Ricon 150D) Homopolymer of Butadiene (Dry Liquid 70% Active) 3,900 70 40,000 @ 25 °C -40 0.89 -- -- -- US, EU, Asia






Styrene-Butadiene Copolymers

Ricon 100 Butadiene-Styrene Random Copolymer (25% Styrene) 4,500 70 40,000 @ 45 °C -15 0.90 -- -- -- US, EU, Asia



Ricon 250 Butadiene-Styrene Random Copolymer (35% Styrene) 5,300 70 900 @ 25 °C -- 0.90 -- -- -- US, EU, Asia

Ricon MA, Ricobond Low Vinyl Content

Ricon 130MA8 Maleinized Polybutadiene 3,100 28 6500 @ 25 °C -82 0.90 2 -- -- US, EU, Asia

Ricon 131MA5 Maleinized Polybutadiene 4,700 28 15,000 @ 25 °C -83 0.90 2 -- -- US, EU, Asia

Ricobond 1731 (Ricobond 1731HS) Maleinized Polybutadiene (Dry Liquid 69% Active) 5,400 28 50,000 @ 45 °C -72 0.91 9 -- -- US, EU, Asia

High Vinyl Content

Ricobond 1756 (Ricobond 1756HS) Maleinized Polybutadiene (Dry Liquid 69% Active) 2,500 70 140,000 @ 55 °C -18 0.91 3 -- -- US, EU, Asia

Krasol* Diol

Krasol LBH 2000 Hydroxyl-Terminated Polybutadiene 2,100 65 13,000 @ 25 °C -35 0.89 -- 1.9 -- US, EU, Asia

Krasol LBH-P 2000 Hydroxyl-Terminated Polybutadiene (Primary-OH) 2,100 65 13,000 @ 25 °C -35 0.89 -- 1.9 -- US, EU, Asia

Krasol LBH 3000 Hydroxyl-Terminated Polybutadiene 3,000 65 20,000 @ 25 °C -35 0.89 -- 1.9 -- US, EU, Asia

Krasol LBH-P 3000 Hydroxyl-Terminated Polybutadiene (Primary-OH) 3,200 65 20,000 @ 25 °C -35 0.89 -- 1.9 -- US, EU, Asia

Hydrogenated

Krasol HLBH-P2000 Hydroxyl-Terminated Hydrogenated Polybutadiene 2,100 -- 1,750 @ 60 °C -46 0.88 -- 1.9 -- US, EU, Asia

Krasol HLBH-P3000 Hydroxyl-Terminated Hydrogenated Polybutadiene 3,100 -- 3,000 @ 60 °C -46 0.88 -- 1.9 -- US, EU, Asia

Poly bd* Polyol

Poly bd R-45HTLO Hydroxyl-Terminated Polybutadiene 2,800 20 5,000 @ 30 °C -75 0.90 -- 2.5 -- US, EU, Asia

Poly bd R-20LM Hydroxyl-Terminated Polybutadiene 1,200 20 1,400 @ 30 °C -70 0.91 -- 2.5 -- US, EU, Asia

Epoxidized

Poly bd 605E Epoxidized Hydroxyl-Terminated Polybutadiene 1,450 20 12,000 @ 30 °C -47 1.01 -- 2.5 450 US, EU, Asia

6 7

Hydrocarbon Resins

8 9

Cray Valley’s hydrocarbon resin products complete a diverse portfolio. The Wingtack and Norsolene lines cover a wide spectrum of aliphatic, aromatic, and pure monomer resin grades. The Wingtack grades are high-quality, low-color C5 resins. The Norsolene A, S, and M series include a range of low to high softening point C9 and C5-C9 resins. In addition, the Norsolene W series are colorless pure monomer resins.

The main outlet for Cray Valley HSC hydrocarbon resins is the adhesives market, including hot melt, pressure sensitive tapes and labels, construction mastics, and specialty adhesives applications. In addition, the hydrocarbon resins are useful tackifiers and compatibilization aids for the rubber market. Other main areas of utility include coatings and thermoplastic modification.

*50% Toluene Solution


Softening Point (RB, °C) Appearance Gardner Color* Specific Gravity @ 20 °C Molecular Weight

(Mn, g/mol) Tg (°C)

Wingtack

Wingtack 10 C5 Hydrocarbon Resin 10 Light yellow liquid 1.5 0.90 370 -31 US, EU, Asia

Wingtack 95 C5 Hydrocarbon Resin 98 Light yellow solid 1.7 0.94 1100 52 US, EU, Asia


Wingtack RWT-7850 C5 Hydrocarbon Resin 102 Light yellow solid 2.4 0.95 1000 56 US, EU, Asia

Wingtack Plus C5 Hydrocarbon Resin 96 Light yellow solid 1.6 0.95 1000 50 US, EU, Asia

Wingtack EXTRA C5 Hydrocarbon Resin 97 Light yellow solid 1.4 0.96 1100 52 US, EU, Asia

Wingtack ET C5 Hydrocarbon Resin 95 Light yellow solid 2.0 0.96 1000 47 US, EU, Asia

Wingtack STS C5 Hydrocarbon Resin 94 Light yellow solid 3.0 0.97 1000 44 US, EU, Asia


Norsolene

Norsolene A-90 C9 Hydrocarbon Resin 97 Yellow solid 5.6 1.10 750 46 US, EU, Asia



Norsolene S-85 C9 Hydrocarbon Resin 87 Yellow solid 6.5 1.07 650 45 US, EU, Asia


Norsolene S95e C9 Hydrocarbon Resin 93 Yellow solid 6.0 1.07 600 40 US, EU, Asia











Norsolene M1080 C9 Hydrocarbon Resin 93 Yellow solid 6.0 1.10 600 40 US, EU, Asia



Norsolene W-85 Pure Monomer Resin 85 Colorless solid <1 1.06 600 35 US, EU, Asia







Cray Valley HSC produces a line of low molecular weight styrene-maleic anhydride copolymer resins with an extended range of monomer ratios. Based on these platforms, a number of value-added derivatives are formed, including specialty esters and imides. In addition, the base products can be esterified to form a variety of water-soluble salts.

The product diversification allows for an equally broad spectrum of end-use applications. The inherent heat resistance properties as well as reactive MA groups can provide value in polymer modification and electronics applications. The liquid forms are excellent dispersants over a broad pH range, providing utility in the coatings, inks, and paper industry. An abundance of MA groups allows SMA resins to be used in applications where targeted chemistry is required, including reactive modification of thermoplastics.

SMA Resins

Product Description Typical Properties Liquid Forms Availability

Ratio Styrene/Maleic Appearance Molecular Weight (Mn, g/mol) Tg (°C) Weight % MA Amine Index

(meq/g)

SMA Base Resins

SMA 1000 Base Resin 1 F, P 2,100 155 42 -- H, HNa, MA US, EU, Asia

SMA 2000 Base Resin 2 F, P 2,700 135 29 -- H US, EU, Asia

SMA 2021 Base Resin 2 F, P 12,000 155 29 -- H US, EU, Asia

SMA 3000 Base Resin 3 F, P 3,050 125 23 -- H, HNa US, EU, Asia

SMA EF30 Base Resin 3 F, P 3,050 125 23 -- -- US, EU, Asia

SMA 3024 Base Resin 3 F, P 10,000 141 23 -- -- US, EU, Asia

SMA 4000 Base Resin 4 F, P 3,600 115 19 -- -- US, EU, Asia




Esters

SMA 1440 Ester Resin -- F 2,900 60 -- -- H, HLS, HK US, EU, Asia

SMA 17352 Ester Resin -- F, P 2,900 125 -- -- H US, EU, Asia

SMA 2625 Ester Resin -- F, P 3,100 110 -- -- H US, EU, Asia

SMA 3840 Ester Resin -- F 4,100 75 -- -- -- US, EU, Asia

Imides

SMA 1000I Imide Resin 1 P 2,100 85 -- 3.15 -- US, EU, Asia




Key

F Flake

P Powder

H Ammonia Hydrolyzed

HNa Sodium Hydrolyzed

MA Methyl Amine Amic Acid

HLS Ammonia Hydrolyzed Low Solids

HK Potassium Hydrolyzed

10 11

Cray Valley HSC provides a selection of metallic monomers. Straight grade and scorch retarding rubber coagent monomers are available for peroxide-cure applications, while our specialty monomers are used in a wide variety of cure systems, including accelerated sulfur vulcanization and metal oxide cure.

Our products find utility in a variety of applications including tires, power transmission belts, rubber sealing systems, coatings, thermoplastics, and adhesives.



Appearance Specific Gravity @ 25 °C

Metallic Monomers Straight Grade

Dymalink 636 Calcium Diacrylate white powder 1.44 US, EU, Asia

Dymalink 705 Zinc Diacrylate white powder 1.68 US, EU, Asia

Dymalink 708 Zinc Dimethacrylate white powder 1.50 US, EU, Asia

Dymalink 709 Zinc Monomethacrylate white powder 1.88 US, EU, Asia

Scorch Retarding

Dymalink 633 Zinc Diacrylate off-white powder 1.59 US, EU, Asia

Dymalink 634 Zinc Dimethacrylate off-white powder 1.48 US, EU, Asia

Specialty Monomers Dymalink 1100 Acrylate Blend (Dry liquid version – 70% active) white powder 1.35 US, EU, Asia

12 13

Thermoplastic Urethanes

14 15

Cray Valley HSC leverages unique polybutadiene diols to produce a line of diene-based thermoplastic urethanes. The TPUs include both unsaturated hydrocarbon soft segments and polar urethane hard segments. The novel structure allows the TPU products to find utility in a number of rubber, adhesive, and thermoplastic applications.


Shore A Hardness Elongation (%) Modulus (PSI) Tensile Strength (PSI)

TPU

2035 TPU Polybutadiene TPU (insoluble) 82 560 950 1710 US, EU, Asia

Reference Guide

16 17

-100 -50 0 50 100 150 200

°C

Ricon® Norsolene®

Poly bd® Wingtack®

Krasol™ SMA®

Glass Transition Temperature (Tg)

Ricon®

Poly bd®Wingtack®

Krasol™

Norsolene® SMA®

100 1000 10000 100000

g/mol in log scale

Molecular Weight (Mn) Technology

Cray Valley HSC and the Total Group

Cray Valley HSC is a division within Total’s Chemicals segment. Founded in 1924, Total is the world’s fifth-largest international oil and gas producer, with operations in more than 130 countries. Total engages in all aspects of the petroleum industry, including upstream operations (oil and gas exploration, development and production, LNG) and downstream operations (refining, marketing, trading, and shipping of crude oil and petroleum products). Total also produces base chemicals and specialty chemicals for the industrial and consumer markets.

Total’s chemicals business is a leader in each of its markets: base chemicals (petrochemicals and fertilizers) and specialty chemicals for the industrial and consumer markets (rubber processing, adhesives, resins, and electroplating).

Backed by the financial resources and technical services of the Chemicals segment of Total, Cray Valley HSC provides a strong global approach to R&D, manufacturing, and customer support.

Plasticizer Crosslinking AdhesionChemical

Intermediate/Polymerization

Dispersion/Surface

ModificationOther

Ricon®

Poly bd®

Krasol™

Wingtack®

Norsolene®

SMA®


www.crayvalley.com

Email: [email protected]

877-US1-CRAY

877-871-2729

www.crayvalley.com

Cray Valley USA, LLC

468 Thomas Jones Way

Suite 100

Exton, PA 19341 USA

The information in this bulletin is believed to be accurate, but all recommendations are made without warranty since the conditions of use are beyond Cray Valley’s control. The listed properties are illustrative only and not product specifications. Cray Valley disclaims any liability in connection with the use of the information and does not warrant against infringement by reason of the use of its products in combination with other material or in any process.

01/2013

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PKL - Cray Valley