Modern Plastics Handbook 2011 Part 5 ppt

The growth of heat stabilizers is dependent on PVC growth. Rigid PVC applications are expected to grow at a faster rate than flexible PVC applications worldwide. This indicates organotins will experience higher growth than mixed metals. Over the next 5 years, heat stabi- lizers are expected to grow at a rate of 6%/year paced by the Asia/Pacific and the developing regions of the world. 4.11 Impact Modifiers 4.11.1 Description Impact modifiers are used in a wide variety of thermoplastic resins to absorb the energy generated by impact and dissipate it in a nonde- structive fashion. The behavior and definition of impact modifiers are complex. The selection of an impact modifier is dependent on compat- ibility, physical solubility, impact performance, and cost. Impact modifiers are primarily used in PVC, engineering resins, and polyolefins. The use levels of impact modifiers vary widely depending upon the modifiers, matrix type, and properties desired. The major types are shown in Table 4.15 along with the resins in which they are primarily used. Plastic Additives 4.41 TABLE 4.14 Selected Heat Stabilizer Suppliers Type Supplier Mixed metal Organotin Lead Akzo ϫϫϫ Asahi Denka Kogyo K.K. ϫϫ— Baerlocher ϫ —— BASF ϫϫϫ Cardinal Chemical — ϫ — Chemson ϫϫϫ Clariant/Hoechst ϫ —— Dainippon Ink and Chemicals ϫϫ— Elf Atochem ϫϫ— Ferro ϫϫϫ Hammond Lead — — ϫ Kolon Chemical ϫ — ϫ Kyodo Chemical ϫϫ— Morton International — ϫϫ Nan Ya Plastics ϫϫϫ Nanjing Chemical Factory ϫϫϫ NOF ϫ —— OMG ϫ —— Reagens SpA ϫϫϫ Sakai Chemical ϫϫϫ Tokyo Fine Chemical ϫϫ— Witco ϫϫ— 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.41 TABLE 4.15 Major Types of Impact Modifiers by Resin Resin Type PVC* PE** PP† PA‡ PET/PBT§ Other MBS (methacrylate butadiene styrene) ϫ ——— — — MABS (methacrylate/acrylonitrile- butadiene-styrene) ϫ ——— ϫ — ABS (acrylonitrile-butadiene-styrene) ϫ ——— ϫ — CPE (chlorinated polyethylene) ϫϫϫ—— — EVA (ethylene vinyl acetate) ϫ ——— — — PMMA (polymethylmethacrylate) ϫ ——— — ϫ EPDM (ethylene propylene diene monomer) ϫϫϫ—— — EPR (ethylene propylene rubber) ϫϫϫ—— — SBR (styrene butadiene rubber) — — — — — ϫ Others — — — — — — Maleated EPDM — — — ϫϫ — Maleated PP and PE — — — ϫϫ — PUR (Polyurethane) — — — — — ϫ SAN-g-EPDM — — — — ϫ — *PVC—polyvinylchloride. **PE—polyethylene. †PP—polypropylene. ‡PA—polyamide. §PET—polyethylene terephthalate; PBT—polybutylene terephthalate. 4.42 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.42 Methacrylate-butadiene-styrene (MBS). Methacrylate-butadiene-styrene represents the highest volume of the styrenic type impact modifiers. This modifier is used in transparent packaging applications due to its clarity. Rigid applications include film, sheet, bottles, credit cards, and interior profiles. MBS has limited use in exterior applications due to poor ultraviolet (UV) stability. Methacrylate/acrylonitrile-butadi- ene-styrene (MABS) is closely related to MBS, but has minor use in the industry and has been completely replaced by MBS in North America. Acrylonitrile-butadiene-styrene (ABS). Acrylonitrile-butadiene-styrene is used in a variety of resins, with about 60% in PVC. The primary ABS applications are in automotive parts, credit cards, and packag- ing. ABS, like MBS, is not suitable for outdoor applications unless it is protected by a UV-resistant cap. ABS, although compatible with MBS, suffers from the disadvantage of not being regarded as an industry standard. Acrylics. Acrylics are similar to MBS and ABS but have butyl acrylate or 2-ethyl-hexyl acrylate graft phases. Acrylics offer greater resistance to UV degradation and are used primarily in PVC siding, window pro- files, and other applications calling for weather resistance. Due to growth in the building and construction industry, acrylics are experi- encing the highest growth rate. Chlorinated polyethylene (CPE). Chlorinated polyethylene modifiers are most commonly used in pipe, fittings, siding, and weatherable profiles. CPE modifiers compete primarily with acrylics in siding applications. CPE can be used in resins other than PVC, for example, PE and PP. Ethylene vinyl acetate (EVA). Ethylene vinyl acetate modifiers have minor usage compared to other types of impact modifiers. EVA finds use in limited segments of the flexible PVC sheet business. Ethylene propylene diene monomer (EPDM). Ethylene propylene diene monomer is used in thermoplastic olefin (TPO) for automotive bumpers and parts as well as scattered consumer durable markets. Maleic anhydride grafted EPDM. Maleic anhydride grafted EPDM reacts with the matrix resin, typically nylon, to become its own compatibilizer. This type of modifier provides for excellent balance in impact, hardness, modulus, and tensile strength and is the major additive component of “super tough” nylon. Plastic Additives 4.43 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.43 4.11.2 Suppliers There are over 30 suppliers of impact modifiers worldwide. Most con- centrate their efforts in one type of modifier as a result of their devel- oped technologies and backward integration. Selected suppliers resell other producers’ technologies in their home regions to broaden their product lines Rohm and Haas, Kaneka, and Atochem are the leading suppliers of impact modifiers worldwide. Each has strong positions in both the acrylic and MBS-related modifiers. Elf Atochem is stronger in acrylics, while Kaneka is stronger in MBS types. Rohm and Haas, including its joint venture with Kureha in the Asia/Pacific region, has a more bal- anced position. Table 4.16 presents the major global suppliers of impact modifiers by type. 4.11.3 Trends and forecasts The need for cost-effective materials that are strong, stiff, and ductile will continue to increase. In many cases the key to success will be the development of tailored impact modifier systems for specific resins. The EPDM market will probably see a decline over the next couple of years due to the advent of reactor-generated polypropylene. This material incorporates the impact modifier in the polymer chain and does not require a secondary compounding operation. The MBS market is decreasing partially due to PVC bottles being replaced by PET. This trend is more evident in Europe due to wide- spread use of water bottles. In contrast, the film and sheet market remain strong. Overall, MBS sales are heavily dependent on the future of PVC, particularly flexible PVC. Flexible PVC, comprising 15% of the total PVC market, is vulnerable to penetration by metal- locene catalyzed polyolefins (for example, “super soft polypropylene”). Acrylic impact modifiers will continue to grow with the growth of rigid PVC in the construction market. Product development in this market will target improved low-temperature impact properties to reduce failures, lengthen the installation season, and lower cost. A significant area for product development is the impact modifica- tion of engineering plastics. The replacement of such conventional materials as metal, glass, and wood by plastics has been underway for years. The applications are typically converted to engineering plastics and then lost to lower-cost polyolefins and/or vinyl type materials. Most of the “easy” applications have already converted to plastic. The remaining ones, particularly in durable goods, require new levels of strength and impact performance. Consumption of impact modifiers worldwide is projected to grow at 5%/year over the next 5 years. 4.44 Chapter Four 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.44 TABLE 4.16 Selected Impact Modifier Suppliers Type ABS/MBS/ EPR/ Supplier Acrylic MABS EVA EPDM CPE Other Baerlocher ϫ ————— Bayer — ϫϫ——— Chisso — — ϫ ——— DSM Copolymer — — — ϫϫ— Dupont/Dow Elastomers — — ϫϫϫ— Elf Atochem ϫϫ———ϫ Exxon — — — ϫϫϫ GE Specialty Chemicals — ϫ ———— Huels — — — — ϫ — JSR — — — — — ϫ Kaneka — ϫ ———ϫ Kureha — — — — — ϫ Mitsubishi Rayon — — — — — ϫ Mitsui Petrochemical — — — — — ϫ Nippon Zeon — — ϫ ——ϫ Osaka Soda — — — — ϫ — Polysar — — — ϫ —— Rohm and Haas ϫϫ———— Shell — — — — — ϫ Showa Denko K.K. — — — — ϫ — Sumitomo Chemical — ϫ — ϫ —— Toyo Soda — — — ϫ —— Ube Cycon — ϫ ———— Uniroyal — — — ϫ — ϫ 4.45 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.45 4.12 Light Stabilizers 4.12.1 Description Light stabilizers are used to protect plastics, particularly polyolefins, from discoloration, embrittlement, and eventual degradation by UV light. The three major classes of light stabilizers are UV absorbers, excited state quenchers, and free-radical terminators. Each class is named for the mechanism by which it prevents degradation. The major types included in each light stabilizer class may be categorized by their chemistries, as shown in Table 4.17. Benzophenone. Benzophenone UV absorbers are mature products and have been used for many years in polyolefins, PVC, and other resins. These products also have wide use in cosmetic preparations as sun- screens and protectants. Benzotriazole. Benzotriazole UV absorbers are highly effective in high- temperature resins such as acrylics and polycarbonate. They also find extensive use in areas outside plastics such as coatings. Benzoates and salicylates. Benzoates and salicylates such as 3,5-di-t- butyl-4hydroxybenzoic acid n-hexadecyl ester, function by rearrang- ing to 2-hydroxybenzophenone analogs when exposed to UV light to perform as UV absorbers. Nickel organic complexes. Nickel organic complexes protect against degradation caused by UV light via excited state quenching. These deactivating metal ion quenchers stop the energy before it can break any molecular bonds and generate free radicals. Nickel complexes are primarily used in polyolefin fiber applications. Some examples of nick- el complexes are nickel dibutyldithiocarbamate and 2,2′ thiobis (4- octylphenolato)-n-butylamine nickel II which are also used in agricultural film because of their resistance to pesticides. Hindered amine light stabilizers (HALS). Hindered amine light stabiliz- ers are the newest type of UV light stabilizer. They were introduced in 1975 by Ciba and Sankyo. HALS do not screen ultraviolet light, but stabilize the resin via free-radical termination. HALS are used at low- er levels than benzophenones and benzotriazoles, and are widely used in polyolefins for their cost-effectiveness and performance. The suc- cessful growth of HALS has been directly related to their substitution for benzophenones and benzotriazoles in many applications as well as their blending with benzophenones. 4.46 Chapter Four 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.46 4.12.2 Suppliers There are about 40 suppliers of light stabilizers worldwide. Some of these companies also produce antioxidants and PVC heat stabilizers. Of these 40 or so suppliers, only Ciba Specialty Chemicals is a signifi- cant player in every region of the world with the broadest product line of light stabilizers. Selected global suppliers of light stabilizers are giv- en in Table 4.18. 4.12.3 Trends and forecasts The entrance of Great Lakes into the European light stabilizer market with a series of acquisitions has been the most significant restructur- ing that has occurred in the light stabilizer market. This move has accelerated the trend toward a more competitive market in these materials. Growth in the light stabilizer business is strongly dependent on the growth of the polyolefin applications. Polyolefins account for about three-quarters of the total global consumption of light stabilizers in plastics. Polyolefins, particularly PP, are replacing metals, engineer- Plastic Additives 4.47 TABLE 4.17 Major Types of Light Stabilizers Type Representative chemistry UV light absorbers Benzophenone 2-hydroxy-4-methoxybenzophenone 2-hydroxy-4-n-octoxybenzophenone 2,4-dihydroxy-4-n-dodecycloxybenzophenone Benzotriazole 2,2-(2-hydroxy-5-tert-octylphenyl) benzotriazole 2-(3′-tert-butyl-2-hydroxy-5-methylphenyl)-5- chlorobenzotriazole 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5′- chlorobenzotriazole 2-(2′hydroxy-3′-5′-di-tert amyl phenyl) benzotriazole 2-(2-hydroxy-5-methylphenyl) benzotriazole Phenyl esters 3,5-di-t-butyl-4hydroxybenzoic acid N-hexadecyl ester Diphenylacrylates Ethyl-2-cyano-3,3-diphenyl acrylate 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate Excited state quenchers Nickel compounds Nickel dibutyldithiocarbamate 2,2′-thiobis (4-octylphenolato)-n-butylamine nickel II Free-radical terminators Hindered amine light stabilizers Bis (2,2,6,6-tetramethyl-4-piperidinyl) (HALS) N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6- hexane diamine polymer with 2,4,6-trichloro- 1,3,5 triazine and 2,4,4-trimethyl- 1,2-pentanamine 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.47 4.48 Chapter Four TABLE 4.18 Selected Light Stabilizer Suppliers Type Supplier HALS Benzotriazole Benzophenone Others 3V Sigma ϫ — ϫ — Akcros (Akzo) — ϫϫ— Asahi Denka Kogyo ϫϫ ϫ — Asia Stabilizer — ϫϫ— BASF ϫ — ϫϫ BF Goodrich ϫ ——— Chemipro Kasei Kaisha — ϫϫϫ Ciba Specialty Chemicals ϫϫ ϫ ϫ Clariant ϫϫ ϫ ϫ Cytec Industries ϫϫ ϫ — Dai-ichi Chemical Industries — — — ϫ Dainippon Ink and Chemicals — — — ϫ Eastman Chemical — — — ϫ Elf Atochem ϫ ——— Everlight Chemical Industrial ϫϫ ϫ — Fairmount Chemical — ϫ —— Ferro — — ϫϫ Great Lakes Chemical ϫϫ ϫ — Honshu Chemical — — ϫ — Iwaki Seiyaku — — — ϫ Johoku Chemical — ϫ —— Kolon Industries — — ϫ — Korea Fine Chemicals — — ϫ — Kyodo Chemicals — ϫϫϫ Liaoyang Organic Chemical ϫ ——ϫ Mitsubishi Petrochemical — — — ϫ Musashino Geigy ϫϫ —— Nissan Ferro Organic Chemical — — — ϫ Osaka Seika Chemical Ind. — ϫϫ— Sakai Chemical Industry — — — ϫ Sankyo ϫ — ϫ — Shipro Kasei — ϫϫϫ Shonan Kagaku Kogyo — — ϫ — Sumitomo Chemical — ϫϫϫ Witco — — ϫ — Yashiro Seiyaku — — — ϫ Yoshitomi Fine Chemicals ϫϫ ϫ — 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.48 ing plastics, and styrenics in automotive and other applications, fur- ther increasing the volume of stabilizers consumed. The use of nickel-containing stabilizers is decreasing in the market- place, particularly in North America, due to potential toxicity concerns. In Europe, nickel continues to be used in agricultural film applications. Design efforts are focusing on down-gauging of exterior plastic parts for weight and cost reduction. This will place increased value on light stabilization to maintain adequate performance at thinner wall sections. HALS will experience the strongest growth due to their widespread use in polyolefins and their cost-effectiveness and performance. Benzotriazoles and benzophenones, however, are more effective than HALS in vinyl and engineering plastics. Significant product development work is being done in HALS tech- nology to produce higher-performance products in polyolefin systems. Low molecular weight alkoxy substituted amine systems and higher molecular weight HALS stabilizers significantly improve the perfor- mance of pigmented TPO parts with regard to color and gloss retention. HALS are being promoted by selected suppliers as effective light stabilizer with excellent capabilities as antioxidants. In some cases, these materials are comparable to well-established antioxidant prod- ucts such as Ciba’s IRGANOX 1010. Suppliers continue to improve on the physical forms of light stabi- lizers. For example, Cytec is introducing a flake form light stabilizer which reduces dusting and increases the shelf life of the products. Consolidation is expected to continue due to margin pressures caused by regulatory issues such as FDA compliance, toxicological testing, environmental compliance, and the continual need for capital investment. This trend may be most apparent in the Asia/Pacific region where there are a large number of small suppliers. Globally, light stabilizers should grow at a rate of 7%/year over the next 5 years, with the less developed regions in Asia/Pacific, Latin America, and Africa leading the way. This robust growth parallels the growth of polyolefins, particularly polypropylene/TPO, and engineering resins into more exterior applications replacing metal and painted plastic. 4.13 Lubricants and Mold Release Agents 4.13.1 Description Lubricants. Lubricants represent a broad class of materials that are used to improve the flow characteristics of plastics during processing. Besides this primary task of improving flow properties, lubricants can act as melt promoters, antiblock, antitack, and antistatic agents as well as color and impact improvers. They can be used in conjunction with metal release agents and heat stabilizers. Lubricants are widely Plastic Additives 4.49 0267146_Ch04_Harper 2/24/00 4:57 PM Page 4.49 [...]... 0. 25 0.40 0. 25 0.20–0.30 0.20 — 0.08 2 25 — 190 260 200 2 35 88 93 82 3–4 1–2 1–2 1.60 0. 15 270 290 82 4 5 1 .50 0. 15 2 65 2 65 82 4 5 0.20 0.02 290 300 120 3–4 0.08 0.04 — 240 1 25 2–3 0.10 0. 25 0.0 05 — 250 — 255 370 160 155 4 5 4 5 Ͻ0.01 — 210 250 — — Ͻ0.01 — 180 2 05 — — Ͻ0.01 — 260 220 — — 0.07 Ͻ0.01 0.03 — — — 250 2 35 210 2 75 255 220 100 — — 2–3 — — 0.10 — 2 35 230 — — 0.30 0.10 0.07 0.10 0.02 0.03 0. 05. .. 2–3 — — 0.10 — 2 35 230 — — 0.30 0.10 0.07 0.10 0.02 0.03 0. 05 0.03 0.03 0.07 — 0.02 — 3 45 2 05 200 1 85 1 75 2 15 330 360 2 05 2 05 1 95 150 2 45 140 1 35 82 100 — — 82 2–3 3–4 2–3 2–3 — — 3–4 While thermoplastic polymers soften at Tg, and if semicrystalline, melt at Tm, cross-linked polymers do not melt and flow (Fig 5. 2c5) Lightly cross-linked polymers soften as the temperature exceeds Tg, but they remain... and shrinkage 5. 1.1 Processing temperatures Polymers are manufactured using two basic polymerization methods: addition and condensation Addition polymerization generally produces rapid chain growth, molecular weights greater than 100,000 daltons, and no by-products In contrast, condensation polymerization provides 0267146_Ch 05_ Harper 2/24/00 4 :54 PM Page 5. 5 Processing of Thermoplastics 5. 5 for lower... blend is polystyrene-polyphenylene (a) (b) (c) (d) mer a mer b Figure 5. 1 Types of copolymers (Adapted from Ref 2.) 0267146_Ch 05_ Harper 5. 4 2/24/00 4 :54 PM Page 5. 4 Chapter Five oxide (modified polyphenylene oxide) Partially miscible blends can exist as a single- or two-phase system, depending on composition and processing conditions When partial miscible blends, such as polycarbonate/acrylonitrile butadiene... ϫ 0267146_Ch04_Harper 4 .58 2/24/00 4 :57 PM Page 4 .58 Chapter Four etrate electrical uses Based on this activity, consumption of nucleating agents is likely to increase at a rate of about 6%/year globally over the next 5 years 4. 15 4. 15. 1 Organic Peroxides Description Organic peroxide initiators serve as sources of free radicals in the preparation of a variety of resins for plastics, elastomers, and... 0267146_Ch 05_ Harper 2/24/00 4 :54 PM Page 5. 1 Chapter 5 Processing of Thermoplastics Carol M F Barry Stephen A Orroth University of Massachusetts Lowell, Massachusetts McKelvey1 defined plastics processing as “operations carried out on polymeric materials or systems to increase their utility.” These types of operations produce flow, chemical change, and/or a permanent change in physical properties.1 Plastics. .. characteristics also vary 0267146_Ch 05_ Harper 2/24/00 4 :54 PM Page 5. 3 Processing of Thermoplastics 5. 3 with the ratio of the components and their arrangement within the copolymer As shown in Fig 5. 1a,2 the repeat units of random copolymers are distributed randomly along the polymer chain Thus, ethylene propylene rubber (EPR) is an elastomer, whereas polyethylene and polypropylene are plastics In poly(styrene-co-acrylonitrile)... molding induce both chemical and physical change in the plastics materials Bonding operations join two or more materials by causing one or both joining surfaces to become molten or flow The former occurs while laminating polyethylene to aluminum or paper, coating of polyvinyl chloride plastisols on 5. 1 0267146_Ch 05_ Harper 5. 2 2/24/00 4 :54 PM Page 5. 2 Chapter Five fabric (to produce vinyl upholstery),... /alcohols Silicones 2/24/00 4 :57 PM Page 4 .53 Akcros (Akzo) AlliedSignal Baerlocher BASF Chemson Clariant Croda Dow Corning Eastman Chemical Elf Atochem Faci Ferro GE Specialty Chemicals Henkel Huels ICI Specialty Chemicals Lonza Morton Plastic Additives Olefina Rhodia Sogis Wacker Silicones Witco Metallic stearates 4 .53 0267146_Ch04_Harper 4 .54 2/24/00 4 :57 PM Page 4 .54 Chapter Four Key technology... do not have welldefined melting temperatures Melt processing temperatures of semicrystalline polymers are usually less than 100°C above their melt temperatures 0267146_Ch 05_ Harper 5. 6 2/24/00 4 :54 PM Page 5. 6 Chapter Five TABLE 5. 1 Suggested Drying Conditions for Generic Resins3,4 Material Acrylonitrile butadiene styrene (ABS) Acetal Acrylic Polyamide-6 (nylon) (PA-6) Polyamide-6, 6 (nylon) (PA-6,6) . 2,2-(2-hydroxy -5- tert-octylphenyl) benzotriazole 2-(3′-tert-butyl-2-hydroxy -5- methylphenyl) -5- chlorobenzotriazole 2-(3′ ,5 -di-tert-butyl-2′-hydroxyphenyl) -5 - chlorobenzotriazole 2-(2′hydroxy-3′ -5 -di-tert. ———— Uniroyal — — — ϫ — ϫ 4. 45 0267146_Ch04_Harper 2/24/00 4 :57 PM Page 4. 45 4.12 Light Stabilizers 4.12.1 Description Light stabilizers are used to protect plastics, particularly polyolefins, from. 2/24/00 4 :57 PM Page 4 .57 etrate electrical uses. Based on this activity, consumption of nucleat- ing agents is likely to increase at a rate of about 6%/year globally over the next 5 years. 4. 15 Organic