Polymer styrene-isoprene-butadiene rubber

Polymers of chloroprene (structure [XII]) are called neoprene and copolymers of butadiene and styrene are called SBR, an acronym for styrene-butadiene rubber. Both are used for many of the same applications as natural rubber. Chloroprene displays the same assortment of possible isomers as isoprene the extra combinations afforded by copolymer composition and structure in SBR offsets the fact that structures [XIIll and [XIV] are identical for butadiene. 

Block copolymer chemistry and architecture is well described in polymer textbooks and monographs [40]. The block copolymers of PSA interest consist of anionically polymerized styrene-isoprene or styrene-butadiene diblocks usually terminating with a second styrene block to form an SIS or SBS triblock, or terminating at a central nucleus to form a radial or star polymer (SI) . Representative structures are shown in Fig. 5. For most PSA formulations the softer SIS is preferred over SBS. In many respects, SIS may be treated as a thermoplastic, thermoprocessible natural rubber with a somewhat higher modulus due to filler effect of the polystyrene fraction. Two longer reviews [41,42] of styrenic block copolymer PSAs have been published. 

Emulsion polymerization is the most important process for production of elastic polymers based on butadiene. Copolymers of butadiene with styrene and acrylonitrile have attained particular significance. Polymerized 2-chlorobutadiene is known as chloroprene rubber. Emulsion polymerization provides the advantage of running a low viscosity during the entire time of polymerization. Hence the temperature can easily be controlled. The polymerizate is formed as a latex similar to natural rubber latex. In this way the production of mixed lattices is relieved. The temperature of polymerization is usually 50°C. Low-temperature polymerization is carried out by the help of redox systems at a temperature of 5°C. This kind of polymerization leads to a higher amount of desired trans-1,4 structures instead of cis-1,4 structures. Chloroprene rubber from poly-2-chlorbutadiene is equally formed by emulsion polymerization. Chloroprene polymerizes considerably more rapidly than butadiene and isoprene. Especially in low-temperature polymerization emulsifiers must show good solubility and... 

Diene polymers refer to polymers synthesized from monomers that contain two carbon-carbon double bonds (i.e., diene monomers). Butadiene and isoprene are typical diene monomers (see Scheme 19.1). Butadiene monomers can link to each other in three ways to produce ds-1,4-polybutadiene, trans-l,4-polybutadi-ene and 1,2-polybutadiene, while isoprene monomers can link to each other in four ways. These dienes are the fundamental monomers which are used to synthesize most synthetic rubbers. Typical diene polymers include polyisoprene, polybutadiene and polychloroprene. Diene-based polymers usually refer to diene polymers as well as to those copolymers of which at least one monomer is a diene. They include various copolymers of diene monomers with other monomers, such as poly(butadiene-styrene) and nitrile butadiene rubbers. Except for natural polyisoprene, which is derived from the sap of the rubber tree, Hevea brasiliensis, all other diene-based polymers are prepared synthetically by polymerization methods. 

Several polymers based on 1,3-dienes are used as elastomers. These include styrene-1,3-butadiene (SBR), styrene-1,3-butadiene terpolymer with an unsaturated carboxylic acid (carboxylated SBR), acrylonitrile-1,3-butadiene (NBR or nitrile rubber) (Secs. 6-8a, 6-8e), isobutylene-isoprene (butyl rubber) (Sec. 5-2i-l), and block copolymers of isoprene or... 

Other commercial copolymers which are typically random are those of vinyl chloride and vinyl acetate (Vinylite), isobutylene and isoprene (butyl rubber), styrene and butadiene (SBR), and acrylonitrile and butadiene (NBR). The accepted nomenclature is illustrated by EP, which is designated poly-ethylene-co-propylene the co designating that the polymer is a copolymer. When the copolymers are arranged in a regular sequence in the chains, i.e., ABAB, the copolymer is called an alternating copolymer. A copolymer consisting of styrene and maleic anhydride (SMA) is a typical alternating copolymer. 

Another large use of normal butenes in the petrochemical industry is in the production of 1,3-butadiene (CH2 = CH = CH = CH2). In the process, a mixture of n-butenes, air, and steam is passed over a catalyst at a temperature of 500°C to 600°C. Butadiene is used extensively to produce synthetic rubbers (see Isoprene) in polymerization reactions. The greatest use of butadiene is for styrene-butadiene rubber, which contains about a 3 1 ratio of butadiene to styrene. Butadiene is also used as a chemical intermediate to produce other synthetic organics such as chloroprene, for adhesives, resins, and a variety of polymers. 

The major general purpose rubbers are natural rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, and ethylene-propylene rubber. These rubbers are used in tires, mechanical goods, and similar applications. Specialty elastomers provide unique properties such as oil resistance or extreme heat stability. Although this differentiation is rather arbitrary, it tends also to classify the polymers according to volumes used. Styrene-butadiene rubber, butadiene rubber, and ethylene-propylene rubber account for 78 percent of all synthetic rubber consumed. 

Vulcanization is an industrial process applied to various polymers from the class of unsaturated polyhydrocarbons. The major practical use of vulcanized elastomers is the tire industry. Tires are made from various polymer blends, including natural rubber, typically between 20 and 50%. The other polymers used in various blends that can be vulcanized include copolymers such as poly(styrene-co-1,3-butadiene) or SBR, poly(acrylonitrile-co-1,3-butadiene-co-styrene) or ABS, poly(isobutylene-co-isoprene), poly(ethylene-co-propylene-co-1,4-hexadiene, etc. 

This discovery culminated in the commercial production and the announcement (41) in 1965 of thermoplastic elastomers from block polymers of styrene and butadiene (S-B-S) and of styrene and isoprene (S-I-S). To rubber scientists and technologists the most outstanding property of S-B-S and S-I-S was the unvulcanized tensile strength compared to that of vulcanized NR and vulcanized SBR carbon black stocks. Stress-strain curves, to break, of these latter materials are compared to that of S-B-S in Figure 2. It was pointed out that the high strength of S-B-S must be due to physical crosslinks. 

In view of the wide application of Py—GC in industry and research, the development of techniques and equipment for automatic analysis by this method is of great practical interest. An automatic Py—GC system was developed by Coulter and Thompson [69] for Curie-type cells with a filament for specific application in the tyre industry. A typical analysis involves the identification and determination of polymers in a tyre material sample. The material of a tyre is essentially a mixture of polymers, most often natural rubber (polyisoprene), synthetic polyisoprene, polybutadiene and butadiene-styrene copolymer. A tube is normally made of a material based on butyl rubber and a copolymer of isobutylene with small amounts of isoprene. In addition to the above ingredients, the material contains another ten to twelve, such as sulphur, zinc oxide, carbon black, mineral oil, pine pitch, resins, antioxidants, accelerators and stearic acid. In analysing very small samples of the tyre material, the chemist must usually answer the following question on the basis of which polymers is the tyre made and what is their ratio The problem is not made easier by the fact that cured rubber is not soluble in any solvent. 

Naturally, the more complex the composition of the substances to be pyrolysed, the more characteristics are needed for identification. For example, in identifying isoprene rubbers (NK, SKN-3, SKIL, Natsyn, Coral, Cariflex IR), the characteristic pyrolysis products are isoprene and dipentene, whereas with butadiene rubbers (SKB, SKD, Budene, Diene NF, Buna CB, Asadene NF, Cariflex BR, Ameripol CB) they are butadiene and vinylcyclohexane. With copolymer rubbers, the number of characteristic products necessary for identification increases to three, viz., butadiene, vinylcyclohexene and styrene are used for butadiene -styrene rubbers (SKS-10, SKS-30, Buna S. Europrene-1500, Solprene) and butadiene, vinylcyclohexene and methylstyrene are used for butadiene-methylstyrene rubbers (SKMS-10, SKMS-30) [139, 140]. Fig. 3.12 [139, 140] shows as an example pyrograms of individual general-purpose rubbers and a four-component mixture of rubbers. The shaded peaks correspond to those components in the pyrolysis products which are used for identification. The ratio of the pyrolysis products changes depending on the composition of the copolymer and the structure of the polymer. 

Rubber is the most important of all elastomers. Natural rubber is obtained from the bark of the rubber tree and has been used by humans for many centuries. It is a polymer with repeating units of isoprene. In 1823, rubber was vulcanized with sulfur whilst heated and this process made it to become the valuable material it is today. In this process, sulfur chain fragments attack the rubber polymer chains, which leads to cross-linking. Most of the rubber used in the world is a synthetic variety called styrene-butadiene rubber. 

General Description Kraton Polymers are a range of unhydrogenated styrenic block copolymers, compounds with an unsaturated rubber midblock (styrene-butadiene-styrene [SBS] and styrene-isoprene-styrene [SIS])J ° ]... 

Polymers Thermoplastic elastomers Styrene-butadiene-styrene (SBS), styrene-butadiene-rubber (SBR), styrene-isoprene-styrene (SIS), styrene-ethyl-butadiene-styrene (SEBS), ethyl-propyl-dien tetropolymer (EPDM), isobutene-isoprene copolymer (NR), polybutadiene (PBD),natural rubber (l),(2),(3),(4), [8]. [9], [10], [II], [13]... 

Mixtures, formulated blends, or copolymers usually provide distinctive pyrolysis fragments that enable qualitative and quantitative analysis of the components to be undertaken, e.g., natural rubber (isoprene, dipentene), butadiene rubber (butadiene, vinylcyclo-hexene), styrene-butadiene rubber (butadiene, vinyl-cyclohexene, styrene). Pyrolyses are performed at a temperature that maximizes the production of a characteristic fragment, perhaps following stepped pyrolysis for unknown samples, and components are quantified by comparison with a calibration graph from pure standards. Different yields of products from mixed homopolymers and from copolymers of similar constitution may be found owing to different thermal stabilities. Appropriate copolymers should thus be used as standards and mass balance should be assessed to allow for nonvolatile additives. The amount of polymer within a matrix (e.g., 0.5%... 

Thermoplastic rubber is a relatively new class of polymer. It has the solubility and thermoplasticity of polystyrene, while at ambient temperatures it has the toughness and resilience of vulcanized natural rubber or polybutadiene. These rubbers are actually block copolymers. The simplest form consists of a rubbery mid-block with two plastic end blocks (A-B-A), as shown in Figure 5.7. Examples of commercial products are Kraton and Solprene . These materials are often compounded with plasticizers to decrease hardness and modulus, eliminate drawing, enhance pressure-sensitive tack, improve low-temperature flexibility, reduce melt and solution viscosity, decrease cohesive strength or increase plasticity if desired, and substantially lower material costs. Low levels of thermoplastic rubbers are sometimes added to other rubber adhesives. These materials are used as components in the following applications PSAs, hot-melt adhesives, heat-activated-assembly adhesives, contact adhesives, reactive contact adhesives, building construction adhesives, sealants, and binders. Two common varieties of thermoplastic rubber adhesives are styrene-butadiene-styrene (S-B-S) and styrene-isoprene-styrene (S-I-S). ... 

Styrene block copolymers are the most widely used TPEs. Styrenic TPEs are usually styrene butadiene styrene (SBS), styrene ethylene butadiene styrene (SEES), and styrene isoprene styrene (SIS). Styrenic TPEs usually have about 30 0 percent bound styrene. Principal styrenic TPE markets are molded shoe soles and other footwear, extruded film/sheet and wire/cable covering, and pressure-sensitive and hot-melt adhesives. They are also popular as grips for bike handles, kitchen utensils, clear medical products, and personal care products. Styrenic block copolymer thermoplastic elastomers are produced by Shell Chemical (Kraton), Firestone Synthetic Rubber and Latex, Division of Bridgestone/Firestone (Stereon), Dexco Polymers (Vector), EniChem Elastomers (Europrene), and other companies. 

Well-known materials are the Kraton polymer range, originally developed by Shell, and are produced in several types. The D series has an unsaturated rubber midblock - styrene/butadiene/styrene (SBS), and styrene/isoprene/styrene (SIS) - and the G series has a saturated midblock - styrene ethylene/butylene styrene (SEES) and styrene ethylene/propylene (SEP). The G series has increased resistance to oxidation and weathering, higher service temperature and better processing stability. 

Some specific recent applications of the chromatography-mass spectrometry technique to various types of polymers include the following PE [130, 131], poly(l-octene), poly(l-decene), poly(l-dodecene) and 1-octene-l-decene-l-dodecene terpolymer [132], chlorinated polyethylene [133], polyolefins [134,135], acrylic acid, methacrylic acid copolymers [136, 137], polyacrylate [138], styrene-butadiene and other rubbers [139-141], nitrile rubber [142], natural rubbers [143,144], chlorinated natural rubber [145,146], polychloroprene [147], PVC [148-150], silicones [151,152], polycarbonates (PC) [153], styrene-isoprene copolymers [154], substituted PS [155], polypropylene carbonate [156], ethylene-vinyl acetate copolymer [157], Nylon 6,6 [158], polyisopropenyl cyclohexane-a-methylstyrene copolymers [195], cresol-novolac epoxy resins [160], polymeric flame retardants [161], poly(4-N-alkylstyrenes) [162], pol)winyl pyrrolidone [31,163], vinyl pyrrolidone-methacryloxysilicone copolymers [164], polybutylcyanoacrylate [165], polysulfide copolymers [1669], poly(diethyl-2-methacryloxy) ethyl phosphate [167, 168], ethane-carbon monoxide copolymers [169], polyetherimide [170], and bisphenol-A [171]. 

Diene Types The diene elastomers are based on polymers prepared from butadiene, isoprene, their derivatives and copolymers. The oldest elastomer, natural rubber (polyisoprene), is in this class (see Section 9.2). Polybutadiene, polychloroprene, styrene-butadiene rubber (SBR), and acrylonitrile-butadiene rubber (NBR) are also in this class. 

Aromatic amine antioxidants are also known as rubber antiaging agents they have the largest production quantity and are used mainly in rubber products. These antioxidants have low prices and remarkable antioxidant effects however, they could change the color of products, which limits their application in light colored and white goods. Significant aromatic amine antioxidants are diphenylamine, jo-phenylenediamine, quinoline, and their derivatives or polymers, and they can be used in natural rubber, styrene butadiene rubber (SBR), chloroprene rubber, and isoprene rubber. 

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