Copolymers of isobutylene

Figure 3.4 is a display of data which confirms the predictions of Eq. (3.46). For T and a constant-the case in these experiments—Eq. (3.46) predicts that a plot of Uj versus 1 /M should yield a straight line with an intercept proportional to 1/M(,. The elastomers on which the experiments were conducted were copolymers of isobutylene containing a small amount of isoprene. The polymers... 

Butyl mbber, a copolymer of isobutjiene with 0.5—2.5% isoprene to make vulcanization possible, is the most important commercial polymer made by cationic polymerization (see Elastomers, synthetic-butyl rubber). The polymerization is initiated by water in conjunction with AlCl and carried out at low temperature (—90 to —100° C) to prevent chain transfer that limits the molecular weight (1). Another important commercial appHcation of cationic polymerization is the manufacture of polybutenes, low molecular weight copolymers of isobutylene and a smaller amount of other butenes (1) used in adhesives, sealants, lubricants, viscosity improvers, etc. 

Polymers account for about 3—4% of the total butylene consumption and about 30% of nonfuels use. Homopolymerization of butylene isomers is relatively unimportant commercially. Only stereoregular poly(l-butene) [9003-29-6] and a small volume of polyisobutylene [25038-49-7] are produced in this manner. High molecular weight polyisobutylenes have found limited use because they cannot be vulcanized. To overcome this deficiency a butyl mbber copolymer of isobutylene with isoprene has been developed. Low molecular weight viscous Hquid polymers of isobutylene are not manufactured because of the high price of purified isobutylene. Copolymerization from relatively inexpensive refinery butane—butylene fractions containing all the butylene isomers yields a range of viscous polymers that satisfy most commercial needs (see Olefin polymers Elastomers, synthetic-butylrubber). 

Butyl Rubber. Butyl mbber was the first low unsaturation elastomer, and was developed ia the United States before World War II by the Standard Oil Co. (now Exxon Chemical). It is a copolymer of isobutylene and isoprene, with just enough of the latter to provide cross-linking sites for sulfur vulcanization. Its molecular stmcture is depicted ia Table 1. 

Monomers for manufacture of butyl mbber are 2-methylpropene [115-11-7] (isobutylene) and 2-methyl-l.3-butadiene [78-79-5] (isoprene) (see Olefins). Polybutenes are copolymers of isobutylene and / -butenes from mixed-C olefin-containing streams. For the production of high mol wt butyl mbber, isobutylene must be of >99.5 wt % purity, and isoprene of >98 wt % purity is used. Water and oxygenated organic compounds iaterfere with the cationic polymerization mechanism, and are minimized by feed purification systems. 

Butyl rubber (BR) and polyisobutylene (PIB) are widely used in adhesives as primary elastomeric binders and as tackifiers and modifiers. The main difference between these polymers is that butyl is a copolymer of isobutylene with a minor amount of isoprene (which introduces unsaturation due to carbon-carbon double bonds), while polyisobutylene is a homopolymer. 

Butyl rubber is a copolymer of isobutylene (97.5%) and isoprene (2.5%). The polymerization is carried out at low temperature (below... 

Standard butyl rubber, which is a copolymer of isobutylene with about 2% of isoprene vulcanises in the same manner as natural rubber but, as it only contains a small proportion of polyisoprene, the cross-link percentage is much reduced. It is therefore not possible to make ebonite from a butyl rubber. The same vulcanisation chemistry, with some modifications, applies to ethylene-propylene terpolymers and brominated butyl rubber. 

Yijin X. and Caiyaun P., Block and star-hlock copolymers by mechanism transformation. 3. S-(PTHF-PSt)4 and S-(PTHF-PSt-PMMA)4 from living CROP to ATRP, Macromolecules, 33, 4750, 2000. Feldthusen J., Ivan B., and Mueller A.H.E., Synthesis of linear and star-shaped block copolymers of isobutylene and methacrylates hy combination of living cationic and anionic polymerizations. Macromolecules, 31, 578, 1998. 

The next criterion was the selection of materials that would yield the desired mechanical properties. Butyl elastomer (HR), a copolymer of isobutylene with a small amount of isoprene, has outstanding low-temperature properties and very high damping, but has very high creep without cross-linking." It was theorized that a blend of SIBS TPE and butyl elastomer, filled to achieve the required minimum density of 2.4 g cm, would be a promising composite for less-lethal ammu-... 

Isobutylene-based elastomers include HR, the copolymer of isobutylene and isoprene, halogenated HR, star-branched versions of these polymers, and the terpolymer isobutylene-p-methylene styrene-bromo-p-methyl styrene (BIMS). A number of recent reviews on isobutylene-based elastomers are available [33-35]. 

Butyl rubber (a copolymer of isobutylene and 1-3 mole per cent isoprene) and its halogenated derivatives have unsaturation in the carbon-carbon backbone and consequently do not have as good aging properties as EPDM. There are also reports (9-12) that ozone-resistant butyl rubber with a high degree of unsaturation can be prepared by copolymerization of isobutylene with either cyclopentadiene or 9-pinene. 

The most industrially significant polymerizations involving the cationic chain growth mechanism are the various polymerizations and copolymerizations of isobutylene. In fact, about 500 million pounds of butyl rubber, a copolymer of isobutylene with small amounts of isoprene, are produced annually in the United States via cationic polymerization [126]. The necessity of using toxic chlorinated hydrocarbon solvents such as dichloromethane or methyl chloride as well as the need to conduct these polymerizations at very low temperatures constitute two major drawbacks to the current industrial method for polymerizing isobutylene which may be solved through the use of C02 as the continuous phase. 

Buna-S Elastomeric copolymer of butadiene and styrene, butyl rubber Elastomeric copolymer of isobutylene and isoprene. 

Similarly, hydrogenation of the copolymer of isobutylene and propene formed in the presence of dihydroxyfluorboric acid at 15-20° yielded a liquid product, 67% of which was heptane (Brooks, 43). At least 95% of the heptane was 2,3-dimethylpentane. In the absence of isobutylene, propene does not undergo polymerization when treated with hydroxyfluo-boric acid at 0-40°. 

Butyl rubber (BR) is a copolymer of isobutylene with small amounts of isoprene produced by aluminum chloride initiated polymerization. About 1 billion pounds of butyl mbber are... 

For (a), hydroxypropyl cellulose (HPC) (6-8), poly(vinyl pyrrolidone) (PVP) (9,10), poly(acrylic acid) (PAA) (9), and poly(dimethyl siloxane) (PDMS) (11) are usually employed. Ober et al. reported that the copolymers of isobutylene/isoprene and various methacrylates, which have weak polarity, are appropriate stabilizers for... 

Cure Systems of Butyl Rubber and EPDM. Nonhalogenated butyl rubber is a copolymer of isobutylene with a small percentage of isoprene which provides cross-linking sites. Because the level of unsaturation is low relative to natural rubber or SBR, cure system design generally requires higher levels of fast accelerators such as the dithiocarbamates. Examples of typical butyl mbber cure systems, their attributes, and principal applications have been reviewed (26). Use of conventional and semi-EV techniques can be used in butyl rubber as shown in Table 7 (21). 

The copolymer of isobutylene with a few percent isoprenc (butyl rubber) can be cured to produce an ozone-resistant elastomer with low permeability to oxygen and nitrogen. Butyl rubber has a Tt of — 70 C a refractive index of 1.5081, and a coefficient of linear expansion of 5.7 X 10 cm/cxn C. Chloro and bromo butyl rubber are more resistant to the permeation of oxygen and nitrogen than butyl rubber. 

To this category belong homopolymers of polyisobutylene, copolymers of isobutylene and isoprene (butyl rubber), chlorobutyl, and bromobutyl. All these have been produced commercially for decades. 

J.M. Downward, USP 3018201 (1962) CA 56, 13153(1962) (Gelatinous expl compns afe provided by mixts contg expls such.as NC, NS or RDX and a nonexplosive gel consisting of water-irwsol petroleum hydrocarbons such as a vulcanized copolymer of isobutylene and isoprene)... 

Standard Oil Co. claims the use of polyisobutylene as a plasticizer for polyvinyl acetate. Copolymers of isobutylene with vinyl ethers and other monomers are mentioned in several patents. For synthetic rubbers, oligomers of butadiene are claimed. Rubberlike polyolefins (10 to 50% is sufficient) are used extensively for plasticizing phenolic resins to increase impact strength. 

Butyl rubber - A copolymer of isobutylene and isoprene rubber ASTM designation HR butyl rubber is the common name for such materials. 

Known as MR. butyl rubber is a copolymer of isobutylene and isoprene. The elastomers contain only (1.5 2.5 mole 9r of isoprene. This is introduced to effect sufficient unsaturatinn to make the rubber vulcanizublc. Polymerizations are usually earned out at low temperature (-80 to -1(KJ C) with methyl chloride as solvent. Anhydrous aluminum chloride and a trace of water serve as catalyst. 

RUBBER (Synthetic). Any of a group of manufactured elastomers that approximate one or more of the properties of natural rubber. Some of these aie sodium polysulfide ( Thiokol ). polychloiopiene (neoprene), butadiene-styrene copolymers (SBR), acrylonitrilebutadiene copolymers (nitril rubber), ethvlenepropylene-diene (EPDM) rubbers, synthetic poly-isoprene ( Coral, Natsyn ), butyl rubber (copolymer of isobutylene and isoprene), polyacrylonitrile ( Hycar ). silicone (polysiloranei. epichlorohy-drin, polyurethane ( Vulkollan ). 

Poly(isobutylene) dicarboxylic acid was prepared by oxidation of the copolymer of isobutylene with a diene 53,54). The most efficient oxidizing agent was the system KMn04-periodic acid. Oxidation of a copolymer of isobutylene and 2,3-dimethyl-butadiene afforded a polymeric bis-ketone54). 

Butyl rubber is one of the older synthetic rubbers, having been developed in 1937. Because of the saturated nature of a polyolefin elastomer, the commercial polymer is actually a copolymer of isobutylene and isoprene. The isoprene is added to provide cure sites. In addition, halogenated (bromo or chloro) derivatives are available. 

The importance of isobutylene in the petrochemical industry is well recognized. Isobutylene is used on a large scale for the production of (i) methacrolein by direct oxidation, (ii) polyisobutylene by polymerization, (iii) synthetic rubber (a copolymer of isobutylene and isoprene), and (iv) methyl tert-butyl ether (MTBE, a gasoline octane-number enhancer) by reaction with methanol. 

Several copolymers of olefins with longer chain are used in practice. Among these, butyl rubber is probably the most commonly utilized. This material is a copolymer of isobutylene with small amounts of isoprene (1-6% wt). The amount of isoprene determines the extent of crosslinking. Pyrolysis of butyl rubber generates mainly products similar to those found in the pyrolysis of poly(isobutylene) including monomer, dimer, up to hexamers, depending on the pyrolysis temperature [135-137]. Besides the... 

The most important of the commercial cationic copolymers is butyl rubber prepared from isobutylene and isoprene. Because of its very low air permeability, butyl rubber finds extensive use in tire inner tubes and protective clothing. It is manufactured by low-temperature (— 100°C) copolymerization of about 97% isobutylene and 3% isoprene in chlorocarbon solvents with AICI3 coinitiator (see Table 8.5). More recently, an ozone-resistant copolymer of isobutylene and cyclopentadiene has been marketed. 

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