Polychloroprenes properties

Summarizing, the variations in the microstructure are responsible for significant changes in the polychloroprene properties. The main modifications produced in the polychloroprene chains affect its properties as follows ... 

Butyl polymers are about 8—10 times more resistant to air permeabiUty compared to natural mbber and have excellent resistance to heat and steam or water. This accounts for its use in gaskets and diaphragms for hot water and steam service. In addition, butyl mbber can be compounded to have low residence properties and has found use in high damping mounts for engines, motors, and similar devices. Halobutyl mbbers can be blended with natural mbber, polychloroprene, and EPDM to greatiy enhance theh permeabiUty resistance. 

Chloroprene Elastomers. Polychloroprene is a polymer of 2-chloro-l,3-butadiene. The elastomer is largely composed of the trans isomer. There are two basic polymer types the W-type and the G-type. G-types are made by using a sulfur-modified process W-types use no sulfur modification. As a result, G-types possess excellent processing and dynamic properties, and tend to be used in V-belts. However, they have poorer aging properties than W-types. The W-types tend to be used in appHcations requiring better aging, such as roUs and mechanical goods (see Elastomers, SYNTHETIC-POLYCm.OROPRENE). 

Neoprenes. Of the synthetic latices, a type that can be processed similarly to natural mbber latex and is adaptable to dipped product manufacture, is neoprene (polychloroprene). Neoprene latices exhibit poor initial wet gel strength, particularly in coagulant dipped work, but the end products can be made with high gum tensile strength, oil and aUphatic solvent resistance, good aging properties, and flame resistance. There are several types of neoprene latex, available at moderately high (ca 50 wt %) and medium soHds content. Differences in composition between the types include the polymer s microstmcture, eg, gel or sol, the type of stablizer, and the total soHds content (Table 22). 

Processing ndProperties. Neoprene has a variety of uses, both in latex and dry mbber form. The uses of the latex for dipping and coating have already been indicated. The dry mbber can be handled in the usual equipment, ie, mbber mills and Banbury mixers, to prepare various compounds. In addition to its excellent solvent resistance, polychloroprene is also much more resistant to oxidation or ozone attack than natural mbber. It is also more resistant to chemicals and has the additional property of flame resistance from the chlorine atoms. It exhibits good resiUence at room temperature, but has poor low temperature properties (crystallization). An interesting feature is its high density (1.23) resulting from the presence of chlorine in the chain this increases the price on a volume basis. 

The emulsion polymerization process enables considerable variation in the properties of polychloroprene, and provides an opportunity to tailor polymers for a wide variety of uses. 

Microstructure. Whereas the predominate stmcture of polychloroprene is the head to tail /n7 j -l,4-chloroprene unit (1), other stmctural units (2,3,4) are also present. The effects of these various stmctural units on the chemical and physical properties of the polymer have been determined. The high concentration of stmcture (1) is responsible for crystallization of polychloroprene and for the abiUty of the material to crystallize under stress. Stmcture (3) is quite important in providing a cure site for vulcanization, but on the other hand reduces the thermal stabiUty of the polymer. Stmctures (3),(4), and especially (2) limit crystallization of the polymer. 

The tendency of polychloroprene to crystallize enhances its value as an adhesive (97). The cured or uncured polymer can crystallize on stretching thereby increasing the strength of gum vulcaniza tes. Elastomers that caimot crystallize have poor gum vulcaniza te properties (98). 

Compound processibiUty is a key factor in the optimiza tion of new polychloroprene types. As a result, commercial compounds can be mixed, shaped, and cured by virtually all the methods used in the mbber industry. A typical polychloroprene compound includes a variety of additives designed to improve compound rheology, cure rate, and vulcanizate properties. 

Curing Systems. Polychloroprene can be cured with many combiaations of metallic oxides, organic accelerators, and retarders (114). The G family of polymers, containing residual thiuram disulfide, can be cured with metallic oxides alone, although certain properties, for example compression set, can be enhanced by addition of an organic accelerator. The W, T, and xanthate modified families require addition of an organic accelerator, often ia combination with a cure retarder, for practical cures. 

Since polychloroprene crystallizes under stress, fine particle size carbon black is not ordinarily needed or used to enhance tensile strength. More frequently, mineral fillers, for example clay, can be added to reduce cost. A light process oil, free of polycycHc aromatics, can be used to improve the flexibihty or hand of films. On the other hand, an ester plasticizer can be used to improve low temperature properties (161). 

Two propylene oxide elastomers have been commercialized, PO—AGE and ECH—PO—AGE. These polymers show excellent low temperature flexibihty and low gas permeabihty. After compounding, PO—AGE copolymer is highly resiUent, and shows excellent flex life and flexibiUty at extremely low temperatures (ca —65°C). It is slightly better than natural mbber in these characteristics. Resistance to oil, fuels, and solvents is moderate to poor. Wear resistance is also poor. Unlike natural mbber, PO—AGE is ozone resistant and resistant to aging at high temperatures. The properties of compounded ECH—PO—AGE he somewhere between those of ECH—EO copolymer and PO—AGE copolymer (22). As the ECH content of the terpolymer increases, fuel resistance increases while low temperature flexibihty decreases. Heat resistance is similar to ECH—EO fuel resistance is similar to polychloroprene. The uncured mbber is soluble in aromatic solvents and ketones. 

The diene rubbers, including polychloroprene, comprise some 90% of the total rubber market. This is due to their generally low cost, the suitability of many of them as tyre rubbers and their good mechanical properties. 

Both side groups and carbon-carbon double bonds can be incorporated into the polymer structure to produce highly resilient rubbers. Two typical examples are polyisoprene and polychloroprene rubbers. On the other hand, the incorporation of polar side groups into the rubber structure imparts a dipolar nature which provides oil resistance to these rubbers. Oil resistance is not found in rubber containing only carbon and hydrogen atoms (e.g. natural rubber). Increasing the number of polar substituents in the rubber usually increases density, reduces gas permeability, increases oil resistance and gives poorer low-temperature properties. 

The elastomers considered in this section have been selected considering the most commonly used in rubber base adhesives natural rubber butyl nibber and polyisobutylenes styrene-butadiene rubber nitrile rubber polychloroprene rubber (neoprene). Typical properties of these rubbers are shown in Table 2. 

Increase in the chain branching in the polychloroprene, reducing the stability in polymer viscosity and deteriorating the processing properties. 

Neoprene AF ( 963). It is a polychloroprene modified with methacrylic acid. Although it is a slow-crystallizing elastomer, the cohesive strength develops very rapidly and it has improved creep resistance at high temperature compared with Neoprene AC or AD. The improved properties of Neoprene AF are derived from the interaction between the carboxyl functionality with the metal oxides added in the solvent-borne polychloroprene adhesives. 

Solution and peel properties of polychloroprenes with fast crystallizing characteristics but different molecular weight... 

Neoprene XD. Developed in the 1980s, this polychloroprene family was prepared using special xanthogendisulphides as chain modifiers, offering improved processability and vulcanizate properties. In solution, these polychloroprenes show slow crystallization and high temperature resistance. 

New Neoprene M- and XD grades. These polychloroprenes were developed in the 1990s and combine low temperature flexibility, improved heat resistance and dynamic properties. 

Polychloroprene elastomer. Neoprene AC and AD are the most commonly used, mainly Neoprene AD because of its superior viscosity stability. For difficult-to-bond substrates, graft polymers Neoprene AD-G or AF) show better performance. For sprayable adhesives or high-viscosity mastics, the Neoprene AG offers excellent results. When specific properties (e.g. increase tack, improve wetting, increase peel strength) need to be met, blends of Neoprene AC or AD with Neoprene AG provide adequate performance. 

Properties of solvents commonly used in polychloroprene adhesives formulations [77]... 

It has to be kept in mind that the polymer properties desired in polychloroprene latex formulations may be totally different from those needed in dry grades. Polychloroprene latices generally exhibit lower contactability than dry polychloro-prenes because of the presence of residual soaps and salts, appreciable gel content and segregation of tackifier [79]. For this reason, the polychloroprene latices have usually medium to low crystallinity. 

The properties of the solvent-bome CR adhesives depend on the molecular weight, degree of branching and rate of crystallization of the polymer. The ability of polychloroprene adhesives to crystallize is unique as compared to other elastomers. The higher the crystallization rate, the faster the adhesive strength development. 

High-pressure lamination constitutes a large market for water-borne polychloroprene adhesives. The choice of the polymer has a high impact on end-use properties. 

Standard-grade PSAs are usually made from styrene-butadiene rubber (SBR), natural rubber, or blends thereof in solution. In addition to rubbers, polyacrylates, polymethylacrylates, polyfvinyl ethers), polychloroprene, and polyisobutenes are often components of the system ([198], pp. 25-39). These are often modified with phenolic resins, or resins based on rosin esters, coumarones, or hydrocarbons. Phenolic resins improve temperature resistance, solvent resistance, and cohesive strength of PSA ([196], pp. 276-278). Antioxidants and tackifiers are also essential components. Sometimes the tackifier will be a lower molecular weight component of the high polymer system. The phenolic resins may be standard resoles, alkyl phenolics, or terpene-phenolic systems ([198], pp. 25-39 and 80-81). Pressure-sensitive dispersions are normally comprised of special acrylic ester copolymers with resin modifiers. The high polymer base used determines adhesive and cohesive properties of the PSA. 

Lee [242] studied the dependence of the physico-mechanical properties of Wollastonite-filled polychloroprene rubber on the type of agent used to pre-treat the filler. The composition contained 26.9 part (weight) of the filler per 100 parts (weight) of the rubber (compositions CR-1100, CR-174, CR-151). The finishing agents were y-aminopropyl triethoxysilane (CR-1100 and CR-174) and vinyl triethoxysilane (CR-151). The mechanical properties of the compositions are listed in Table 7 below. The author proposed an empirical equation to relate the modulus with the equilibrium work of adhesion in the following form ... 

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