Monomeric plasticizers

Polarity Parameter. Despite their appareat simplicity, these parameters, ( ), show a good correlatioa with plasticizer activity for nonpolymeric plasticizers (10). The parameter is defiaed 2ls (j) = [M A j Po)]/1000 where M = molar mass of plasticizer, = number of carboa atoms ia the plasticizer excluding aromatic and carboxyHc acid carbon atoms, and Pg — number of polar (eg, carbonyl) groups present. The 1000 factor is used to produce values of convenient magnitude. Polarity parameters provide useful predictions of the activity of monomeric plasticizers, but are not able to compare activity of plasticizers from different families. 

Diesters. Many of the diester derivatives are commercially important. The diesters are important plasticizers, polymer intermediates, and synthetic lubricants. The diesters of azelaic and sebacic acids are useflil as monomeric plasticizing agents these perform weU at low temperatures and are less water-soluble and less volatile than are diesters of adipic acid. Azelate diesters, eg, di- -hexyl, di(2-ethylhexyl), and dibutyl, are useflil plasticizing agents for poly(vinyl chloride), synthetic mbbers, nitroceUulose, and other derivatized ceUuloses (104). The di-hexyl azelates and dibutyl sebacate are sanctioned by the U.S. Food and Dmg Administration for use in poly(vinyl chloride) films and in other plastics with direct contact to food. The di(2-ethylhexyl) and dibenzyl sebacates are also valuable plasticizers. Monomeric plasticizers have also been prepared from other diacids, notably dodecanedioic, brassyflc, and 8-eth5lhexadecanedioic (88), but these have not enjoyed the commercialization of the sebacic and azelaic diesters. 

For the same reasons cited above, the linear undecyl and dodecyl phthalates were compared to DIDP and DTDP.. Linear undecyl phthalate (DLllP) demonstrates some rather impressive performance characteristics in relation to the materials against which it was compared. It has excellent permanence for a monomeric plasticizer, very good low temperature properties, and outstanding resistance to soapy water. The same statements are generally true of DL12P, except that it was the least compatible of the plasticizers tested and probably would be used best in combinations with more compatible plasticizers. 

Migration of ions through the plasticizer is frequently considered to be a function of the mobility of the plasticizer itself (2,5). In many electrical applications, where fugitive monomeric plasticizers like DOP can cause damage, they can be replaced by non-fugitive polymeric plasticizers such as viscous liquid polyesters. Comparison of DOP vs. a typical polymeric plasticizer, Rohm Haas Paraplex 0-25 poly (propylene sebacate), showed no significant improvement in volume resistivity (Table VI), particularly when its lower plasticizing efficiency was considered. Thus plasticizer mobilitv alone does not help us explain volume resistivity (5). 

PRACTICAL GUIDE TO THE IDENTIFICATION OF MONOMERIC PLASTICIZERS IN FLEXIBLE PVC COMPOUNDS... 

Used in conjunction with a monomeric plasticizer and a metal oxide to make an inherently hydrophobic material more hydrophilic. Commonly used in toys and medical equipment. 

Monoplex . [CJ. Hall] Adipates, sebacaies, tallaies monomeric plasticizers, stabilizers, lubricants fivPVC... 

Beilstein Handbook Reference) AI3-09505 BRN 1726635 2-Butenedioic acid (2E)-, dibutyl ester 2-Butenedioic acid, dibulyl ester, (E)- Butyl fumarate Dibutyl fumarate Dibutylester kyseliny fumarove EINECS 203-327-9 Fumaric acid, di-n-butyl ester Fumaric acid, dibutyl ester NSC 140 RC Comonomer DBF Stafex DBF Staflex DBF. Used In monomeric plasticizers copolymers and as a chemical intermediate. Liquid mp = -13.5 bp n 285 , bp4 " 150° d = 0.9775 insoluble in HaO, soluble in CHCI3, MeaCO. AC Ind. Inc. Monomer-Polymer Dajac Penta Mfg. Unitex. 203-327-9... 

Beilstein Handbook Reference) AI3-00393 Bis(n-butyl) sebacate BRN 1798308 Butyl sebacate Decanedioic acid, dibutyl ester Dl-n-butyl sebacate Dibutyl 1,8-octanedicarboxylate Dibu l decanedioate Dibutyl sebacate Oibutyi sebacinate Dibutylester kyseliny sebakove EINECS 203-672-5 FEMA No. 2373 HSDB 309 Kodaflex DBS Monoplex DBS NSC 3893 Plasthall DBS Polycizer DBS PX 404 Reomol DBS Sebacic acid, dibutyl ester Staflex DBS Uniflex DBS. Monomeric plasticizer for plastics and rubber (cellulosics, PVC food wraps, nitrite and neoprene rubbers). Used as an excipient in various pharmaceutical coaling formulations. Viscous liquid mp = -10° bp = 344.5°, bp3 = 180° d = 0.9405 insoluble in H2O, soluble in Et20, CQ4. Hall C.P. Union Camp. 

Bellstein Handbook Reference) Adimoll DH Adipic acid, dihexyl ester AI3-07963 BRN 1798668 Di-n-hexyl adipate Dihexyl adipate Dihexyl hexanedioate EINECS 203-757-7 Hexanedioic xid, dihexyl ester Di-n-hexyl hexanedioate Plasticizer dihexyl adipate. Monomeric plasticizer. Bayer AG. 

Adimoii DN Adipic acid, diisononyi ester CCRIS 2004 Diisononyl adipate Diisononyl hexanedioate EINECS 251-646-7 Hexanedioic acid, diisononyl ester PX-209. A reagent grade, monomeric plasticizer. Aristech Bayer AG. 

Uniflex . [Union Camp] Polymeric or monomeric plasticizers, processing aid, lubricant esters for nibbos, thenno-plastics, fiber lubricants, metalwtnking oils. 

In practice, esters from adipic, sebacic, and phthalic acid are frequently used as polyester plasticizers. The value of n may vary from 3 to 40 for adipates and from 3 to 35 for sebacates. Polyester plasticizers are seldom used alone. They are used in combination with monomeric plasticizers to reduce the volatility of the mixed solvents. They offer a higher resistance to plasticizer migration and to extract by kerosene, oils, water, and surfactants. Polyester plasticizers are used specially in PVC-based blends and in nitrocellulose varnishes. 

Both monomeric and polymeric plasticizers are suitable for plasticization. Practically all monomeric plasticizers for PVC can be used. Suitable polymeric plasticizers include polyadipates, chlorinated paraffins, carbamide resins, and epoxides. Vinyl chloride copolymers are compatible with most conventional pigments and extenders. Despite their high intrinsic stability, paints based on vinyl chloride copolymers have to be stabilized against dehydrochlorination in the presence of heat and/or UV radiation for some applications. Epoxy compounds are often sufficient for thermal stabilization. 

The above table shows that if the monomeric plasticizer (even having a very high molecular weight) is used (formulation D), it generates high emission of gaseous substances. But these emissions can be substantially reduced if blending is used instead of plasticization by classical plasticizers, as can be seen from formulations A-C. 

Similarly to the production process of polyblends, the macromolecules are physically mixed with another substance for external plasticization. By contrast with polyblends, however, low molecular substances (monomeric plasticizers with molar masses of 350-600 g mol ) or oligomers (so-called polymeric plasticizers with molar masses of 2,000-4,000 g mol ), are used for external plasticization. 

Features Polymeric better resistance to oils, fats, greases than monomeric plasticizers... 

Uses Modifier, monomeric plasticizer for PVC, PVAc, paints comonomer for vinyl resins, copolymers intermediate Manuf./Dlstrlb. ChemService DSM Fine Chems. Austria Lenape Ind. Monomer-Polymer Dajac Labs NOF Pechiney Chems. Div. Penta Mfg. Unitex... 

Purity of monomeric plasticizers can be determined with a high precision using gas chromatography. Flame ionization or thermal conductivity detectors are used. Capillary... 

ASTM D3465-00 Standard Test Method for Purity of Monomeric Plasticizers by Gas Chromatography... 

The main drawback of monomeric plasticizers is their tendency to migrate from the polymer or to be leached out by contacting media. In anticipation of permanence problems caused by monomeric plasticizers, oligomeric... 

Di(2-ethylhexyl) azelate n. (dioctyl azelate, DOZ) (CH2)7[C00CH2-CH(C2H5) QH9]2. a plasticizer for vinyl chloride polymers and copolymers. It is one of the most compatible of the low-temperature, monomeric plasticizers, has low volatility, and imparts low extractability by water and soapy water. This plasticizer has been approved for food-contact use. 

Octyl epoxy tallate n. A monomeric plasticizer and heat and light stabilizer for vinyls and cellulosics. It imparts good low-temperature flexibility, has low volatility, and is used primarily in coated fabrics, garden hose, film and sheeting, and slush-molded parts. 

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