Polyether-polyols

FIGURE 17.14 2D separation of PEO-g-PVA copolymer 2, first dimension LCCC, second dimension SEC (reprinted from Gutzler et al., 2005, with permission of Wiley-VCH Publishers, Germany). (See color plate.) 

As can be seen, there are significant differences between copolymers 1 and 2. Copolymer 1 having a high PEO-to-PVA ratio exhibits a quite broad distribution with regard to chemical composition and a significant amount of nongrafted PEO. In contrast, copolymer 2 having a low PEO-to-PVA ratio does not contain free PEO. 

To obtain an even better separation, SEC was performed in a second dimension following the LCCC analysis. As has been described previously, the resolution of a 2D experiment may be significantly higher as compared to the single chromatographic separations. A typical experimental result is shown in Fig. 17.14 (Gutzler et al., 2005). 

The comparison of the 2D plot of a graft copolymer with the 2D plot of the precursor PEO shows clearly that the graft copolymer sample does not contain any free PEO. This result was also confirmed by MALDI-TOF mass spectrometry. Next to the requirement of being PEO free, the PEO-g-PVA copolymers showed a good combination of film-forming properties, a fast dissolution, and a low solution viscosity in water. The phase separated morphology, as demonstrated by TEM, DSC, DMTA, and WAXS experiments, provided the PEO-g-PVA copolymers with relatively constant mechanical properties. 

Statistical and block copolymers based on ethylene oxide (EO) and propylene oxide (PO) are important precursors of polyurethanes. Their detailed chemical structure, that is, the chemical composition, block length, and molar mass of the individual blocks may be decisive for the properties of the final product. For triblock copolymers HO (EO) (PO)m(EO) OH, the detailed analysis relates to the determination of the total molar mass and the degrees of polymerization of the inner PPO block (m) and the outer PEO blocks (n). 

---

Hydroxyl Number. The molecular weight of polyether polyols for urethanes is usually expressed as its hydroxyl number or percent hydroxyl. When KOH (56,100 meg/mol) is the base, the hydroxyl number is defined as 56,100/equivalent weight (eq wt). Writing the equation as eq wt = 56,100/OH No. allows one to calculate the equivalents of polyol used in a urethane formulation, and then the amount of isocyanate required. The molecular weight can be calculated from these equations if the fiinctionahty, is known mol wt = / eq wt. 

The hydroxyl number can be deterrnined in a number of ways such as acetylation, phthalation, reaction with phenyl isocyanate, and ir and nmr methods. An imidazole-catalyzed phthalation has been used to measure the hydroxyl number for a number of commercial polyether polyols and compared (favorably) to ASTM D2849 (uncatalyzed phthalation) (99). The uncatalyzed method requires two hours at 98°C compared to 15 minutes at the same temperature. 

The tendency of aliphatic ethers toward oxidation requires the use of antioxidants such as hindered phenoHcs (eg, BHT), secondary aromatic amines, and phosphites. This is especially tme in polyether polyols used in making polyurethanes (PUR) because they may become discolored and the increase in acid number affects PUR production. The antioxidants also reduce oxidation during PUR production where the temperature could reach 230°C. A number of new antioxidant products and combinations have become available (115,120,124—139) (see Antioxidants). 

L. B. Barry and M. C. Richardson, "Novel AO System for Polyether Polyol Stabilization," 33rdMnnualPolyurethane Technical Marketing Conference, Odando, Fla., Sept. 30—Oct. 3, 1990. 

R. A. Hill, "New Antioxidant Package for Polyether Polyols, with Reduced Fogging Behaviour," 34thMnnualPolyurethane Technical Marketing Conference, New Odeans, La., Oct. 21—24,1992. 

TDA-derived polyols are made by alkoxylation. Polypropylene oxide adducts of I DA (14) and TDA-initiated polyether polyols (13,15) are used in rigid polyurethane foams and continue to be included in new formulations (62) as well as older appHcations. 

Propylene oxide [75-56-9] (methyloxirane, 1,2-epoxypropane) is a significant organic chemical used primarily as a reaction intermediate for production of polyether polyols, propylene glycol, alkanolamines (qv), glycol ethers, and many other useful products (see Glycols). Propylene oxide was first prepared in 1861 by Oser and first polymerized by Levene and Walti in 1927 (1). Propylene oxide is manufactured by two basic processes the traditional chlorohydrin process (see Chlorohydrins) and the hydroperoxide process, where either / fZ-butanol (see Butyl alcohols) or styrene (qv) is a co-product. Research continues in an effort to develop a direct oxidation process to be used commercially. 

Polymerization to Polyether Polyols. The addition polymerization of propylene oxide to form polyether polyols is very important commercially. Polyols are made by addition of epoxides to initiators, ie, compounds that contain an active hydrogen, such as alcohols or amines. The polymerization occurs with either anionic (base) or cationic (acidic) catalysis. The base catalysis is preferred commercially (25,27). 

Ammonia, and Amines. Isopropanolamine is the product of propylene oxide and ammonia ia the presence of water (see Alkanolamines). Propylene oxide reacts with isopropanolamine or other primary or secondary amines to produce A/- and A/,A/-disubstituted isopropanolamines. Propylene oxide further reacts with the hydroxyl group of the alkanolamines to form polyether polyol derivatives of tertiary amines (50), or of secondary amines ia the presence of a strong base catalyst (51). 

Propylene oxide has found use in the preparation of polyether polyols from recycled poly(ethylene terephthalate) (264), haUde removal from amine salts via halohydrin formation (265), preparation of flame retardants (266), alkoxylation of amines (267,268), modification of catalysts (269), and preparation of cellulose ethers (270,271). 

Polymerization Solvent. Sulfolane can be used alone or in combination with a cosolvent as a polymerization solvent for polyureas, polysulfones, polysUoxanes, polyether polyols, polybenzimidazoles, polyphenylene ethers, poly(l,4-benzamide) (poly(imino-l,4-phenylenecarbonyl)), sUylated poly(amides), poly(arylene ether ketones), polythioamides, and poly(vinylnaphthalene/fumaronitrile) initiated by laser (134—144). Advantages of using sulfolane as a polymerization solvent include increased polymerization rate, ease of polymer purification, better solubilizing characteristics, and improved thermal stabUity. The increased polymerization rate has been attributed not only to an increase in the reaction temperature because of the higher boiling point of sulfolane, but also to a decrease in the activation energy of polymerization as a result of the contribution from the sulfonic group of the solvent. 

Polyether Polyols. Polyether polyols are addition products derived from cyclic ethers (Table 4). The alkylene oxide polymerisation is usually initiated by alkah hydroxides, especially potassium hydroxide. In the base-catalysed polymerisation of propylene oxide, some rearrangement occurs to give aHyl alcohol. Further reaction of aHyl alcohol with propylene oxide produces a monofunctional alcohol. Therefore, polyether polyols derived from propylene oxide are not truly diftmctional. By using sine hexacyano cobaltate as catalyst, a more diftmctional polyol is obtained (20). Olin has introduced the diftmctional polyether polyols under the trade name POLY-L. Trichlorobutylene oxide-derived polyether polyols are useful as reactive fire retardants. Poly(tetramethylene glycol) (PTMG) is produced in the acid-catalysed homopolymerisation of tetrahydrofuran. Copolymers derived from tetrahydrofuran and ethylene oxide are also produced. 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

Polyester Polyols. Initially polyester polyols were the preferred raw materials for polyurethanes, but in the 1990s the less expensive polyether polyols dominate the polyurethane market. Inexpensive aromatic polyester polyols have been introduced for rigid foam appHcations. These are obtained from residues of terephthaHc acid production or by transesterification of dimethyl terephthalate (DMT) or poly(ethylene terephthalate) (PET) scrap with glycols. 

Most flexible foams produced are based on polyether polyols ca 8—10% (15—20% in Europe) of the total production is based on polyester polyols. Elexible polyether foams have excellent cushioning properties, are flexible over a wide range of temperatures, and can resist fatigue, aging, chemicals, and mold growth. Polyester-based foams are superior in resistance to dry cleaning and can be flame-bonded to textiles. 

In more recent years, molded flexible foam products are becoming more popular. The bulk of the molded flexible urethane foam is employed in the transportation industry, where it is highly suitable for the manufacture of seat cushions, back cushions, and bucket-seat padding. TDI prepolymers were used in flexible foam mol ding ia conjunction with polyether polyols. The introduction of organotin catalysts and efficient siHcone surfactants faciHtates one-shot foam mol ding, which is the most economical production method. 

Semiflexible molded polyurethane foams are used in other automotive appHcations, such as instmment panels, dashboards, arm rests, head rests, door liners, and vibrational control devices. An important property of semiflexible foam is low resiHency and low elasticity, which results in a slow rate of recovery after deflection. The isocyanate used in the manufacture of semiflexible foams is PMDI, sometimes used in combination with TDI or TDI prepolymers. Both polyester as well as polyether polyols are used in the production of these water-blown foams. Sometimes integral skin molded foams are produced. 

Polyurethane sealant formulations use TDI or MDI prepolymers made from polyether polyols. The sealants contain 30—50% of the prepolymer the remainder consists of pigments, fiUers, plastici2ers, adhesion promoters, and other additives. The curing of the sealant is conducted with atmospheric moisture. One-component windshield sealants utili2e diethyl malonate-blocked MDI prepolymers (46). Several polyurethane hybrid systems, containing epoxies, siUcones, or polysulfide, are also used. 

Other polyamine derivatives are used to break the oil/water emulsions produced at times by petroleum wells. Materials such as polyether polyols prepared by reaction of EDA with propylene and ethylene oxides (309) the products derived from various ethyleneamines reacting with isocyanate-capped polyols and quaternized with dimethyl sulfate (310) and mixtures of PEHA with oxyalkylated alkylphenol—formaldehyde resins (311) have been used. 

Both the Henecke process and the variations described above are today widely used in conjunction with polyether polyols, discussed in the next three sections. 

Most moisture-curing liquid adhesives utilize poly(oxypropylene) (PPG) polyols, as shown above. These raw materials produce among the lowest-viscosity prepolymers but may not have sufficient modulus at higher temperatures for some applications. A certain percentage of polyester polyols may also be utilized to boost performance, but these may cause a large increase in viscosity, and so they are more often used in conjunction with polyether polyols to provide a high-performance adhesive with workable viscosities. Poly(butadiene) polyols may be utilized for specific adhesion characteristics. 

Polyester polyols account for only ca. 10% of the total polyol market, which is dominated by polyether polyols such as hydroxy-terminated polyoxyethylene or polyoxypropylene. Polyester polyols are preferred for applications where better mechanical properties, wear resistance, and UV stability are required. The largest application of polyester polyols is flexible specialty polyurethane foam in the furniture, packaging, and automotive industries. Polyester polyols are also used for nonfoam applications such as coatings, paints, sealants, and adhesives 47... 

---