Polymer polyols graft polyethers

The utilisation of the high MW aminic polyether polyols in the synthesis of polymer polyols [graft polyether polyols and polyisocyanate polyaddition (PIPA) polyols] is presented in Chapter 6 [148, 151]. 

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. 

Modified polyether polyols have appeared in recent years, i.e., graft polyether polyols (polymer polyols, copolymer polyols) which were first developed by Union Carbide Corp. in the mid-1960 s. 

Graft Polyol Technology. Graft polyols (or polymer polyols) are prepared by grafting both acrylonitrile and styrene monomer or acrylonitrile alone to conventional polyether polyols. Graft polyols provide increased load-bearing ability as well as cell-opening, which prevent or minimize the formation of closed-cell foams, because closed-cell flexible foams readily shrink. 

Normally a 70/30 to 50/50 blend of a 4500-6500 EO-capped polyether triol with a polymer polyol is used, together with an 80 20 blend of TDI (80/20 isomer ratio) and polymeric MDI. Recently, higher-solids-content graft polyols, e.g., 30-50% solid polyols, have become available in the market. 

Shell developed a special line of polymer polyols based exclusively on styrene [11], the stabilisation of the resulting dispersion of polystyrene in liquid polyether being given by special NAD [8, 9, 32, 33] and of course not to the graft species, which in the case of polystyrene are practically absent. 

The structure (6.8) is another type of NAD formed in situ by transfer reaction with the tertiary amine type polyethers. Addition of a high molecular weight polyether initiated by an alkanolamine, ethylene diamine, N-methyl substituted propylene diamine, or N,N dimethyl dipropylene diamines in the polyether polyol used for grafting leads to the formation of very stable polymeric dispersions [37]. The solid fraction has particles of low median diameter (<1.5 pm). The resulting polymer polyols have low viscosities which give good stabilisation of the polymeric dispersion. 

The macromers used in the stabilisation of polymer dispersions are in fact polyether polyols with terminal double bonds, able to copolymerise with vinylic monomers (ACN, styrene) and to form graft species during the radical copolymerisation. The resulting graft polyether polyol, formed in situ by the copolymerisation process, is in fact a NAD ... 

MA can be used as comonomer together with the vinylic monomers (ternary copolymerisation ACN - styrene - MA) and the graft species is formed in situ by the reaction of the resulting copolymer ACN - styrene - MA with the polyether polyol, by its terminal hydroxyl groups. Another variant is to use a styrene - MA copolymer as NAD. This copolymer proved to be a very good NAD for high styrene content polymer dispersions in polyethers. Of course the real NAD is made by the reaction of a MA unit with the terminal hydroxyl group of the poly ether [57]. 

Generally, the nonreactive NAD is used in higher concentrations, than the macromers in graft polyether polyols synthesis, of around 10-15% compared to the final polymer polyol. 

The hydroxyl number of a polymer polyol is lower than the hydroxyl number of the initial polyether polyol used for grafting. The hydroxyl number decrease is a function of the polymer polyol solid content (generally the solid part has no hydroxyl groups). For the estimated hydroxyl number calculation at a known solid content, equation 6.17 is used ... 

Therefore, by grafting a polyether polyol with an OH of 36 mg KOH/g with 20% vinylic monomers, the theoretical hydroxyl number of the resulting polymer polyol is 28.8 mg KOH/g. 

PHD polymer polyols are a special class of filled polyols developed successfully by Bayer, PHD being the abbreviation of the German name polyharnstoff dispersion or polyurea dispersions [67-69]. PHD polyols contain organic urea, oligomeric or polymeric polyurea, finely dispersed in liquid polyether polyols [67-73]. The difference between PHD polyols and graft polyether polyols is the different nature of the solid polymer dispersed (it is a heterocatenary polymer - polyurea - instead of carbocatenary polymer) which is obtained by another synthetic procedure (polyaddition reaction between a diisocyanate and a diamine instead of radical polymerisation). The reaction between the diisocyanate and the diamine, takes place in situ (reaction 6.19), in liquid poly ether. The resultant polyurea being insoluble in polyether, precipitates in the form of very fine particles ... 

Usually the viscosity of PHD polymer polyols is higher than the viscosity of graft polyether polyols, at the same solids content. For example a graft polyether polyol, with a 20% solid fraction (copoly[ACN - styrene]), has a viscosity of 2000-3000 MPa-s at 25 °C, but a PHD polyol, with the same solids concentration has a viscosity of 3000-3500 MPa-s at 25 °C [10, 67-69]. This high viscosity is direct evidence of the intensive interaction, by secondary forces, between the polyurea filler and the continuous liquid polyether phase. 

As was the case for graft and PHD polymer polyols, by using PIPA polyols, an increase in hardness, tensile strength and tear strength of the resultant flexible PU foams was observed, as compared to the PU foams made with unfilled polyether polyols. 

In the practice, the most important polymer polyols are graft polyether polyols, PHD and PIPA polyols, but other good quality polymer dispersions in liquid polyethers have been created, which at this moment are not industrially important, such as ... 

These "polymer-polyols" are made by the in situ polymerization of vinyl monomers such as acrylonitrile (although grafting with other monomers has also been reported in a liquid polyol solution, e.g., polyether triol of molecular weight 3000) to give stable dispersions of the polymeric portion in the liquid polyol. Grafting is carried out with azobis(isobutyronitrile) or dibenzoyl peroxide as initiators at 80-90 °C. A polymer-polyol containing about 20% acrylonitrile appeared to be the best compromise between polyol viscosity and urethane foam properties (108). 

More recently, filled polyethers (so called polymer polyols ) have been introduced. These contain dispersed organic filler such as acrylonitrile-styrene copolymer or polyurea, some of which is grafted on to the polyether chain. Filled polyethers are used principally for flexible foams of high resilience. 

Many of the same basic raw materials shown in Table II for RIM fascia systems are also used in high modulus systems. Additionally, however, polyether polyols "filled" with dispersions of polyureas are used( 2) These are the so-called PHD polyols developed by Bayer AG, the PHD being an abbreviation for Polyharnstoff-Dispersion. These polyols provide the same "filler" effect as the graft polyols (Table II) for increasing the modulus of the polymer without increasing the amount of extender. 

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