Unsaturated polyurethanes

Smith et al. (179) described the preparation of a hard and adherent coating by irradiation of an unsaturated polyurethane-polycaprolactone resin. 

One of the developments in the field of PSAs is the category of UV-crosslinkable, solvent-free, low-viscosity acrylic PSAs systems. These systems contain unsaturated polyurethanes and multifunctional acrylates in contrast to other PSA systems comprising acrylic polyester and photoreactive acrylic hot melts. They are likely to have significant market potential based on the degree of cohesion achieved (measured according to the self-adhesive failure temperature (°C)). 

Multifunctional acrylates, unsaturated low-viscosity acrylic polyesters, and unsaturated polyurethanes or their mixtures only permit the formulation of solvent-free, photoreactive A-PSAs with desired viscosity (Figure 4.10). Data presented here is taken from a study, which, was done with three various UV-reactive diluents the selection of reactive diluents was made based on their solubility, photoreactivity, UV crosslinkability, and, if available, glass-transition temperature contribution. 

Other coating systems contain cationically modified copolymers obtained by polymerization of acrylic monomers in presence of unsaturated polyurethane macromonomer [22], and water-dilutable dispersions of cationically modified and urethane modified methacrylic copolymers obtained by solution polymerization [23]. 

Polyols. Several important polyhydric alcohols or polyols are made from formaldehyde. The principal ones include pentaerythritol, made from acetaldehyde and formaldehyde trimethylolpropane, made from -butyraldehyde and formaldehyde and neopentyl glycol, made from isobutyraldehyde and formaldehyde. These polyols find use in the alkyd resin (qv) and synthetic lubricants markets. Pentaerythritol [115-77-5] is also used to produce rosin/tall oil esters and explosives (pentaerythritol tetranitrate). Trimethylolpropane [77-99-6] is also used in urethane coatings, polyurethane foams, and multiftmctional monomers. Neopentyl glycol [126-30-7] finds use in plastics produced from unsaturated polyester resins and in coatings based on saturated polyesters. 

Trimethyl-l,3-pentanediol (7) is a white, crystalline soHd. It is used in surface coating and unsaturated polyester resins. It also appears promising as an intermediate for synthetic lubricants and polyurethane elastomers and foams. 

The unsaturation present at the end of the polyether chain acts as a chain terminator ia the polyurethane reaction and reduces some of the desired physical properties. Much work has been done ia iadustry to reduce unsaturation while continuing to use the same reactors and hoi ding down the cost. In a study (102) usiag 18-crown-6 ether with potassium hydroxide to polymerise PO, a rate enhancement of approximately 10 was found at 110°C and slightly higher at lower temperature. The activation energy for this process was found to be 65 kj/mol (mol ratio, r = 1.5 crown ether/KOH) compared to 78 kj/mol for the KOH-catalysed polymerisation of PO. It was also feasible to prepare a PPO with 10, 000 having narrow distribution at 40°C with added crown ether (r = 1.5) (103). The polymerisation rate under these conditions is about the same as that without crown ether at 80°C. 

A hst of polyol producers is shown in Table 6. Each producer has a varied line of PPO and EOPO copolymers for polyurethane use. Polyols are usually produced in a semibatch mode in stainless steel autoclaves using basic catalysis. Autoclaves in use range from one gallon (3.785 L) size in research faciUties to 20,000 gallon (75.7 m ) commercial vessels. In semibatch operation, starter and catalyst are charged to the reactor and the water formed is removed under vacuum. Sometimes an intermediate is made and stored because a 30—100 dilution of starter with PO would require an extraordinary reactor to provide adequate stirring. PO and/or EO are added continuously until the desired OH No. is reached the reaction is stopped and the catalyst is removed. A uniform addition rate and temperature profile is required to keep unsaturation the same from batch to batch. The KOH catalyst can be removed by absorbent treatment (140), extraction into water (141), neutralization and/or crystallization of the salt (142—147), and ion exchange (148—150). 

A. T. Chen, and co-workers, "Comparison of the Dynamic Properties of Polyurethane Elastomers Based on Low Unsaturation Polyoxypropylene Glycols and Poly(tetramethylene oxide) Glycols," Polyurethanes World Congress 1993, Vancouver, B.C., Canada, Oct. 10—13,1993. 

Propylene oxide (qv) uses include manufacture of polyurethanes, unsaturated polyester, propylene glycols (qv) and polyethers, and propan o1 amines (see Alkanolamnes Glycols Polyethers Polyesters, unsaturated Urethane polyt rs). 

Polymers. The molecular weights of polymers used in high energy electron radiation-curable coating systems are ca 1,000—25,000 and the polymers usually contain acryUc, methacrylic, or fumaric vinyl unsaturation along or attached to the polymer backbone (4,48). Aromatic or aUphatic diisocyanates react with glycols or alcohol-terrninated polyether or polyester to form either isocyanate or hydroxyl functional polyurethane intermediates. The isocyanate functional polyurethane intermediates react with hydroxyl functional polyurethane and with acryUc or methacrylic acids to form reactive p olyurethanes. 

PVF resins are generally compatible with phthalate, phosphate, adipate, and diben2oate plastici2ers, and with phenoHc, melamine—formaldehyde, urea—formaldehyde, unsaturated polyester, epoxy, polyurethane, and cellulose acetate butylate resins. They are incompatible with polyamide, ethyl cellulose, and poly(vinyl chloride) resins (141). 

Flame-Retardant Applications. The flame resistance of polyolefins, unsaturated polyester, mbber, and many other synthetic materials can be improved by the iaclusion of chloriaated paraffias. The soHd 70% chlorine product is the preferred choice ia most polymeric systems, but the Hquid grades are widely used ia mbbers, polyurethane, and textile treatments. 

We achieved, that by contact of polyurethane foam with water solution of molybdophosphate, contain by pH 1-2,5 mixture of saturated (5 NMR P=-3.20 p.p.m. apply to 85 % H PO ) and unsaturated monovacant (x=0-t-4) (5 NMR P = -0,96 p.p.m.) heteropolycomplexes Keggin staicture, equilibrium discharge in the direction produced of saturated heteropolycomplex of Dowson stmcture and on the surface of polyurethan foam formed 18-molybdo-2-phosphate acid ( P = -2,40 p.p.m. in ether extract). The formed surfaces heteropolycomplex is stable for action 1 M solution of strong acids and basics and have ion exchanged properties in static and dynamic conditions to relation to macro and micro amount of M(I) ... 

To overcome brittleness these materials are sometimes blended with rubbery materials and with polyurethanes. These polymers may contain unsaturated groups, particularly at the chain ends, so that graft structures may be produced rather than simple mixtures. 

Over the years many blends of polyurethanes with other polymers have been prepared. One recent example is the blending of polyurethane intermediates with methyl methacrylate monomer and some unsaturated polyester resin. With a suitable balance of catalysts and initiators, addition and rearrangement reactions occur simultaneously but independently to give interpenetrating polymer networks. The use of the acrylic monomer lowers cost and viscosity whilst blends with 20% (MMA + polyester) have a superior impact strength. 

Poly(ethylene terephtlhalate) Phenol-formaldehyde Polyimide Polyisobutylene Poly(methyl methacrylate), acrylic Poly-4-methylpentene-1 Polyoxymethylene polyformaldehyde, acetal Polypropylene Polyphenylene ether Polyphenylene oxide Poly(phenylene sulphide) Poly(phenylene sulphone) Polystyrene Polysulfone Polytetrafluoroethylene Polyurethane Poly(vinyl acetate) Poly(vinyl alcohol) Poly(vinyl butyral) Poly(vinyl chloride) Poly(vinylidene chloride) Poly(vinylidene fluoride) Poly(vinyl formal) Polyvinylcarbazole Styrene Acrylonitrile Styrene butadiene rubber Styrene-butadiene-styrene Urea-formaldehyde Unsaturated polyester... 

Fatty acids, both saturated and unsaturated, have found a variety of applications. Brassilic acid (1,11-un-decanedicarboxylic acid [BA]), an important monomer used in many polymer applications, is prepared from erucic acid (Scheme 2), obtained from rapeseed and crambe abyssinica oils by ozonolysis and oxidative cleavage [127]. For example, an oligomer of BA with 1,3-butane diol-lauric acid system is an effective plasticizer for polyvinylchloride. Polyester-based polyurethane elastomers are prepared from BA by condensing with ethylene glycol-propylene glycol. Polyamides based on BA are known to impart moisture resistance. 

Coating materials may be based on short or medium-oil alkyds (e.g. primers for door and window frames) nitrocellulose or thermoplastic acrylics (e.g. lacquers for paper or furniture finishes) amino resin-alkyd coatings, with or without nitrocellulose inclusions, but with a strong acid catalyst to promote low temperature cure (furniture finishes) two-pack polyurethanes (furniture, flat boards) unsaturated polyester resins in styrene with free-radical cure initiated by peroxides (furniture) or unsaturated acrylic oligomers and monomers cured by u.v. radiation or electron beams (coatings for record sleeves paperback covers, knock-down furniture or flush interior doors). 

Polyester-based networks are typically prepared from polyester prepolymers bearing unsaturations which can be crosslinked. The crosslinking process is either an autoxidation in the presence of air oxygen (alkyd resins) or a copolymerization with unsaturated comonomers in the presence of radical initiators (unsaturated polyester resins). It should also be mentioned that hydroxy-terminated saturated polyesters are one of the basis prepolymers used in polyurethane network preparation (see Chapter 5). 

Example 11. One-Component, Moisture-Cure Polyurethane Sealant. This example is of a low-hardness, high-elongation, moisture-curable polyurethane sealant. The material is based on a low-%NCO prepolymer made from 4,4 -MDI and a low-unsaturation (low-monol-content) Acclaim polyol from Bayer. It is adapted from (a) J. Lear et al., Adhesives Age, February 1999, pp. 18-23 and (b) B. Lawrey, et al., presented at UTECH 2000, The Hague, The Netherlands, March 30, 2000, Crain Communications London, 2000. 

Economic and ecological aspects of chemical recycling are examined, and the application of such processes to the recovery of monomers and intermediates from PETP, polyamides, polyurethanes, polycarbonates, unsaturated polyesters, polyacetals, PMMA and PS is discussed. 17 refs. SNIA... 

P.O.34 is rarely used in polyolefins. In such media, it only withstands exposure to 200°C, and its opaque colorations show insufficient lightfastness. P.O.34 tends to bloom, especially in extrusion products made of low molecular weight LDPE types. The pigment is, however, recommended for a variety of other media. These range from aromatic polyurethane foams to cast resins of unsaturated polyester, in which the pigment slightly delays the hardening process. 

P.R.164 was also found in cast resin composed of methacrylate and unsaturated polyester. The pigment does not affect the hardening process of such media, which may be carried out, for instance, by using peroxides. An important field of application was in the coloration of various polyurethanes, for which the pigment was also sold in the form of a pigment preparation. 

P.R.144 is also suited to use in other plastics, such as polystyrene, polyurethane, elastomers, or cast resins, including those made from unsaturated polyester. 

P.R.248 exhibits excellent bleed resistance in plasticized PVC. Transparent specimens equal step 8 on the Blue Scale for lightfastness, while 1/3 SD samples match step 7. The pigment does not perform as well in terms of weatherfastness, for instance in PVC plastisols for coil coating. P.R.248 was also recommended for use in elastomers, polyurethane, and unsaturated polyester. 

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