Polyurethane additives

Step-growth polymerization processes must be carefully designed in order to avoid reaction conditions that promote deleterious side reactions that may result in the loss of monomer functionality or the volatilization of monomers. For example, initial transesterification between DMT and EG is conducted in the presence of Lewis acid catalysts at temperatures (200°C) that do not result in the premature volatilization of EG (neat EG boiling point 197°C). In addition, polyurethane formation requires the absence of protic impurities such as water to avoid the premature formation of carbamic acids followed by decarboxylation and formation of the reactive amine.50 Thus, reaction conditions must be carefully chosen to avoid undesirable consumption of the functional groups, and 1 1 stoichiometry must be maintained throughout the polymerization process. 

The effects of different primers (metallic zinc, aluminum, and phosphate) over steel and an additional polyurethane topcoat over an epoxy... 

Fig. 42. Comparison of the concentration dependences of the stationary currents of glucose electrodes using gelatin membrane-entrapped GOD sandwiched between two dialysis membranes (1) and with an additional polyurethane membrane next to the solution (2).

Antibacterial membranes with a multicomponent system containing Ag, AgBr, Ti02, and hydroxyapatite as four active components were used to obtain more efficient antibacterial activity. Additionally polyurethane nanofiber webs containing silver nanoparticles using the electrospinning technique were obtained with the stability of nanoparticles after washing cycles... 

Stone, H., Basics of Polyurethane Eoam and the Use of Combustion Modifying Additives, Polyurethane Eoam Association, presentation at San Erancisco meeting, April 29, 2003, http // www.pfa.org//EFC9 Handout.html. 

Addition Polyurethanes Polyamide 6 Polyoxymethylene PMMA (polymethylmethacrylate) PBMA (polybutylmethacrylate) Acrylic copolymers Methacrylic copolymers Styrene copolymers Water-soluble polyamide... 

Uses. 3-Pentenenitrile, 3PN, is used entirely by the manufacturers to make adiponitrile. i7j -2-Pentenenitrile, 2PN, can be cycli2ed catalyticaHy at high temperature to produce pyndine, a solvent and agncultural chemical intermediate. 2PN is also chlorinated to manufacture pentachloropyndine, an intermediate in the insecticide Dursban produced by Dow. Addition of ammonia to 2PN foUowed by reduction leads to 1,3-pentadiamine (Dytek ep), which is used as a curing agent for epoxy coatings and as a chain modifier in polyurethanes. 

Another type of polyol often used in the manufacture of flexible polyurethane foams contains a dispersed soHd phase of organic chemical particles (234—236). The continuous phase is one of the polyols described above for either slab or molded foam as required. The dispersed phase reacts in the polyol using an addition reaction with styrene and acrylonitrile monomers in one type or a coupling reaction with an amine such as hydrazine and isocyanate in another. The soHds content ranges from about 21% with either system to nearly 40% in the styrene—acrylonitrile system. The dispersed soHds confer increased load bearing and in the case of flexible molded foams also act as a ceU opener. 

Foamed plastics (qv) were developed in Europe and the United States in the mid-to-late 1930s. In the mid-1940s, extmded foamed polystyrene (XEPS) was produced commercially, foUowed by polyurethanes and expanded (molded) polystyrene (EPS) which were manufactured from beads (1,2). In response to the requirement for more fire-resistant ceUular plastics, polyisocyanurate foams and modified urethanes containing additives were developed in the late 1960s urea—formaldehyde, phenoHc, and other foams were also used in Europe at this time. 

Addition Polymers. The most commonly referenced reaction of isocyanates iavolves their addition to polyhydroxyl, polyamine, or polycarboxyhc acid compounds to yield addition polymers. Due to the wide diversity of raw material characteristics and the broad range of functionahty, polyurethane polymers having a wide range of processiag and performance characteristics are available. 

Aromatic Isocyanates. In North America, aromatic isocyanates ate heavily used as monomers for addition and condensation polymers. The principal appflcafions include both flexible and rigid polyurethane foam and nonceUulat appflcations, such as coatings, adhesives, elastomers, and fibers. 

Poly(propylene oxide) [25322-69-4] may be abbreviated PPO and copolymers of PO and ethylene oxide (EO) are referred to as EOPO. Diol poly(propylene oxide) is commonly referred to by the common name poly(propylene glycol) (PPG). Propylene oxide [75-56-9] and poly(propylene oxide) and its copolymers, with ethylene oxide, have by far the largest volume and importance in the polyurethane (PUR) and surfactant industry compared to all other polyepoxides. Articles reviewing propylene oxide (1), poly(propylene oxide) (2—4), other poly(aIkylene oxides) (4), and polyurethanes (5—7) are cited to lead the interested reader to additional detail not in the scope of this article. 

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). 

In addition to the primary appHcation of PTMEG ia polyurethanes, polyureas, and polyesters, a considerable number of reports of other block and graft polymers highlighting PTME units have appeared. Methods have been developed that allow the conversion of a cationicaHy polymerizing system to an anionic one or vice versa (6,182). 

Several factors were utilized in bringing formaldehyde release down. In particular, resin manufacturer executed more careful control of variables such as pH, formaldehyde content, and control of methylolation. There has also been a progressive decrease in the resin content of pad baths. The common practice of applying the same level of resin to a 50% cotton—50% polyester fabric as to a 100% cotton fabric was demonstrated to be unnecessary and counter productive (89). Smooth-dry performance can be enhanced by using additives such as polyacrylates, polyurethanes, or siUcones without affecting formaldehyde release. 

---