Trimer foams

Trimer foams, 201 Trimerization, 226-227 Trimethylol propane (TMP), 224 Trimethylsilyl 3,5-diacetoxybenzoate, synthesis and polycondensations of, 118... 

Though closed-cell rigid polyurethane foams are excellent thermal insulators, they suffer form the drawback of unsatisfactory fire resistance even in the presence of phosphorus- and halogen-based fire retardants. In this context, polyisocyanurates, which are also based on isocyanates, have shown considerable promise. Isocyanurate has greater flame resistance then urethane. Although rigid polyurethane is specified for the temperatures up to 200°F (93°C), rigid polyisocyanurate foams, often called trimer foams, withstand use temperatures to 300°F (149°C). Physical properties and insulation efficiency are similar for both types. 

Commonly used isocyanates are toluene dhsocyanate, methylene diphenyl isocyanate, and polymeric isocyanates. Polyols used are macroglycols based on either polyester or polyether. The former [poly(ethylene phthalate) or poly(ethylene 1,6-hexanedioate)] have hydroxyl groups that are free to react with the isocyanate. Most flexible foam is made from 80/20 toluene dhsocyanate (which refers to the ratio of 2,4-toluene dhsocyanate to 2,6-toluene dhsocyanate). High-resilience foam contains about 80% 80/20 toluene dhsocyanate and 20% poly(methylene diphenyl isocyanate), while semi-flexible foam is almost always 100% poly(methylene diphenyl isocyanate). Much of the latter reacts by trimerization to form isocyanurate rings. 

Commercially, polymeric MDI is trimerized duting the manufacture of rigid foam to provide improved thermal stabiUty and flammabiUty performance. Numerous catalysts are known to promote the reaction. Tertiary amines and alkaU salts of carboxyUc acids are among the most effective. The common step ia all catalyzed trimerizations is the activatioa of the C=N double boad of the isocyanate group. The example (18) highlights the alkoxide assisted formation of the cycHc dimer and the importance of the subsequent iatermediates. Similar oligomerization steps have beea described previously for other catalysts (61). 

Urethane network polymers are also formed by trimerization of part of the isocyanate groups. This approach is used in the formation of rigid polyurethane-modified isocyanurate (PUIR) foams (3). 

Polymeric isocyanates or PMDI ate cmde products that vary in exact composition. The main constituents are 40—60% 4,4 -MDI the remainder is the other isomers of MDI, trimeric species, and higher molecular weight oligomers. Important product variables are functionaHty and acidity. Rigid polyurethane foams are mainly manufactured from PMDI. The so-called pure MDI is a low melting soHd that is used for high performance polyurethane elastomers and spandex fibers. Liquid MDI products are used in RIM polyurethane elastomers. 

Trimerization to isocyanurates (Scheme 4.14) is commonly used as a method for modifying the physical properties of both raw materials and polymeric products. For example, trimerization of aliphatic isocyanates is used to increase monomer functionality and reduce volatility (Section 4.2.2). This is especially important in raw materials for coatings applications where higher functionality is needed for crosslinking and decreased volatility is essential to reduce VOCs. Another application is rigid isocyanurate foams for insulation and structural support (Section 4.1.1) where trimerization is utilized to increase thermal stability and reduce combustibility and smoke formation. Effective trimer catalysts include potassium salts of carboxylic acids and quaternary ammonium salts for aliphatic isocyanates and Mannich bases for aromatic isocyanates. 

HDI is a monomer used in the production of polyurethane foams and other related products, and is found in some industrial paints and spray painting operations. It is a compound which reacts readily with water and alcohols (Von Burg 1993). It has a vapor pressure of 0.05 mm Hg at room temperature, but can be present in aerosol form allowing a potentially higher exposure to individuals. The HDI-BT trimer is often present for similar industrial uses. It would be expected to have a lower vapor pressure however, the aerosol form can also be present, allowing potentially higher exposure of HDI-BT to individuals. HDI reacts slowly with water to form carbon dioxide (HSDB 1996). The base-catalyzed reaction of HDI with alcohols should be carried out in inert solvents the reaction may occur with explosive violence in the absence of solvents (NFPA 1994). 

Modification of poly(carbodiimide) foams with polyols afford hybride foams containing urethane sections. However, the thermal stabilities of the poly (urethane carbodiimide) foams are lower. Using isocyanate trimerization catalysts, such as l,3,5-tris(3-dimethylaminopropyl)hexahydro-s-triazine, in combination with the phospholene oxide catalyst gives poly(isocyanurate carbodiimide) foams with improved high temperature properties. The cellular poly(carbodiimide) foams derived from PMDI incorporate six-membered ring structures in their network polymer structure. ... 

Modification of the poly(carbodiimide) foams, using polyols as comonomers, is possible, but the excellent thermal and flammability properties are reduced. Poly(carbodiimide isocyanurate) foams can also be continuously produced using 1,3,5-tris-(3-dimethylaminopropyl)-hexahydro-s-triazine as the cocatalyst. Other trimerization catalysts, such as potassium 2-ethylhexanoate and quaternary ammonium carboxylate (Dabco TMR 2) are also used as cocatalysts in the formation of poly(carbodiimide isocyanurate)... 

Multi-functional, non-foaming polyester dyeing auxiliary. Recommended for leveling, trimer and crease mark control in jet and beck dyeing applications. 

Multipurpose high temperature dyeing assistant for polyester which promotes lubrication, leveling, dispersing, trimer and crease mark control. Non-foaming. 

Buricus (201) and Nicholas and Gmitter (58) reported on TDI prepolymer-based isocyanurate foams prepared by trimerizing NCO-terminated jn-epolymers. TGA data (58) showed that there was no... 

In order to meet the requirements for low friabUity and low combustibility the following formulations (Table 28) were disclosed for laminate production (72). The resultant foam has a trimer content of... 

Urethane-Modified Isocyanurate Foams. Urethane-modified isocyanurate foams are prepared by the trimerization of a polyisocyanate in the presence of a polyol, a trimerization catalyst, a blowing agent, and a surfactant. The foams have high flame and temperature resistance. The combined use of an isocyanurate foam and glass fiber not only improves the physical properties, e.g., flexural strength, friability, etc. but it also improves the flame resistance because the char formed from the foam acts as thermal barrier and protects it from flame and heat. This type of composite, therefore, is widely used for buUding applications in the U.S.A. Urethane-modified isocyanurate foam systems have also been used in the SRIM process (26, 36, 37). 

Burkus [22] was one of the first to report the preparation of isocyanurate-containing urethanes from polyester urethane prepolymers reacted with a triethy-lamine propylene oxide trimerization catalyst. Burkus [15,15a] also reported the preparation of rigid foams by a similar trimerization process. 

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