CS240326B1 - Method of production of polyurethanes - Google Patents

Abstract

The invention describes a method for producing polyurethanes, mainly polyurethane foams, by reacting polyols with di- to polyisocyanates in the presence of catalysts, stabilizers, flame retardants, and possibly other auxiliaries. The preparation of polyurethanes is carried out in the presence of a catalyst based on oxygen compounds of manganese and/or cobalt and/or iron and/or nickel in an amount of 0.001 to 0.5 wt. % of metal per polyol in the presence of oxygen and/or nitrogen-containing complexing compounds in an amount of 0.01 to 5 wt. % per polyol.

Description

240326

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the preparation of polyurethanes, in particular polyurethane foams, of polyol-di-polyisocyanate reaction polymers having the presence of a catalyst mixture on the basis of the VIIIa and VIII groups of the periodic table. .. · '' - · ·

Polyurethane foams are produced by reacting aromatic or cycloaliphatic isocyanates with functional groups in the molecule greater than 1, with compounds containing more than 1 active hydrogen in the molecule, in the presence of a catalyst, blowing agent, stabilizer, emulsifier, retarder burns, possibly other additives. They can be prepared in a single-stage or pre-planned manner. Numerous NCO-containing compounds can be used as isocyanates, but crude 4,4'-diphenylmethane diisocyanate or toluene diisocyanate are particularly suitable. The second major component consists of a polyol component which contains a compound with active hydrogen, e.g. polyetherpolyol or polyester-polyol, optionally mixtures thereof and auxiliaries for the preparation of polyurethanes. In practice, polyetherpolyols and polyesters of olefins are most commonly used.

Possible polyester polyolysis products usually based on dicarboxylic acids or their anhydrides with divalent or polyhydric alcohols. Adipic acid is suitable for the preparation thereof, further may be: oxalic, malonic, succinic, glutaric, pimelic, cortic or azelaic; unsaturated dicarboxylic acids such as maleic, fumaric, itaconic or anhydrides such as phthalic anhydride and maleic anhydride. Suitable alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol or polybutylene glycols. Among the polyhydric alcohols are, for example, glycerol, hecanetriol, butanetriol, trimethylolpropane, trimethylolethane, pentaerythritol, mannitol or sorbitol and others.

Polyether polyols, which may be used alone or in admixture with polyester polyols, are the products of the reaction of polyhydric alcohols, polycarboxylic acids or phenol polyunsaturated compounds with a low molecular weight 1,2-epoxy compound. Examples of low molecular weight 1,2-epoxy compounds include e-ethylene oxide, propylene oxide, butylene oxide, isobutene oxide, 2,3-epoxyhexane, triethyl-2,3-epoxy octane, epichlorohydrin, epibromohydrin, styrene oxide, glycidyl ether and the like. The epoxides used to prepare the polyether polyols are, in particular, those compounds which are formed by substitution of hydrocarbons, ethers, sulfides, sulfones or esters by mono-epoxy and which contain at most 18 carbon atoms per molecule. In particular, low molecular weight alkylene oxides are used for the preparation of polyurethane foam. Furthermore, they may be polyester-amides or mixtures thereof with polyesters prepared in a known manner from polyhydric acids, alcohols, optionally amines, polyol ethers (NSR Pat. 1 105 156) or polyacetals (NSR Pat. 039,744 and 1,045,095). The starting materials for the production of polyols for polyurethanes are commercial products of considerable purity and, in addition, the polyols obtained are very carefully purified from alkali catalysts, which in general are not more than 1 in polyether polyols. 10 “3pere. (10 ppm). Other available sources are used for technical and economic reasons, in many cases secondary levels. Processes for the preparation of polyurethanes from polyesterpolyols based on by-products or secondary raw materials are known, where distillation residues from the production of dimethyl terephthalate or terephthalic acid (MS AO 229 504 and AO No. 229 503) are used as acidic components and cyclohexanone production residues by oxidation of cyclohexane (MS auto-test 233 472). These distillation residues concentrate the metal compounds, especially cobalt, manganese and iron, or any amount of calcium, magnesium, and silicon supplied as catalysts, together with the catalysts, into the prior art steps for the production of dimethyl terephthalate and the like. These impurities undergo a process of polyesterification and / or re-esterification into a final product. The properties of polyurethane foams have a distinctive effect on the nature and amount of auxiliary agents, including activators, stabilizers, emulsifiers, blowing agents, fillers and the like.

A number of known compounds can be used as activator (Saunders JH, Frisch KC: Polyurethanes; Russian Chimija Polyurethane, Chimija, Moscow 1968), but especially tertiary amines such as N, N (-dimethylcyclohexylamine, dimethylethanol-amine) , triethylenediamine, dimethylaniline, pyridine, ethylmorpholine, quinoline and the like, and furthermore, gartokartic compounds such as dibutyltin dilaurate, n-butyltin trichloride, trimethyltinhydroxide, dimethyltin dichloride, mercuric acetate, antimony salts, bismuth, and the like. resp., secondary compounds, especially in the preparation of said polyol polyols, the catalytic effect of the metals present, especially the salts of manganese, cobalt, molybdenum, iron, or other metals, can be considered. synergistic effect occurs, especially when using tin salts and tertiary amines. Not only affect the rate katalyzátorovmožno course reakciehydroxylovej groups izozkyanátom, aleaj .propertyName formation and foam. Thus, in the preparation of polyurethane foams, a catalytic system is used which consists of salts of manganese, iron, cobalt, eventually nickel with tin compounds (NSR Pat. No. 1,193,244). 240326

However, unlike the above data, the presence of the Mn, Fe, Co and Ni compounds in the polyester polyol or in its constituents, in the preparation of polyurethane foams, is that the polyurethane preparation times, especially the foam drying time, are very rapid. As a result, the flowability of the polyurethane foam is insufficient and such a system cannot be used to produce many products.

According to the present invention, a process for producing polyurethanes, in particular polyurethane foams, by reacting a polyol component containing a compound with at least two active compounds and a di- to polyisocyanate in the presence of catalysts, stabilizers and other auxiliaries is carried out using a manganese oxide catalyst. and / or cobalt and / or iron and / or nickel in an amount of 0.001 to 0.5% by weight. % of the metal to the polyol in the presence of oxygen and / or nitrogen complexing compounds in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight. to poly-ol. An advantage of the process for preparing polyurethanes, in particular polyurethane foams, according to the present invention is the fact that a high quality foam, very good physical-mechanical properties, with a prolonged gel time and good flowability are prepared by the catalyst system. According to the invention, a process for the preparation of polyurethanes of such polyols, especially polyester polyols, in which the organometallic compounds of the cohalt, manganese, iron, nickel and other metals are present, is particularly preferred.

Such polyesterpolyols are prepared by a variety of raw materials, e.g., dimethyl terephthalate and / or terephthalic acid (e.g., U.S. Patent No. 218,170), or from cyclohexanone production by oxidation of cyclohexane (MS. In the case of conventional catalysts, the foaming times are very fast, with the foam time being the same as the loss of tack time. then the quality of the foam is deteriorated, and a high gelling time high foam is prepared in the presence of tertiary amine with the organo-compounds of the metals VIIIb or VIII of the periodic system in combination with dicarboxylic acids, beta-diketone derivatives , heterocyclic nitrogen compounds, alkylocite Such compounds include, for example, benzoylacetone, alizarin, alpha-nitroso-beta-naphthol, diphenylthiocarbone, cyclopentadiene, diacetyldioxime, acetyl acetone, acetonylacetone, N-methylimidazole, 2-ethylimidazole, 2,4- dimethylimidazole and others. It will be understood that the catalyst system may be combined with known catalysts, e.g. amines, tin compounds, and the like.

Suitable isocyanate components in the present invention include many organic diisocyanates to polyisocyanates, for example aryl polyisocyanates, benzene or naphthalene series, which are more reactive and toxic as aliphatic compounds. Examples of these compounds are: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, phenyldiisocyanate, alpha-naphthyl diisocyanate, 4-toluene diisocyanate, methylene bis- (4-phenyldiisocyanate), 3 -ditoluene-4,4'-diisocyanate, 2,4-dichlorophenyldiisocyanate, hexamethylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylpropanediisocyanate, followed by polymethylene- and polyphenylisocyanate or mixtures thereof. High molecular weight diisocyanates are liquid products of the reaction of diisocyanates with polyhydroxy compounds or polamines. In addition, polyisothiocyanates or mixtures of polyisocyanates can be used. Similarly, technical unpurified or dry polyisocyanates, e.g. crude 4,4'-methanediphenyl diisocyanate, are also used. In some instances, a suitable isocyanate component is a prepolymer, the product after partially reacting the polyester polyol or mixtures thereof with the diisocyanate. The choice of the type of diisocyanate used depends on the properties of the starting material of the desired product properties.

According to the process of the present invention, molybdenum manganese, iron, cobalt or nickel is used in the form of metal salts in one or a mixture thereof. Preferably divalent salts of metals can be used: Fe + 3, Fe + 2, Co + 2, Ni + 2 or Mn + 2. They may be applied alone or in combination and mixed with metals, respectively. salts of the metal-like power eg Fe + 3, Fe + 2. Equally, metals and their salts can be used.

The metal soap anionic component may be simply formulated as R '(COO ") n, wherein R"' is an aliphatic hydrocarbon or cycloaliphatic hydrocarbon such as an alkyl, alkenyl, or corresponding cycloaliphatic moiety of less than 20 carbon atoms. Furthermore, it may be an aryl radical such as a phenyl, substituted phenyl or naphthyl radical, such as benzyl, styryl, cinnamyl, toluyl, xyryl, naphenyl, and the like, n is 1, 2. Typical examples from which soaps may be prepared are acids: acetic, propionic, butter, capro, caprylic, stearic or oleic, naphthenic, tall oil and other known acid mixtures. most used are iron (III) stearate, manganese (II) stearate, cobalt (II) stearate, cobalt (II) naphthenate, iron (III) linoleate, manganese (II) linoleate, iron (II) stearate or nickel stearate. -

In particular, the compounding compound 24032B, which contains free electron-pair, or at least two double bonds in the molecule, may be used mainly in compounds having at their atom, e.g., oxygen, nitrogen, sulfur, phosphorus and the like. By forming a bond between the metal non-metal, a coordination compound is formed of the complex or chelate, which has different effects on the formation of polyurethanes such as self-forming. The tertiary amine in combination with the co-compound forms a catalytic system with excellent foaming properties.

The use of the complex catalysts of the present invention is of great importance in the application of foam with the requirement of high foam adherence to construction materials, e.g. in the manufacture of cooling equipment, filling hollow spaces in building industry. Substantial overload of reaction times, e.g. in any case, achieving a significant difference in bonding time and ending the foam growth does not deteriorate the physico-mechanical properties of the foam; Further details that more closely point to the positive effect of the catalytic system, the course of formation, and the properties of the foam are clear from the examples. Přikladl

Hard polyurethane foam is prepared by mixing a polyol component consisting of 100 g of SlovapropT-450 polyether polyol (hydroxyl number 450 mg KOH / g, acid value 0.2 mg KOH / g, viscosity at 25 ° C 2.5 Pas), 2 g silicone stabilizer -for Tegostab B 1903, 1.5 g of triethylamine mixed stannous octoate activator (10k 1), 1.0 g cobalt naphthenate and 40 gtrichlorofluoromethane (Freon-11) with 120 gs 4,4'-methylenediphenyl diisocyanate (Desmodur 44V) . The foam has a uniform structure and characteristic foaming times: start time 16 s; foam growth time 45 s and 48 s stick time. Example 2

To prepare the hard polyurethane foam, use the formulation of Example 1, but with the difference that 1.2 g of N-methylimidazole is added to the polyol component. Foam with unchanged structure has significant overturning characteristic foaming times: 24's start time; foam growth time 100 s; Loss of stickiness 120 sec

For the preparation of the rigid polyurethane foam, polyester polyol prepared by re-differentiation of distillation residues from the production of dimethyl terephthalate with diethylene glycol and peneterythritol is used in a weight ratio of 7.5 to 7 to 1 according to MS. AQ 218 170, containing cobalt, iron and manganese compounds.

To 100 g of polyester polyol (hydroxyl number 452 mg KOH / g, acid number 0.8 mgKOH / g, cobalt content 0.12% w / w, manganese content 0.01% w / w, iron content 0.005% w / w) 0 8 g of N, N'-dimethyl-cyclohexylamine, 2 g of TegostabB 1903 stabilizer and 45 g of Freon-11. After mixing, 130 g of Desmodur 44V are added and after thorough mixing the mixture is poured into the mold. A short polyurethane foam is obtained. foaming: 18 s; 50 s; 50 sec

The polyol component is prepared by mixing 50 g of the polyester polyol Vupanol-100 specified in Example 3 with 50 g of the Slovaprop T-450 polyether polyol specified in Example 1, 2 g of the silicone stabilizer Te-gostab B 8404, 0.8 g of N, N. 120 g of crude 4,4 ' -methylenediphenyl diisocyanate are used as the polyisocyanate. ' -dimethylcyclohexylamine, 0.8 g of acetylacetone and 35 g of Freon-11. The foam has a uniform uniform structure and characteristic foam times of 28 seconds; 120 s; 130 sec. Example 5

The rigid polyurethane foam is prepared by reacting 100 g of Slovaprop T-450 polyether polyol as specified in Example 1, containing 1.1 g of naphthenate-butylate, 0.4 g of ferrous naphthenate, 1.6 g of 1,4-dimethylpiperazine, O 2 g of octoacetate, 0.2 g of propionic acid, 2 g of Tegostab B 1903, 0.5 g of water and 30 g of Freon-11 with 135 g of crude 4,4 ' -methanediphenyl diisocyanate. Prepared foam oobj. a weight of 45 kg / m 3 is of good uniformity, has a prolonged gel-life and is characterized by good leakage. Typical foaming times are 30 sec; 160 sec; 190 p

Cold poppy polyurethane foam resins are prepared by mixing a polyol component consisting of 100 g of polyether polyol Slovaprop TMP-35 (hydroxyl number 35 mg KOH / g, primary content of OH groups 68%, acid number 0.1 mgKOH / g), 2 5 g of water, 1.0 g of stabilizer Teostostab B 4113, 5 g of trichlorofluoromethane, 2.7 g of triethanolamine, 0.4 g of dimethylethanol amine, 0.2 g of triethylamine, 0.3 g of Dabco, 0.5 g of cobalt nitrate; And 1 g of a mixture of 4,4'-methanediphenyldiisocyanate and toluene diisocyanate (60:40 by weight). Typical times are: TZ 14 s; SZ 70 s; AZ 75 s. Example 7 Preparation of cold poppy polyurethane foam is carried out according to Example 6, with

Claims (2)

'First Method of production . polyurethanes, in particular polyurethane foams, by reacting a polyol component containing the compound with at least two active hydrogen and a di- to polyisocyanate in the presence of catalysts, stabilizers and other excipients, characterized in that a catalyst based on oxygen compounds of manganese and / or cobalt and / or iron and / or nickel in an amount of 0.001 wt. % to 0.5 wt. % metal to polyol in the presence of oxygen and / or nitrogen complexing compounds in an amount of 0.01 wt. until INVENTION 5 wt.%, Preferably 0.1 to 3 wt. to polyol. 2. Process according to claim 1, characterized in that a catalyst based on oxygen-containing compounds of manganese and / or cobalt and / or iron and / or nickel is used in an amount of 0.01 to 0.5% by weight. % metal to polyol in the presence of oxygen and / or nitrogen compounds in an amount of 0.01 to 5 wt.%, preferably 0.1 to 3 wt. polyol, which cobalt, manganese, iron and nickel and / or their compounds bind and / or form complexing compounds with them. *