CS201783B1 - Process for producing polyestres, preferably polyester polyols - Google Patents

Abstract

The invention relates to a method for preparing polyester polyols by polyesterification of di- and polycarboxylic acids with di- and polyhydric alcohols under the catalytic effect of organometallic compounds of iron, antimony, titanium, zirconium, genanium and lead and/or in combination with terephthalic acid in a weight ratio of 1:0.01 to 1:10, and preferably 1:3 in a total weight of 0.001 to 2 wt. per batch of raw materials. The process is particularly advantageous for preparing polyester polyols for polyurethanes, because the esterification catalyst present is also a strong catalyst for the synthesis of polyurethanes.

Description

\ ntor \\ »iili-zii STRESINKA JOZEF ing. CSo., MALČOVSKÝ EUGEN ing.,

WET JOZEF ing., PRIEVIDZA and VALENT VOJTECH ing., TRNAVA

Process for producing polyestres, preferably polyester polyols

The present invention relates to a process for the preparation of polyester polyols with polyester and polycarboxylic acids having two or more alcohols with the catalytic action of organometallic compounds of oine, antimony, titanium, zirconium, genium and lead and / or in combination with a termium of tannin: to 1: 10, and preferably 1: 3 in a total weight of 0.001 to 2 fa. for raw material feed.

The process is particularly advantageous for the preparation of polyester polyols for polyurethanes since the esterified catalyst present is at the same time a strong catalyst for polyurethane.

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The present invention provides a process for the manufacture of polyethers or polyester polyols, particularly suitable for the preparation of polyurethanes.

The polyesters or polyetherpolyols and in Seobeon are used to prepare dicarboxylic or polycarbonic acids or anhydrides and double or multiply alcohols depending on the type of raw materials used, the desired acid number and the free hydroxyl group content of the final product. As acids, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, cork, azelaic acids can be used.

-1,2,3-tricarbonesA and 1,4-oyclohexanedicarboxylic acid. Suitable alcohols are polyhydric aliphatic or aromatic alcohols, in particular ethylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, 1,2-propylene glycol, 1,4-tetramethylene glycol, 1,2-butylene glycol, 1,4-butanediol, 1,4-butanediol. -pentenediol, 1,6-hexAndiol,

1,7-heptAndiol, glyoerin, 1,1,1-trimethylolpropene, 1,1,1-trimethylolethene, neopentyl glycol, 1,2,6-hexanetriol, dibromoneopentyl glycol, 1,10-decanediol, pentaerythritol and 2,2-bis- (4-Hydroxyoyclohexyl) propAn.

The reaction is usually carried out at a temperature of 130 to 240 ° C. The reaction mixture is heated so that the reaction water is readily removed from the reaction medium. For this purpose ea uses nitrogen, carbon dioxide or hydrocarbons, for example toluene, xylan, which carry the water in the form of an azeotropic mixture. Hooi reakoia proceeds in the first stage even without the presence of the catalyst, it is necessary to work in the presence of the catalyst to achieve a low acid value in a relatively short time. Its volta is also based on the use of polyesters or polyester polyols since many catalytic systems support the application of undesirable side effects in the application.

An important group of catalysts that promote the reaction of di- and polycarbonic acids with di- and polyalcohols are acidic catalysts such as hydrochloric acid, orthophosphoric acid, aluminum sulfate, p-toluenesulfonic acid A, ethylleiric acid A, hydrofluoric acid, boron trifluoride and the like. A common disadvantage is that they cause product coloration and may even be used at lower temperatures, which negatively affects the fineness of the polyeeterification, especially if the product requires low acidic cells.

Polyetherpolyols containing substances of an acidic nature have reduced reactivity, for example in the reaction with diisocyanates due to the formation of pre-useful compounds with amine terarium salts used as catalysts for the formation of polyurethanes. Although in some cases organic acids are used for retarding polyurethane reactants, several acids are unsuitable for the preparation of polyester polyols.

The use of ammonium alkali reacts with compounds such as hydroxides, alcoholates and alkali carbonates, and does not exhibit an enhanced catalytic effect over non-catalytic polyethererification. A wide variety of catalysts, such as zinc oxide, lead oxide, calcium oxide and other compounds, which can be used in

201 783 genuine polyester.

The alkaline reacting compounds in the polyeeterpolyoloohols, used in particular for the preparation of polyurethanes, influence the formation of side reactions. Some of these substances are highly catalysts of trimeric diisocyanates and are therefore unsuitable for the preparation of polyester polyols when used in catalytic active concentrates.

For preparing polyesters and polyester polyols, tin compounds such as Sn phthalate, Sn oxalate / US Pat. No. 8,194,791 (Sn) 00CR / ₂ , wherein R is a saturated or unsaturated aliphatic chain having 7 to 17 carbon atoms. JS file. 3,162 616 /. However, these are catalytically less effective, at least in the last phase of the polyesterification. In addition, the catalyst is hydrolyzed to form water-borne compounds and sediment formation.

For polycondensation, a wide variety of titanium and zirconium catalysts, e.g. titanetetrahalides / V. Brit. pat. No. 8,775,318], lanthanum titanate / U.S. Pat. No. 8,916,474), titanyloxalate of metals / French. pat. No. 8,369,810], tetralkyltitanate (V). Brit. pat. No. 8,793,111, Quaternary, amine, alkali or alkaline earth salts of titanium alkoxides (U.S. Pat. file No. 2,727,881 /. The inorganic titanium compounds have the disadvantage that they are poorly soluble in the reaction mixture and thus catalytically poorly active. Organic titanium compounds, e.g. Tetraslropropyltitanate / Offiolal Digest, Mareo 1963, p. However, they are very hygroscopic. When used in higher concentrators, titanium deposits in the reactor, pipelines, and thus production disturbances, are produced. At higher temperatures and concentrators, they can catalyze the cyclization of butanediol to form tetrahydrofuran and water. Increasing the titanium content of the polyester polyol negatively affects the polyurethane preparation.

It is therefore proposed to use as a catalyst a titanium compound which is prepared by converting a plurality of precipitated titanium dioxide with 6-hydroxycarbonic acids and tero. aliphatic amines in aqueous solution. For DIRECTIONS T10 ₂ is used navrbnjú tetraalkyl orthotitanate / Ger. No. 8,214,775 /.

In addition to these drawbacks, a common feature of titanium compounds is that they deteriorate the color of the product, 80 being particularly disadvantageous for preparing polyester polyols for polyurethanes and for producing transparent materials. Zirconium compounds, on the other hand, do not color the product to such an extent, but also the catalytic activity is in some systems, glycol-dicarboxylic acid, low.

It is also known to use a complex compound of triethanolamine and a metal of the group: magnesium, calcium, lanthanum, titanium, zirconium, cobalt, zinc, cadmium, manganese, mercury, genaanlum, and lead / Cs. pat. No. 8,138,959, the hydroxy group of triethanolamine is involved in the formation of the complex.

According to the present invention, polyesters, preferably polyester polyols of polycarbonic acids and polyols, are produced by catalytic polyesterification, generally while discharging the resulting water in the form of an azeotrope, such that the reaction occurs under darkness of a mixture of titanium-based catalysts and / or at least one zirconium compound. % of an element of the group oin, antiman, germanium, lead and / or tertiary amine in a weight ratio of 1 t 0.01 to 1 t 10, preferably 1 to 3 relative to each other, in an amount of 0.001 to 2 µm by weight based on the starting raw materials.

The process according to the invention achieves a substantial reduction in the reaction time without the formation of by-products. Polyesters, especially polyester polyols, are water-clear. By suitably combining the catalysts, the desired reactivity of the polyeeterpolyol in the reaction with the diisocyanates according to the type of polyurethane being prepared can be achieved.

From the point of view of the efficiency of the process according to the invention, it is important to select a catalytic system which is possible over a wide range of mannitol. One component of the system are titanium and / or zirconium based substances which can be applied individually or together.

The second component is either a compound or compounds of the elements from the group oin, anti-manganese, germanium and lead and / or a teramamine amine, the most preferred X1 ratio of said components being 1 t 3,

Example 1

Rata »·! The apparatus consists of a four-necked flask equipped with a stirrer, a contact thermometer set for azeotropic deetileal, and a nitrogen inlet.

Weigh 730 g of adipic acid, 552 g of diethylene glycol, 33.3 g of trimethylolpropane, 35 g of xylene into flask ea and use 0.13 g of tetrabutoxytitane and 0.25 g of dibutylloindilaurate as catalyst ea. of reaction water by azeotropic distillation with xylene. After the polyestrpolyol has an acid number below 1 mg KOH / g, the product is cooled to 150 ° C and xylene is distilled off under vacuum and completely. The reaction time of the polyesterifolia is 5 hours. This gives a colorless polyeeterpolyol having an acid number of 0.4 mg KOH / g, a hydroxyl value of 55.0 mg KOH / g, a viscosity at 75 ° 0 of 1.25 Pae, a water content of 0.01 fa by weight, a color below 1 ° 0ardnera.

Example 2

1290 g of adipic acid and 600 g of ethylene glycol are weighed into a four-necked sulfonation flask as in Example 1 e. 0.1 g of tetrabutoxytitane and 0.3 g of triethylamitte are used as catalyst ea. The contents of the flask ea are gradually heated to 200 ° C, the de-icing of the reaction water e and nitrogen is produced at a flow rate of 25 liters / hour. The reaction time of the polyesterifiable is 12 hours. The polyesterpolyol prepared had an acid number of 0.9 mg KOH / g, a hydroxyl number of 54.6 mg KOH / g, a water content of 0.03% by weight, a melting point of 53 ° C, a viscosity at 75 ° C of 0.62 Pas.

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Example 3

Polyethererification 1370 g of adipic acid with 935 β 1,4-butyl-glycol using a catalyst of 0.08 g of tetrabutoxytitanium and 0.8 β of lead stearate is made in the presence of 115 β xylene as the reaction water scavenger. The temperature of the reaction mixture is increased gradually to 220 ° C, the polyether permeation time is 4 hours. The polyetherpolyol after distillation of xylene has an acid number of 0.65 mg KOH / g, a hydroxyl value of 56 mg KOH / g, a water content below 0.01% by weight. color below 1 ° Gardner.

Example 4

870 g of adipic acid, 300 g of ethylene glycol, 50 g of xylene, 0.5 g of tetrabutyl zirconium, 0.01 g of triethylamine and 0.03 of antimony trioxide are weighed into a reaction flask as described in Example 1 and reacted at 200 ° C for 2 hours. yielding a product with an acid number of 130 mg KOH / g, which in the Salc step is reacted with 210 g of monoglycol ethyl ether. The reaction time is 15 hours · The product obtained after distillation of xylene is a miscellaneous liquid with an acid number of 1.6 mg KOH / g, a hydroxyl number of 1 mg KOH / g, a water content of 0.03 # mass · The final product when used as a plasticizer very good properties without any negative effects.

OBJECT OF THE INVENTION

Claims (1)

OBJECT OF THE INVENTION Method for producing polyesters, preferably polyester polyols, from polycarbonate cyeeline and polyols by catalytic polyethererification, generally with azeotropic water formation, characterized in that the reaction is carried out in the presence of a mixture of titanium catalysts and / or at least one zirconium compound. from the group of ola, antimony, germanium, lead and / or teramine amine in a relative weight ratio of components of 1 * 0.01 to 1: 10, preferably 1: 3, in an amount of 0.001 to 2% by weight, calculated on the starting materials.