CS201839B1 - Process for producing a modified unsaturated polyester resin - Google Patents

Abstract

The invention relates to a method for producing a modified unsaturated polyester resin, or its copolymers, with a reactive solvent, in which waste from another process is used as a starting material without a negative impact on the properties of the final resin and, conversely, with a beneficial impact from the point of view of economy and ecology. The polyester is prepared from dicarboxylic acids and/or their anhydrides, di- and/or polyols and from distillation residues from the regeneration of ethylene glycol from the production of polyethylene glycol terephthalate, the amount of distillation residues used being in the range of 10 to 80 wt., calculated on the acids and/or their anhydrides used, and the polyesterification is carried out in the first stage at a temperature of 90 to 120 °C and in the next stage at a temperature of 190 to 220%.

Description

1 201839

It is an object of the invention to provide a process for the production of a modified unsaturated polyester or polyunsaturated polyester. its copolymers, by reactive dissolving agent, in which the waste of another prooes utilizes the eye of the raw materials, without adversely affecting the properties of the fluffy, and vice versa, the beneficial impact and the economy and the ecology.

Polyasulfonated polyester is produced from di- or polyols by polyestarification with dicarboxylic acids or anhydrides, starting materials used are individual substances produced. The substances and the quantitative properties in the vigorous media influence the properties of the final product. The use of a mixture of various industries, where there is a change in quantitative composition, appears to be unattractive in view of industrial use, since it has not been possible to provide permanent reproducibility for the finished product.

According to the present invention, the modified non-saturated polyester resin or copolymers are produced by reacting with the reactive solvents polyester-diol and / or polyols with dicarboxylic acids and / or anhydrides at an elevated temperature, whereby the water is preferably discharged in the form of polyester The azeetro-p-ice mixture with xylene and the reaction product after partial cooling is added to the auxiliaries such as stabilizers, paraffin, dissolved so that the polyester is prepared from the di-carboxylic acids and / or the anhydrides, dl- and / or polyols and from the distillate. % of ethylene glycol regsulfate residue from the production of polyethylene glycol terephthalate, the amount of distillation residues used being in the range of 10 to 80% by weight. calculated on the used acids and / or anhydrides and polyesterifiers, the first step is carried out at a temperature of 90 to 120 ° C and in a further step at a temperature of 190 to 220 ° C. The advantage of the process according to the invention is, in particular, that waste which is difficult to dispose of in ecological terms is used as a raw material starting material, and in addition to the organic component, the inorganic component which is practically a polyesterifunctional catalyst is used efficiently. Salíia's advantage is that women's variability in complex waste is technologically simple to obtain the product of the owner in the range of acceptable tolerance. The starting materials are dicarboxylic acids and / or anhydrides, as well as the literature and literature. Most preferred are fumaric, malelic, roep, non-unsaturated .alpha., .Beta.-dicarboxylic acids. Joj anhydride, from acidified dicarboxylic acids and aromatic dicarboxylic acids isolated with isophthalic acid and phthalic anhydride. Di- and polyols fail through the starting feedstock and are still used in 2 to 6 carbon atoms in the molecule. Ioh calculation one-time known from the literature and practice. The most preferred diol is propylnollyl (propanediol - 1.2).

According to the invention, and as a further starting material, it uses distillation residues from the re-generating of ethylene glycol, which are produced in the production of poly (ethylene glycol terephthalate) 2 201839 vzoroa

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excreted from dimethyl terephthalate and ethylene glycol, which account for about 40% of the total amount of waste.

Ethylene glycol distillate residues at the room temperature are paste-like and usually composed as follows: ethylene glycol diethylene glycol bia (hydroxyethyl) terephthalene oligomers of bis (hydroxyethyl) terephthalate doGeO2, MgO, MnO, ZnO, respectively. TiO2 monohydroxystyl terephthalate up to 31.5% mass 17.0 masses 24.0 mass% 21.0 mass

The oscillation composition is due, first, to the fact that, in addition to the ethylene glycol content (OH number in the range of 15 to 30), the distillation residue is mainly due to particulate matter, in particular to oligomers, when the distillation residues are discharged into the containers. overwhelms the packaging.

Especially preferred is the treatment of these distillation residues with estersification or purification. polycondensation, after treatment to an approximate conjugate content of hydroxyl groups suitable for the acid content, respectively. iohahydrides for the eoterifica- The treatment can be carried out either by distilling off or adding ethylene glycol or glycol so that the hydroxyl content of the resulting mixture is 24 to 26%.

The molar amounts of the acids in theory, in the case of polyosterification, correspond to the amounts of glycols used, but from a practical point of view, a small excess of glycol calculated on the total amount of the dicarboxylic acids used is preferred. An excess of debris can be eliminated in priobofau or in the polyestersification reaction.

The molar amount of individual d1-carboxylic acids and bis (hydroxyethyl) terephthalate is different depending on what properties are expected from the resulting resin. For example, a low proportion of fumaric acid results in increased flexibility, shrinkage stress, and the amount of heat released during curing.

In order to prepare such a modified resin, there is absolutely no specific alignment, since the preparation is carried out in a standard manner for alignment, customary for this type of reaction. It is preferable to work in an atmosphere of carbon dioxide or nitrogen because the esterifluoroacetate in the presence of air results in the formation of a dyed, viscous, and stable product. The reaction temperature in the polystyrene & phase step is up to 230 ° C, optimally up to 200 ° C, while the reaction water released by the polyosteric acid is continuously removed by either a simple or azeotropic distillate. 3 201839

The esterification process can be monitored according to the amount of water released by the polyester or the water. by analytical determination of the acid number of the reaction mixture. The reaction is usually complete when the acid number of the reaction mixture is 40. The unsaturated polyesters can then be dissolved in the reactive ethylenic unsaturated solvent, preferably in styrene, at 20 to 10% by weight. calculated on the amount of polyester present.

The formation of a and is carried out by the polymerization catalysts used in particular in the hardening of unsaturated polyester elements. For cold curing, for example, a catalytic system consisting of cyclohexanone peroxide or methyl ethyl ketone peroxide and a metal urea, optionally dibenzoyl peroxide and a target, is suitable. amine · Example 1: A batch consisting of 147 g of maleic anhydride 222 g of phthalic anhydride 121.6 g of monopropylnglycol 220.2 g of deetilizing residues containing 24 to 26% of OH-group is charged to the esterification apparatus. within 1 hour the batch melted and heated to 110 ° C. The temperature of 110 ° C is maintained for 30 min · The behorn temperature is then raised to 210 ° C for 4-5 hours. At this temperature, up to an acid number of 38-42 mg KOH / g is continued in the esterification. The polyester is cooled to 175 ° C, aa 3.125 g of hydroohinone and 0.35 β para-fin are added. After further cooling to 100 ° C, 386 g of ahyvima was added and the nutrient was cooled to room temperature. Example 2 Feed consisting of 220.5 β of maleic anhydride 333 g of phthalic anhydride 159 g of diethylene glycol 330 g of deetilizing residues containing 24 to 26% OH - are charged to the esterification apparatus. A temperature of 110 ° C is maintained for 1 hour and maintained for 30 minutes. Then the temperature is raised to 210 ° C for 4-5 hours. At this temperature it is esterified to an acid value of 38 to 42 mg KOH / g, the polyester is cooled to 175 ° C, 0.188 g of hydroohinone and 0.53 β of paraffin are added. After further cooling to 100 [deg.] C., 600 g of styrene are added and the salt is cooled to room temperature.

Claims (2)

4 201839 Example 3 Containing 147 g of maleic anhydride 222.2 g of phthalambydride (g) of diethylene glycol 248 g of distillation residue containing 24 to 26% of OH-group are metered into the esterification apparatus. A temperature of 110 ° C is reached within 1 hour and maintained for 30 min. Thereafter, the temperature is gradually raised to 210 ° C over 4-5 h. In this case, it is esterified up to an acid number of 30. The polyester and are cooled to 175 DEG C., and 0.15 g of hydroohinone and 0.4 g of paraffin are added. The dilution with styran and after further cooling to 100 ° C, 350 kg of styrene are added. Thereafter, the animal is cooled to room temperature. P R E D E T OF THE INVENTION CLAIMS 1. A process for the production of a modified unsaturated polyether resin or a cepelymerate and an annual solvent thereof by polyesterification of di- and / or polyols with dicarboxylic acids and / or anhydrides at elevated temperatures, during the course of the polyester reaction. water is evolved and, preferably in the form of an azeotrope mixture with xylene, and auxiliary substances such as stabilizers, paraffin, solvents are added to the product after partial treatment, and the polyester is prepared from dicarbonyl acids and (or iohahydrides, di- and / or polyols and from the distillation of ethylene glycol regeneration from the production of polyethylene glycol terephthalate, the amount of distillates and residuals used being in the range of 10 to 80% by weight). calculated on the used acid and / or anhydride and polyester esterification is carried out in a first stage at a temperature of 90 to 120 ° C and in a further step at a temperature of 190 to 220 ° C. 2. Process according to claim 1, characterized in that the distillate residues from the ethylene glycol regeaeration from the production of polyethylene glycol terephthalate and before polyesterification are treated by adding at least one C 6-Ciclu alkyl group to an amount of 20 to 20% by weight of total hydroxyl groups. 30%, preferably 24 to 26%, the deviation from the predetermined value being max.