CS232307B1 - Processing of binding agent on unsaturated polyester bitumen base - Google Patents

Abstract

Production of binders based on unsaturated polyester resins suitable mainly for production dicarboxylic based coating agents acids and / or their anhydrides triacids or precursors thereof (olefin oxides), generally catalyzed by esterification, resp. polyesterification and initiated * crosslinking by olefinically unsaturated aonoaers (styrene, vinyltoluene, divinylbenzene, acetates) so that the dicarboxylic acid dicarboxylic acid and / or anhydrides acids consist of 30 to 100% (50-80%) of the additional acid products aaleinic and mainly allyanic anhydride with dianal to C1 () (5-norbornene-2,3-anhydrides) -dicarboxylic acid and adducts with dicyclopentadiene and 4-ethyl-4-tetrahydrophthalic anhydrides and 3-aethyl-A-2 - -tetrahydrophthalic acid).

Description

The invention relates to the production of binders based on unsaturated polyester resins, in particular uninhibited types of polyester resins, suitable, in particular, for the preparation of high gloss gloss coatings after curing and very good adhesion to substrates.

It is known that the suppression of oxygen inhibition when curing unsaturated polyester resins, and thus their tackiness, is most easily achieved by preventing the resin from contacting the air, e.g. by the addition of waxy substances which, although they dissolve in the resin, their solubility decreases during curing of the lacquer film. As a result, they are deposited excretely on the surface in the form of a thin film which prevents the polyester from coming into contact with air. Non-polar paraffin with a melting point of 54 to 56 ° C, which is the least soluble in the resin and is therefore effective in very small quantities, has proven to be the most suitable for this purpose. However, the use of paraffin as well as other waxy fabrics has the disadvantage that the surface of the paraffin-cured polyester lacquer films is always opaque by the action of the treated paraffin, so that it has to be ground and polished.

This makes processing considerably more expensive, notwithstanding the fact that the presence of paraffin in the resin also impairs adhesion to the substrate, since all the paraffin is not deposited on the surface, but is split between the lacquer film and the substrate. Also, pouring or spraying the surface without removing the wax layer results in impairment of casting.

In order to eliminate oxygen inhibition during curing, it has been suggested to add some other substances to the resin, such as cellulose acetobutyrate, nitrocellulose and others, but a slightly protective effect is always inferior to the protective paraffin layer. Alkyl ethers of higher alcohols (DAS 1 008 435, US Pat. 2 852 489, DAS 1 020 428), as well as various special glycols (V. British. Pat. and acids such as e.g. tetrahydrophthalic acid (U.S. Pat. No. 118,366), adducts of maleic anhydride and anthracene or maleic anhydride on rosin (DAS 1,069,871), and the like. The disadvantage, however, is their technically demanding preparation and high price of these raw materials.

Although the production of unsaturated polyester resins is well known (Mleziva J. et al .: Polyesters, their Production and Processing, a. 344-498, SNTL - Publishing House of Technical Literature, Prague / 1978 /), using various starting materials and their technology. The technical and economic parameters of the final products can be improved.

According to the invention, a process for the production of binders based on unsaturated polyester resins suitable mainly for the production of paints, based on dicarboxylic acids and / or dicarboxylic acid anhydrides, monovalent to trivalent alcohols and / or olefins, usually catalyzed by esterification and / or polyesterification and initiated % by crosslinking by means of olefinically unsaturated monomers, such that the dicarboxylic acids and / or dicarboxylic acid anhydrides as starting material consist of 30 to 100 wt. adičnýeh products of maleic acid and / or maleic anhydride with dienes to C, _o.

An advantage of the process of making the unsaturated polyester resin binders of the present invention is the raw material availability of the maleic anhydride and acid addition products. maleic with dianes C ₄ to C, θ, especially cyclopentadiene and dicyclopentadiene, high leek and increased adhesion of the produced resins also on smooth and non-porous surfaces. In addition, the high gloss makes it possible to increase the productivity of the production of quality products and by applying the binders prepared according to the invention. E.g. in the furniture industry it is possible to omit or at least limit the polishing operations.

Suitable dicarboxylic acids and their anhydrides are, in particular, technically and commercially available phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid ealeinic acid, fumaric acid, maleic anhydride, adipic acid, glutaric acid, succinic acid and the like. Important is in particular acids and acid anhydrides of maleic acid addition, and especially maleic anhydride to dienes to _{C] o.} Of these, the 5-norbornene-2,3-dicarboxylic acid anhydrides (endo and exoform), respectively, are most important. bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, 4-ethyl-4'-tetrahydro-phthalic acid and its anhydride, 3-methyl-4'-tetrahydro-phthalic acid and its anhydride, and 4- tetrahydrophthalic acid, tetrahydrophthalic anhydride and the dicyclopentadiene addition product by maleic acid, respectively. moleic anhydride, optionally alkenes with maleic anhydride. As monohydric alcohols are suitable primary aliphatic alcohols and C _f g hereinunder cykohexanol, sec-alcohols, ^Cg-C18 ·

Of particular interest are diols and trivalent alcohols, of which in particular ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diols C1 to C, and their precursors - olefin oxides (ethylene oxide, propylene oxide, olefin oxide to C1g), neopentyl glycol , glycerol, trimethylolpropane, partially esterified pentaerythritol and dipentaerythritol. As esterification and polyesterification catalysts, conventional esterification catalysts (strong acids such as acid to trihydrogenphosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid, then metal oxides such as germanium oxide, alumina, antimony trioxide, molybdenum trioxide, organo compounds and titanium and tin) are applied. /.

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Suitable olefinically unsaturated monomers are, in particular, starch, alpha-methylstyrene, vinyltoluene, methacrylic acid and its esters, divinylbenzene, monochlorostran, dialyl phthalate. As initiators of copolymerization of unsaturated polyesters with olefinically unsaturated monomers are free radical generating substances such as hydroperoxides (tert-butyl hydroperoxide, cumenyl hydroperoxide), dialkylperoxides (di-tert-butylperoxide), diacylperoxides (dibenzoyl peroxide, dilauroyl peroxide, dilauroyl peroxide) however, ketone peroxides (methyl ethyl ketone peroxide, methylcyclohexanone peroxide) and aldehydeoperoxides. Peroxides are usually combined with accelerators to cure the resins at room temperatures and below (above 0 ° C). These include, in particular, tert-alkylamines which are suitably combined with diacyl peroxides, further compounds, in particular cobalt, manganese and vanadium salts, which are suitably combined with ketone peroxides and hydroperoxides.

Together with the free-radical initiators and accelerators, or only as the source itself, they allow the formation of free radicals necessary for the free-radical copolymerization that will cause the resin to cure! different types of radiation (UV-radiation, gamma-ray radiation, laser beams, etc.), but the most important from the technical point of view is ultraviolet radiation.

Resins according to the invention are suitable to be produced under an inert atmosphere. Monomers and optionally unsaturated polyester resins can be stabilized using known polymerization inhibitors (hydroquinone, reacrolol, pyrocatechol, alpha-naphthol, methyl-1,4-benzoquinone, methyl- and dimethylhydroquinone ftp.).

* Further details of the process for making binders based on unsaturated polyester resins are apparent from the example in U.S. Pat.

Example 1

Into the polyesterification flask was added 270 g of the addition product prepared according to claim 3. 232,306 from the distillation residues of the pyrolysis C 1 fraction and meleine anhydride. The yellow-brown addition product has a bromine number of 90.99% Br / 100 g; acid number 401.4 mg KOH / g; saponification number 628.2 mg KOH / g; contains (in% by weight) 0,01 dicyclopentadiene, 0,47 maleic anhydride, 36,3 5-norbornene-2,3-dicarboxylic acid anhydride (endo-stereospecific form), 48,4 5-norbomannan-2,3- anhydride dicarboxylic acid (exo-stereo * Specific form) and 2% 5-norbomene-2,3-dicarboxylic acid.

93.3 g of phthalic anhydride, 61.76 g of maleic anhydride and 0.316 g of trihydrogenphosphoric acid are then added, followed by 97.6 g of ethylene glycol with 110.2 g of 1,2-propylene glycol and 64 g of xylan.

The reaction mixture aa is then esterified, respectively. Polyesterification is carried out at a temperature of 175-180 [deg.] C. and the water is discharged predominantly as an xylene azeotrope until the acid number of the reaction mixture reaches 52-55 mg KOH / g. After vacuum distillation of xylene and any unreacted diols, 0.105 g of hydroquinone are added and 309 g of pre-stabilized aging are added at 95-100 ° C. After cooling to 25 ° C, 1 g of a peroxide initiator (methyl ethyl ketone peroxide) and 0.3 g of a xylene solution of cobalt naphthenate with conc. 20 wt. After homogenization, this bituminous mixture is applied to a wood or metal substrate, where it is cured at room temperature. in addition, the curing is accelerated by ultraviolet radiation. The resin surface after curing is flexible, smooth and glossy.

Example 2

270.0 g of a mixture of addition products prepared similar to Example 1 but a slightly altered composition bromine number = 95.4 g Br / 100 g were weighed into a polyesterification flask; acid number = 364.4 mg KOH / g; saponification number = 645.4 mg KOH / g; containing 0.05 wt.

C ^ -uhTovodíkov; 0.25% dicyclopentadiene; 1.57% aaleinic anhydride; 48.7% 5-norbomene-2,3-dicarboxylic anhydride (endo-form); 33.9% 5-norbornene-2,3-dicarboxylic anhydride (oxo form); 1.3% of 3-methyl-4-tetrrahydrophthalic anhydride; 0.8% 4-methyl-Δ -tetrahydrophthalic anhydride.

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Furthermore, 59.2 g of phthalic anhydride, 84.13 g of maleic anhydride, 97.6 g of ethylene glycol and 110.20 g of 1,2-propylene glycol are melted by esterification at a temperature of 190 to 195 ° C so that the temperature of the descending condenser does not exceed 105 °. C. After reaching an acid number of 90 to 100 mg KOH / g, the reaction mixture is cooled to 145-150 ° C, 60 g of cyclohexanol are added and the mixture is further esterified. The esterification is completed when the acid number reaches 50 to mg KOH / g at 195 ° C. Thereafter, unreacted alcohols are distilled off, at 0.105 g hydroquinone and, after cooling to 95-100 ° C, 320 g styrene are added.

885 g of an unsaturated polyester resin having a viscosity of 20 mPa · s (20 ° C) having cured properties are obtained as described in Example 1.

Claims (3)

The reaction mixture is then esterified, respectively. polyesterifers at 175-180 ° C and water is predominantly azeotroped with xylene until the acid number of the reaction mixture is 52-55 mg KOH / g. After vacuum distillation of xylene and possibly unreacted diols, 0.105 g of hydroehinone and 309 g of pre-stabilized aging are added at 95-100 ° C. After cooling to 25 ° C, 1 g of peroxidic initiator (methyl ethyl ketone peroxide) and 0.3 g of xylene cobalt naphthenic solution of conc. 20 wt. After homogenization, the bituminous mixture is applied to a wood or metal substrate, where it cures or is cured at room temperature. in addition, the curing is accelerated by ultraviolet irradiation. The resin surface after curing is flexible, smooth and shiny. EXAMPLE 2 270.0 g of a mixture of addition products prepared as described in Example 1, but a slightly modified bromine number = 95.4 g Br / 100 g, acid value = 364.4 mg KOH / g were weighed into a polyesterification flask; saponification number = 645.4 mg KOH / g; containing 0.05 wt. C5-hydrocarbons; 0.25% dicyclopentadiene; 1.57% maleic anhydride; 48.7% 5-nor-boronene-2,3-dicarboxylic acid anhydride (endo-form); 33.9% 5-norbornene-2,3-dicarboxylic acid anhydride (oxo-form); 1.3% 3-methyl-4-tetrahydro-phthalic anhydride; 0.8% 4-methyl-β-tetrahydrophthalic anhydride. phthalic anhydride (59.2 g), maleic anhydride (84.13 g), ethylene glycol (97.6 g) and 1,2-propylene glycol (110.20 g) are esterified by melting at 190-195 ° C so that the temperature of the descending condenser head does not rise 105 ° C. After reaching an acid number of 90 to 100 mg KOH / g, the reaction mixture is cooled to 145-150 ° C, 60 g of cyclohexane are added and the mixture is further esterified. The esterification is terminated at an acid value of 50-55 mg KOH / g at 195 ° C. Thereafter, the unreacted alcohols are distilled off, and 0.105 g of hydroehinone is added at 80 DEG C. and 320 g of styrene after cooling to 95 DEG to 100 DEG. 885 g of unsaturated polyester resin with a viscosity of 20 mPa.s (20 ° C) with curing properties are obtained as described in Example 1. \ t A process for producing binders based on unsaturated polyester resins suitable mainly for the production of paints, dicarboxylic acids and / or dicarboxylic acid anhydrides, monovalent to trivalent alcohols and / or olefin oxides, generally by catalysed esterification and / or polyeeterification and initiated crosslinking by olefinically unsaturated monomers characterized in that the dicarboxylic acids and / or anhydride dicarboxylic acids as starting materials consist of 30 to 100% maleic acid and / or maleic anhydride addition products with dienes C4 to C10. * 2. A process for producing binders based on unsaturated polyester resins according to claim 1, characterized in that the dicarboxylic acids and / or dicarboxylic acid anhydrides consist of 30 to 100%, preferably 50 to 80% by weight, of 5-norbornene-2,3-dicarboxylic acid anhydrides, optionally also with dicyclopentadiene addition products of malenic acid. 3. A process for producing binders based on unsaturated polyester resins according to claim 1, wherein the dicarboxylic acids and / or dicarboxylic anhydrides are from 30 to 100% by weight. they consist of the products of the reaction of maleic anhydride at 140 to 300 ° C with the distillation residues of the pyrolysis C-fraction. Severografia, n. P., MOST Price 2,40 Kcs