HU177571B - Process for producing modificated condensed resins - Google Patents

Description

Process for the preparation of modified condensation resins

The present invention relates to a process for preparing modified condensation resins and combination lacquers containing such resins.

In addition to polyhydric alcohols and polybasic acids, an aldehyde is used for the condensation and the reaction is carried out in the presence of organic or inorganic metal compounds. By incorporating said components into the condensation resins, they improve their performance properties and quality.

Polyester resins, one of the major groups of condensation resins, are known to be (poly) condensation products of polyhydric alcohols and polybasic acids. The polybasic carboxylic acids are saturated or unsaturated, aliphatic, aromatic or hydroaromatic. Such carboxylic acids include maleic acid, maleic anhydride, 1 adipic acid, citric acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride. Among the polyhydric alcohols used are: ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, glycerol, trimethylolpropane, 2 pentaerythritol, and also pentamethylene glycol, trimethylolethane, hexanethiol, xylitol, mannitol, polyether polyol ethanol, polyoxyethylene glycol, epoxy diol, epoxy. In addition to or in place of polyhydric alcohols, 2 monovalent, saturated or unsaturated, monovalent or branched, predominantly straight or branched chain carbon monoxide moieties may be used. fatty alcohols. Examples are pentanol, hexanol, dodecanol, octadecanol. Monovalent alcohols are usually used when the proportion of tricarboxylic acids or higher carboxylic acids involved in condensation is significant.

Depending on the variable components qualities of the condensation resin is widely secured ^and MID changed. The general grouping of polyester resins for condensation resins may be based on their aliphatic monocarboxylic acid content (long chain fatty acid content). Polyester (alkyd) resins in the lacquer industry are mostly modified, with the addition of fatty acids, the structure of the alkyd resins can be loosened, and unsaturated fatty acids can produce air-drying products similar to drying oils. Fatty acids are unsaturated or saturated aliphatic or cycloaliphatic carboxylic acids of natural or synthetic origin, mostly vegetable oils. Oil-modified alkyd resins may be divided into fatty alkyd resins with a fat content of more than 60%, semi-fatty oils with a fat content of between 45% and 60% or with an oil content less than 45% by their oil content. Alkyd resins, when dissolved in a suitable solvent, in association with a number of other types of compounds and / or excipients, can be prepared in the form of resin solutions of variable properties which are suitable for use in a wide variety of applications. Are they usually produced in a one-step process, with fatty acids combined with phthalic anhydride and polyhydric alcohol? esterified. Their production is described in more detail in the following books, among others: Drinberg, AJ: Technology of Film-Making Materials, Budapest, 1958; Wagner, H. - Sarx, HF: Lackkunstharze, Munich, 1959; Payne, HF: Organic Coating Technology, New York.

1954; Martens, C.R.: Alkyd Resins.

AJ. Am Oil. 42 (2), 96-98 (1965) Chemist's Soc., For example, pentaerythritol modified with polyhydric alcohols and polyhydric acids is used in the preparation of alkyd resins. Alkyd resins made from modified pentaerythritol, phthalic anhydride, and tall oil fatty acids have good application properties.

Ellis, The Chemistry of Synthetic Resins, pp. 951-954 and 980, describes the preparation and use of alkali resins and heavy metal salts of phthalic acid monoalkyl esters. The high acidic materials of about 100 are neutralized with alkali and then converted to the corresponding heavy metal derivatives in aqueous solution by heavy metal salts. Heavy metal derivatives can be used as driers in paints and varnishes, promoting the compatibility of nitrocellulose and cellulose acetate with other synthetic resins. reducing the softening point;

934-940 of the cited reference book. According to pages 5 to 8, alkyd resins can be modified with many other types of synthetic resins, and the properties of the finished products can be modified accordingly.

Due to the wide range of possible applications, there is an increasing demand for condensation (alkyd) resins used in the lacquer industry. Of the alkyd resins which form a large group of condensation resins, both air-drying and thermosetting types are important. Their common disadvantage is poor chemical resistance, especially acid and alkali resistance. Their adhesion, hardness and drying of air-drying types are not always adequate, some resins are thermosensitive. During cooking, the viscosity increase in the reaction mixture is not uniform, with sudden increases in viscosity, caused by a disproportionate increase in the higher molecular weight portions, which also poses a risk of gelling. Because of the danger of glesles, the resin action must be terminated before the reaction is completed, so that the proportion of low molecular weight components remaining in the reaction mixture is high, which adversely affects the properties of the coating film. Uneven increase in viscosity during cooking at lower condensation rates and higher acid numbers in the presence of significant levels of unsaturated fatty acids. In this case, the polymerization reaction takes place and the molecular weight increase due to the polymerization inhibits the development of the polycondensation reaction, and the condensation reaction may be completely stopped while the polymerisation reaction proceeds. This can cause a sharp increase in viscosity, which is an obstacle to the continued and safe production of resin. In lacquer technologies, cooking with alkyd resins is usually completed at a viscosity of 1000 cP, and in many cases such an acidity value is inadequate. This problem is particularly acute when using alcohols with more than 3 functional groups (pentaerythritol, xylitol, mannitol). In the manufacture of fatty alkyds, only an excess of 25-30% pentaerythritol can be used to produce a product with a satisfactory degree of condensation. Such a product has a lower average molecular weight due to the high alcohol excess and the number of hydroxy sweepings in the molecule which degrades the physical and chemical resistance of the formed coatings. Alcohols containing less functional groups (such as glycols) are used in appropriate proportions instead of pentaerythritol to increase physical and chemical resistance. For the same glikolok.bevitele higher degree of condensation (lower acid number) can be cl _i, b ^ _onatj? However, if weaker than pentaeritritalapú alkyd resins mek.tul f & ^ ^ jdŐa EAI. The use of multifunctional alcohols (polyols) is a major problem in the preparation of further alkyd resins, especially in the case of condensation products without monocarboxylic acid. In order to avoid prematurely gelling during the cooking time, a higher excess of polyol is used.

SUMMARY OF THE INVENTION It is an object of the present invention to improve the quality properties of condensation (alkyd) resins, in particular their chemical resistance, adhesion, and drying properties, and increase their elasticity. Other objectives include achieving a uniform increase in viscosity during cooking of the resin, safe handling and control of production, reduced acidity with improved condensation rate of the resin, increased uniformity of molecular weight distribution, and kept to a narrower range. '

The disadvantages of the prior art can be overcome and these objects can be achieved by employing the process of the present invention for the condensation of polyhydric alcohols and polybasic acids at temperatures between 180 ° C and 280 ° C, characterized by the following features:

(a) an aliphatic, aromatic, hydroaromatic, saturated or unsaturated aldehyde or a mixture thereof, up to a maximum of 66% by weight of the functional groups of the alcohols used for condensation; and

(b) between 0,001 and 3,5% 'by weight of the alcohols introduced, in quantities of lithium, sodium, potassium, zinc, lead. calcium. strontium. organic or inorganic compounds, or mixtures thereof, of barium, antimony, titanium, or zirconium metals, soluble or dispersible in the condensation reaction mixture.

After the condensation reaction, the reaction mixture is dissolved in a suitable solvent or solvent mixture and, if desired, mixed with other known lacquer components.

Among the aldehydes useful in the present invention, the following are highlighted. formaldehyde, acetaldehyde, butyridehyde, pelargonaldehyde (nonanal), stearyl aldehyde (octadecanal, crotonaldehyde (butenal), 2-isobutyl-2-propenal (Aizobutylacrolein), 2,4-hexadienal, octadecenal, benzaldehyde, coumaldehyde) ), phenylacetaldehyde, naphthylaldehyde, cinnamic aldehyde, cyclohexane aldebid, cyclohexene aldehyde.

Suitable inorganic or organic metal compounds are those. lithium chloride, lithium hydroxide, lithium carbonate, lithium hydrophosphate, lithium acetate, lithium butylphosphate, lithium isopropylphosphate, the corresponding sodium and potassium compounds of the same compounds, zinc chloride, zinc oxide, zinc oxides, zinc oxides, zinc oxides, zinc oxides, calcium, stroncitun · barium compounds, antimony oxide, antimony hydroxide, titanium dioxide, titanium hydroxide, triethanolamine titanate, crazyltitanate, zirconium oxide, zirconium carbonate, zirconium octoate. Organic or inorganic metal compounds which may be used are organic or inorganic salts of tin such as tin chloride, tin octoate and the like. too. The listed metals are preferably used in an amount of 0.05 to 1.0% by weight based on the weight of the polyhydric alcohols added to the reaction mixture.

The resulting condensation reakqóelegyet an aliphatic, hydroaromatic yagy .aromás szénindrogén, krezc ^. ^ EpQl aliphatic or £ ikloalifás ester / élészter ether over _{r b} r (nná8xl '^ ^{9' riOBlí} '^ • ^va 8y ftp'

The resin solutions according to the invention may be combined with other resins depending on the desired quality of the final product. The following are listed: urea resin, melamine resin, phenolic resin, cellulose derivatives, vinyl derivatives, acrylates, chlorine rubber, polyisocyanate. The resins produced according to the invention are suitable for improving the properties of other lower quality resins.

A common advantage of the process condensation resins is that they are air dried, more resistant to burning or overburning, harder, more resilient, and more resistant to alkaline reagents than the coating films of condensed synthetic resins without aldehyde or metal compound. The improvement in properties is particularly significant in the case of fused coating films.

It is assumed that the incorporation of aldehyde groups into condensation resins is via acetal groups, and that the acetal bond has been found to be more stable and heat resistant than the ester bond. In addition to the acetal groups, the metals incorporated into the condensed molecules, on the one hand, uniformly increase the viscosity during cooking of the resins, eliminate the risk of gelling, the molecular weight distribution of the finished synthetic resin is even and narrow, the condensation level improves. Metal compounds contribute to the chemical resistance, adhesion, drying and heat resistance of lacquer coatings. Thus, according to the invention, the application properties of the lacquer industry are enhanced, on the one hand, in the field of alkyd resins, and, on the other hand, in the case of air-drying fatty alkyd resins. It is particularly advantageous to use the invention to improve the properties of different types of lacquer compositions.

The process of the present invention will be described in more detail in the Examples. The quality properties of the condensation resins produced by the examples are greatly improved, however, due to the variety of components that may be used, all possible methods are omitted to avoid profitability. However, it will be apparent to those skilled in the art that, in practice of the process of the present invention, many varnish compositions having technical advantages over known condensation resins can be prepared, even beyond the scope of the examples.

Example 1

Into a flask equipped with an intensive stirrer, a thermometer and a condenser fitted with a water separator are added 2800 parts by weight of soybean fatty acid, 1088 parts by weight of pentaerythritol, 1184 parts by weight of phthalic anhydride, 36 parts by weight of butyric anhydride and 3 parts by weight of eironium. With vigorous stirring, the reaction mixture is heated to 250-260 ° C so that the temperature rise is 25-30 ° C per hour from 100 ° C. The reaction mixture is maintained at 250-260 ° C until the acidity of the mixture is reduced to 10 and the viscosity, dissolved in white spirit, is 1: 1 at 25-100 ° C (900-1200 cP). The lacquer thus obtained is utilized as a well-drying product with or without pigment in the air.

Example 2

Into a flask equipped with an intensive stirrer, a thermometer and a condenser fitted with a water separating cap, we add 1800 parts by weight of tallow fatty acid, 1000 parts by weight of pentaerythritol, 123 parts by weight of glycerol, 1184 parts by weight of phthalic anhydride , 5 parts by weight of lithium hydroxide, 0.5 parts by weight of calcium dihydrogen phosphate and 2 parts by weight of triethanolamine titaniumate. With vigorous stirring and in an inert atmosphere, the reaction mixture is heated to 250-260 ° C so that the temperature rises from 100 ° C to 25-30 ° C per hour. The reaction mixture is maintained at 250-260 ° C until the acid number drops below 15 and the viscosity when dissolved in white spirit is 1: 1 at 1000-1500 cP at 25 ° C. The resulting varnish can be used as a well air-drying product with or without pigmentation.

Example 3

In a flask equipped with an intense stirrer, a thermometer and a condenser fitted with a water separator, 2800 parts by weight of sunflower fatty acid, 816 parts by weight of pentaerythritol,

245.5 parts by weight of glycerol, 1036 parts by weight of phthalic anhydride, 166 parts by weight of terephthalic acid, 69 parts by weight of 2,6-non-denatured, 0.5 parts by weight of zinc chloride, 0,5 parts by weight of sodium carbonate, 0,5 parts by weight of antimony; 5 parts by weight of zirconium carbonate and 0.5 parts by weight of cresyl titanium. Under vigorous stirring and in an inert atmosphere, the reaction mixture is heated to 250-260 ° C so that the temperature rises from 100 ° C to 25 ° C per hour. The reaction mixture was heated from 250 to 260 ^J C, until an acid number lower than 10, the viscosity is dissolved in white spirit f: 1 25 C-800 I300cP. The lacquer thus obtained can be used with or without pigment as a well-air-drying product.

Example 4

Into a flask equipped with an intense stirrer, a thermometer and a condenser fitted with a water separator, were added 864 parts by weight of 144 average molar saturated synthetic fatty acids, 1480 parts by weight of phthalic anhydride, 98 parts by weight of maleic anhydride, trimethylolpropane, 615 parts glycerol, 0.5 parts lead octanol, 0.5 parts potassium isopropyl phosphate, 0.5 parts potassium carbonate, 0.5 parts strontium naphthenate, 0.5 parts sodium sodium acetate, and 0.5 parts eirconium. Under vigorous stirring and inert atmosphere, the reaction mixture is heated to 220-230 ° C so that the temperature rises from 100 ° C to 20-25 ° C per hour. The reaction mixture is maintained at 220-230 ° C until the acid number drops below 10 and the viscosity when dissolved in xylene is about 1000 cP in a 1: 1 ratio. The resulting varnish can be well combined with melamine, urea, or phenolic resin and the combination can be used as a thermosetting varnish with or without pigmentation.

Example 5

864 parts by weight are prepared in a flask with an intensive stirrer, a thermometer and a condenser fitted with a water separator

Saturated synthetic fatty acids having from 7 to 10 carbon atoms, 1480 parts by weight of phthalic anhydride, 146 parts by weight of adipic acid, 1230 parts by weight of glycerol, 142 parts by weight of pelargonaldehyde, 148 parts by weight of p-isopropylbenzaldehyde, 132 parts by weight of cinnamon aldehyde, , 1 part by weight of lithium butyl phosphate and 1 part by weight of triethanolamine titaniumate. Under vigorous stirring and under an atmosphere, the reaction mixture is heated to 200-240 ° C. The reaction mixture is maintained at 200-240 ° C until the acid number drops below 10 and the viscosity when dissolved in xylene is about 1500 cP in a 1: 1 ratio. The resulting lacquer is well combined with isocyanates such as Desmodur N and can be used as an air-drying two-component polyurethane lacquer with or without pigmentation.

Example 6

1940 parts by weight of dimethyl terephthalate, 610 parts by weight of ethylene glycol, 130 parts by weight of pentaerythritol, 400 parts by weight of glycerol, 100 parts by weight of benzaldehyde and 2 parts by weight of antimony oxide are placed in a flask equipped with an intense stirrer, thermometer and water separator. With vigorous stirring and in an inert atmosphere, the reaction mixture is heated to 200-250 ° C and the reaction mixture is maintained at this temperature until the product has a softening point of 90-105 ° C. The resin thus obtained is soluble in a 3: 1 cresol xylene solvent mixture and the product can be used as a thermosetting lacquer.

Example 7

Into a flask equipped with an intense stirrer, a thermometer, a water separating condenser, 584 parts by weight of adipic acid, 270 parts by weight of butylene glycol, 268 parts by weight of trimethylolpropane, 15 parts by weight of paraformaldehyde, 0.05 parts by weight of zinc chloride and 0.01 parts by weight of tin. Under vigorous stirring and inert atmosphere, the reaction mixture is heated to 240 ° C. At this temperature, the reaction mixture reaches 4 acid numbers over three hours. The finished alkyd resin was cooled and made into a 75% solution with 3: 1 xylene: cyclohexanone. 1 part by weight of the 75% alkyd resin solution thus prepared is mixed with 75% solution (13.5% isocyanate) in 1 part by weight of a solution of 1 mol of trimethylolpropane and 3 mol of toluene diisocyanate (Desmodur L-75). The resulting mixture was adjusted to a consistency suitable for brush application with xylene: cyclohexanone (3: 1). When applied to wood, the resulting film reaches a drying rate of 1 after 20 minutes, a drying rate of 7 after 4.5 hours, can be sanded after 2 to 2.5 hours, and a wear value of 600 after 72 hours of conditioning.

The same alkyd resin, prepared without paraformaldehyde and zinc and tin catalyst at 240 ° C after 6 hours, reduces the acid number of the product to 5. This alkyd resin is similarly prepared with Desmodur L-75 lacquer and applied to wood to dry level 1 after 30 minutes, to finish drying pond 7 hours, to sand after 3.5 to 4 hours, and after 72 hours conditioning wear value is 400.

Example 8 (Comparative)

The ingredients corresponding to compositions A, B, and C below are prepared in a flask equipped with a vigorous stirrer, a thermometer, and a water-cooled condenser.

THE B C phthalic anhydride 1258 1258 1258 pentaerythritol 1088 1088 1088 tall oil fatty acid 2800 2800 2800 paraformaldehyde - 30 30 ZnCl ₂ - - 3 LiOH - - First zirconium octoate - - 6

Under vigorous stirring, each reaction mixture is heated to 240 ° C at the same rate and cooked at 240 ° C until the viscosity of the sample solution diluted 50% in white spirit reaches 1200 cP.

The product corresponding to composition A) achieves the desired viscosity within 15 hours, the acid number is then 20, and the acid number 20 is already at 700 cP, since then it has remained unchanged, only the viscosity of the product has increased.

The product corresponding to composition B) achieves the desired viscosity within 14 hours, at which time the acid number is 16, which reaches a steady decrease during cooking.

The product corresponding to composition C) achieves the desired viscosity within 7 hours, at which time the acid number is 8.5, which values reach steadily.

An alkyd resin of compositions A, B and C is prepared in a 50% solution of white spirit. To each was added 0.9% cobalt desiccant (containing 6% metal Co) and 2.5% lead desiccant (containing 20% metal lead). A film of the same thickness (about 50 microns) is carefully applied to each of the carefully cleaned stainless steel sheets. The drying time (according to MS 9696/23), water uptake (MS 96 96/12) and Buchholz hardness (MS 9696/26) of each film are examined. The result is summarized in the following table:

__drying_ water uptake Buchholz1. Grade 6 Hardness

THE 120 minutes 7 days 3.3% 71 B 80 minutes 5 days 3.5% 91 C 50 minutes 3 days 1.8% 142

The change in acid number and viscosity of the resins corresponding to composition A 'B and C shows that the polycondensation of composition A and B is lower (as shown by the higher acid number) than that of composition C. Accordingly, composition C resin has a higher average molecular weight and thus a higher quality as evidenced by the film properties test results. The quality of alkyd resins is determined by the length of the linear backbone formed by the polycondensation reaction of the polyol and the polycarboxylic acid. The measure of this degree of polycondensation is the acid number, the lower the acid number, the higher the degree of face condensation, the better the quality of the resin. Saturated or unsaturated fatty acids are incorporated into the side of this linear chain. The polymerization of these fatty acids and their possible polymerization does not substantially affect the properties of the base resin formed by the polycondenser at the same composition, EM confirms A. Viscosity of resin composition is equal to composition. The same viscosities are found in

The resin compositions A and B were obtained by polymerization of unsaturated fatty acid (tallow fatty acid), and the resulting increase in molecular weight is not of such a scale and nature as to further improve the film quality.

Example 9

730 parts by weight of adipic acid, 360 parts by weight of butylene glycol, 268 parts by weight of trimethylolpropane, 112 parts by weight of cyclohexane aldehyde and 3 kg of tinoctate are placed in a flask equipped with an intensive stirrer, thermometer and water separating condenser. Under vigorous stirring and inert atmosphere, the reaction mixture is heated to 240 ° C. The mixture is kept at this temperature and the acid value of the product drops below 4 in 4 hours. The finished alkyd resin was cooled and made into a 50% solution in cyclohexanone. 1 part by weight of the 50% alkyd resin solution thus prepared is mixed with 2 parts by weight of 60% melamine resin. The melamine resin is a 60% solution of butyl etherated hexamethylolmelamine, but may also be replaced by a 60% solution of butyl ether tetramethyl urea or butyl ether phenyl phenyl formaldehyde. The applied film of the resin mixture would cure at 120 ° C in one hour, with an Erichsen elasticity of 10, 100% adhesion, 3 H hardness, 3 hours in unchanged 10% NaOH in 100 ° C water. unchanged after 10 h, unchanged after 10 h in 10% HCl.

Similar results are obtained when 110 parts by weight of cyclohexanaldehyde are used in the preparation of the alkyd resin instead of 110 parts by weight of cyclohexanaldehyde.

When the alkyd component of the above alkyd-melamine resin combination is prepared without cyclohexanaldehyde and tinoctoate, the film, which is fired at 120 ° C for 1 hour, has an Erichsen elasticity of 9, 100% adhesion, and 2H pencil hardness at 100 ° C. in water after 3 hours the film is slightly opalescent, in 10% NaOH solution after 2 hours the film is opaque, in 10% HCl the film is opaque after 2 hours.

Claims (3)

Patent claims A process for the preparation of modified polyester resins by condensation of polyhydric alcohols and mono- and / or polybasic acids at temperatures between 180 and 280 ° C and optionally mixing the resulting product with urea resin, melamine resin, phenol resin or polyisocyanate, condensation, in the proportion of 5 to 66 mol%, based on the functional groups of the alcohols, of an aliphatic, aromatic, hydro-5 aromatic, saturated or unsaturated aldehyde or a mixture thereof and 0.001 to 3.5% by weight of lithium, sodium, potassium , zinc, lead, calcium, strontium, barium, antimony, titanium, zirconium or tin, soluble in the condensation reaction O or dispersible in the presence of an organic or inorganic compound or mixture thereof, and after the condensation reaction, the condensation resin is dissolved in an aliphatic, hydroaromatic or aromatic hydrocarbon solvent and, if desired, known It is mixed with other resin components in 5 ways. (Priority: November 11, 1980) Process for the preparation of modified polyester resins by condensation of polyhydric alcohols and mono- and / or polybasic acids at temperatures between 180 ° C and 280 ° C and optionally mixing the resulting product with urea resin, melamine resin, phenolic resin or polyisocyanates, that condensation, in the proportion of 5 to 66 mol% based on the functional groups of the alcohols introduced, is an aliphatic aromatic, 5 Hydroaromatic, saturated or unsaturated aldehydes, or mixtures thereof, and from 0.001 to 3.5% by weight, based on the weight of alcohols, of metals of lithium, sodium, potassium, zinc, lead, calcium, strontium, barium, antimony, titanium or zirconium the condensation reaction is dissolved in an aliphatic, hydroaromatic or aromatic hydrocarbon solvent and, if desired, known in the art, is carried out in the presence of an organic or inorganic compound or mixture thereof which is soluble or dispersible in a condensation reaction mixture. It is mixed with other resin components in 5 ways. (Priority: March 19, 1979) 3. The process according to claim 1, wherein the aldehyde is formaldehyde, acetaldehyde, hutiraldehyde, pelargonaldehyde (nonanal, stearylaldehyde (octadecanal), crotonaldehyde (butenal), 2-isobutyl-2-propenal (-isobutyl) -isobutyl). , 2,4-hexadiene, octadecenated, benzaldehyde, coumaldehyde (4-isopropylbenzaldehyde), phenylacetaldehyde, naphthyl aldehyde, cinnamon aldehyde, cyclohexane aldehyde, cyclohexene aldehyde (March 19, 1979). ) Responsible for publishing: Director of Economic and Legal Publishing House 826684.66-42 Alföldi Nyomda, Debrecen - Chief Executive Officer: István Benkő Director