DE2357762A1 - Polymers from diolefins, phenols and dicarboxylic acids - with good adhesion and physical props - Google Patents

Abstract

Diolefin polymers are reacted with phenols and unsatd. carboxylic acids or anhydrides contg. an ethylenic double bond. The diolefin is chosen from (a) diene homopolymers from dienes of 4-10C; (b) copolymers of >=2 dienes of type (a); (c) copolymers of dienes with minor molar quantities of a copolymsd. monomer and (d) a mixt. of >=2 components from (a) to (c), the quantity of phenol being 2-40% of the starting polymer, and the quantity of carboxylic acid or anhydride being 2-55%. The copolymer monomers are (f) unsatd. aromatic hydrocarbons boiling between 20 degrees and 190 degrees C or (g) unsatd. aliphatic hydrocarbons with a mean content of 5C, or (h) their mixts, HCHO may be incorporated in the prod. by condensn. in the ratio HCHO:phenol is 0.2:3.5. Unsatd. terpenes may also be included in the prod. The polymers have good adhesion, flexural strength, resistance to abrasion and yellowing and good compatibility with other resins; they are used in coatings, paints adhesives and printing inks.

Description

REICHHOLD-ALBERT-CHEMIE AKTTENGESELLSCKAFET, H a m b ύ r

Reaction products of diolefin polymer reactants with phenols and maleic anhydride and processes for their preparation

(Addition ru patent ............... patent application P 22 60 376.5)

The main patent .. ........... ./Patent application P 22 60 376.5) concerns implementation »-» products of diolefin polymers with phenols and olefinically unsaturated ones Dicarboxylic acids or their anhydrides, the diolefin polymer

a) a homopolymer of a diene with 4 bie M) carbon atoms and / or

b) a copolymer of the aforementioned dienes - with possibly minor molar amounts of one or more monomers - is,

the homo- or copolymer is preferably relatively low molecular weight and the phenol content · 2 < to 40, preferably 3 to 30% by weight and the proportion of unsaturated dicarboxylic acids or their anhydrides 2 to 55, preferably 5 to 30% by weight, each based on the starting polymer. According to claim 3 of the main patent, formaldehyde can additionally be condensed into the products mentioned, wherein the molar ratio of phenol incorporated to formaldehyde incorporated can be 1: (0.2-0.8). The products obtained in this way have proven their worth, but it was desirable to expand their possible uses.

In further development of the subject * of the main patent, it has now been found that high-quality products according to der.Erfindung then obtained when the molar ratio of the formaldehyde condensed into the products to form phenol (0.2 to 3.5): I, preferably at least 0.8:!., A ratio is expedient up to 1.8: 1.

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Under "relatively low molecular weight" are polymers with an average molar purpose of at least 30Ό,

Kular weight of up to 15 OQG /, preferably from 6GO to 10 OW to understand. If the products are to have the properties of hard resins or are hard resins, one will generally start from polymers with an average molecular weight of up to 5000, the minimum value being about 500, for example. If softer products are desired, starting polymers with an average molecular weight of up to J ^! 400 preferred. But it is sometimes also possible to use polymers with a higher molecular weight, fB-. to use up to 100,000. · '

Contrary to the opinion of experts, according to which formaldehyde is a phenolic resin generally only incorporated in a proportion of up to about 2 moles per mole of phenol According to the teaching of the present invention, the possibility is created for the first time to use phenol-containing resins with a substantial proportion of phenol which can contain up to 40 Z of built-in phenol to incorporate such high proportions of formaldehyde per mole of phenol. They can do the phenolic Components not bound formaldehyde proportions or in other ways react. For example, the reactive groups, for example in the form of the methylol groups of the products according to the invention, can also react with the as Starting material used diolefin polymers and / or unsaturated terpenes, like rosin, be accessible.

According to a known method, mineral oil resins

and phenol-formaldehyde resin in the presence of unsaturated carboxylic acids such as Maleic anhydride, reacted with each other and the products obtained therefrom Used as a binder for door printing inks and paints. After that it is necessary to first select a phenolic resin with the desired specific characteristics to produce, which will only be implemented in the second stage. As with the starting phenolic resin the reactive sites on the phenolic nuclei are largely occupied by the condensation, the phenolic resin can be used in this reaction only react with the methylol groups. As a result, the phenolic nuclei cannot be added to the double bond of the starting mineral oil resin.

Another advantage of the invention over the prior art is that that the products can be produced in a one-pot process. on In this way, products with an increased content of built-in phenol can also be used

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getting produced. This is made possible by condensing formaldehyde onto those phenol nuclei which were first added to the diene polymer. With the mediation of the methylol groups formed from the formaldehyde, additional phenol components can now be condensed on. This increases the number of hydroxyl groups and the free core sites at which further reactions can be carried out. In addition, the solubility of the products in various solvents, as well as the compatibility with a number of other resins or resin combinations, can change, as a result of which the products according to the invention can be used more widely. - '. '"■ .-" _ ■ - ■ _ ■ ;. ^: .

In the reaction products according to the invention, the radicals of the phenols are in 6- and / or p-position bonded to carbon atoms of the - "-. Polymers. Additionally Some of the phenolic hydroxyls can be ether-like on carbon atoms of the polymer be bound as evidenced by IR analysis.

In particular, the products obtained from low molecular weight polymers are, depending on the amount attached - that is, in the case of both small and large amounts - phenol or unsaturated acids or their anhydrides, in particular maleic anhydride, sometimes still partially unsaturated and, as a result, further addition and / or polymerization reactions accessible. The maleic anhydride adds to the double bonds not consumed by phenol addition in various ways, for example by Diels-Alder reaction and / or in the form of substituted alkenyl succinic acids. Also esterified bonds, for example by adding the double bonds ift dl · Cerfcoiiyl groups, are

möglich.Restliche double bonds of the polymers can also be consumed by cyclization React ion.

The invention also relates to a process for the preparation of reaction products of diolefin polymers with phenols and olefinically unsaturated ones Dicarboxylic acids or their anhydrides, where

a) a homopolymer of a diene with 4 to 10 carbon atoms and / or

b) a Copolymerieat the aforementioned dienes - optionally substituted with _R minor molar amounts of one or more copolymer iiler Barer monomers: -

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reacted in a reaction stage with a phenol with 2 to 55 wt .-% of unsaturated dicarboxylic acids or anhydrides thereof, based on the Ausp.angspolymerisat will n ^ w orauf no t vice releasing te phenolic moieties are removed and

Formaldehyde_ is added according to patent

(Patent application P 22 60 376.5), which is characterized in that the molar ratio from condensed formaldehyde to the phenolic components 0.2 to 3.5, preferably 0.8 to 1.8.

Different possible variants and embodiments of the method e.g. the reaction in the presence of catalysts and / or solvents, the selection of the reaction conditions, the sequence and the like, are possible as in the main patent.

The aforementioned diene homo- and / or copolymers a) and h), the copolymerizable Monomers, the olefinically unsaturated dicarboxylic acids or their anhydrides and the suitable phenols and catalysts and their proportions or mutual quantitative ratios are with the exception of the claimed Molar ratio phenol: formaldehyde the same as in the main patent.

According to the present invention, too, has a relatively low proportion of catalyst the advantages that the catalyst can be removed more easily and that the manufacture of the products has fewer corrosion problems than when using higher amounts of catalyst.

The inventive method has the advantages that light-colored products in good Yield and with significantly higher proportions of phenol and maleic anhydride than according to known processes, according to which only phenol or only maleic anhydride is added, and that surprisingly no yellowing occurs. Concomitantly used catalyst can

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separate from the reaction equipment without difficulty. Unless the The amount of catalyst is rather small, it can also remain in the products if the small amount is used in the intended use of the Products does not interfere.

The reaction products also have the advantage that their content of Phenol or unsaturated acids or their anhydrides, in particular their maleic anhydride content, can vary over a wide range. You can also be high in phenol and maleic anhydride at the same time " content, which is determined by IR spectrographic analysis, have, however, the above figures always in relation to the starting polymer are calculated.

Their viscosity can vary within a very wide range. The products can, for example, be liquid, low or high viscosity or solid.

In general, the viscosity increases with an increasing content of phenols and unsaturated dicarboxylic acids or acid anhydrides, in particular maleic anhydride. The hydroxyl and acid numbers can vary over a wide range. The solubilities in polar and non-polar solvents can be controlled by setting a certain polarity. With increasing hydroxyl numbers, the products show increasing compatibility with other phenolic resins. Next products of the invention are much more stable against oxidation by air as a wise also to thermal stress than the known phenolic or Jfaleinsäureanhydrid-Addukte.Außerdem they ⁿ verbeseerte Lös1ichkeif and compatibility with a variety of resin groups. Furthermore, the melting points of the products according to the invention can be varied depending on the phenol, formaldehyde and dicarboxylic acid or anhydride content. For example, the melting point of the products can be increased up to about 240 ° C. as desired.

The "rfindungsgemäienUnsetzungsprodukte can still partially ungesMttig _c

and have iodine numbers of over 100. As a result, they are still further addition and / or polymerization * and / or cyclization reactions accessible·

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The products according to the invention are elastic, soluble in solvents such as aliphatic or aromatic hydrocarbons, in chlorohydrocarbons such as trichlorethylene, tetrachlorohydrocarbons, chlorobenzene, and also in acetic acid esters and chloroform or the like. The solubilities can be adjusted by means of the built-in phenolic and maleic acid, partly ihydride compounds. The products according to the invention represent ?,. ^v . "Good binders for paints, adhesives and printing inks can be made accessible to other areas of application by modification, for example esterification of the carboxyl groups formed by hydrolysis of maleic anhydride with polyhydric alcohols or by salt formation. Coatings made from the products show good gloss," Good adhesive strength, good flexural strength, abrasion resistance, excellent compatibility with pigments and, in particular, products with a higher phenol content do not yellow when stoved. The lower viscosity products are particularly suitable, e.g. those with a phenol content of 3 to 20% by weight and a maleic anhydride content of 5 to 25 , preferably up to 20% by weight, especially for paints. Products with a phenol content of 10 to 30, preferably up to 25% by weight and a maleic anhydride content of 15 to 30% by weight - percentages are based on the starting polymer especially as a printing ink bin suitable for demittel. Products with a high phenol content, even over 30% by weight , and a high maleic anhydride content are suitable for water-soluble paints.

The products according to the invention are also valuable in other respects Products. In particular, they are due to the saponifiable groups suitable for the production of water-soluble binders. They can be further modified both during their formation and by subsequent reaction e.g. with terpenes and / or with fatty filen, i.e. the addition of these Substances can be made before, during or after the reaction. The products can therefore additionally at least according to one embodiment of the invention contain an unsaturated terpene. Ale terpenes come from the main patent mentioned, but preferably rosin, in question. Also can be the phenolic Hydroxyl group esterified (e.g. with acetic anhydride) or etherified (e.g. by reaction with alkylene oxides such as epichlorohydrin). Furthermore is curing with hexamethylenetetramine or reaction with Reeolen is possible.

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Λη positions still free in the phenol nucleus can also be substituted, e.g. with aryl or alkyl and / or aralkyl radicals, such as methyl, ethyl, propyl or isononyl radicals or can be obtained by addition of styrene, or .With unsaturated radicals, such as alkenyl radicals, for example the nonenyl radical or the like, and also with halogen atoms, such as chlorine or bromine will. -.- ■ "-.

The products obtained by reaction with epichlorohydrin are customary Way, e.g. with amines or acid anhydrides, hardenable. Mixed adducts with Terpenes, especially natural resin acids, are particularly good for that Areas of application mentioned above ...

In the following examples, unless otherwise stated, the viscosity was each measured in 50% toluene solution at 20 ° C.

Examples

1. 900 g of polycyclopentadiene are made from 143 p-tert-butylphenol in a core mixture and 90 g of xylene dissolved in the heat. Then it is heated to 110 ° C. "Now 108 g of maleic anhydride are added first and then 30 g of paraformaldehyde too. The mixture is then heated to in the course of 3 hours to 180 C and keeps the mixture at this temperature for 30 minutes. Within another. Stand is heated up to 250 G, whereby lighter distill off volatile components. Towards the end of the reaction, reduced pressure (60 mm) is used. A yellow-brown resin is obtained with a melting point of 151 C and a viscosity of 156 cP. The yield is 1112 g = -94%. The acid number is 3 f. The molar ratio of phenol to formaldehyde is 1: 0.95.

2. 300 p, folycyelopentadiene and 30 g rosin are dissolved in a mixture of 30 g xylene and 10 g phenol in the heat. At 120 ° C., 45 g of maleic anhydride and 6 g of paraformaldehyde are then added. The ratio of phenol to formaldehyde is 1: 1.8. The reaction mixture is then kept under reduced pressure (60 mm) for a short time for 5 to 6 hours. This gives 357 g ■ 98 X of a yellow resin having the melting] oint 188-194 C and the Virkosität of 148 cP.

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3. 300 g of polycyclopentadiene are in a mixture of 30 g of xylene and

5 g of phenol dissolved in the heat. Then 36 g of maleic anhydride and 30 g of acrylic acid and then 6 g of paraformaldehyde are added at 120.degree. The ratio of phenol to formaldehyde is I: 3.4. The mixture is then heated continuously to 250 ° C. over the course of 5 hours and worked at this temperature for 20 minutes under reduced pressure. This gives a yellow resin of melting point 220 C 33S g ■ = 90 I and einer'Viskosität of 597 cP.

4. 300 g of polycyclopentadiene are dissolved in 141 g of phenol at 120 to 130.degree. A mixture of 12 g of paraformaldehyde (phenol: formaldehyde ■ I: .O, 25) and 45 g of maleic anhydride is then added. Heated within 2 hours one then up to 180 C and holds the mixture for one hour at this Temperature.' Now the mixture is further heated up to 250 C and under reduced Pressure _ (60 inn) the unreacted portions are distilled off. 375 g of a yellow-brown resin with a melting point of 184 ° C. and one Viscosity of 497 ei '.

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Claims (1)

- sr - P a t en t a ns ρ back ! Reaction products of diolefin polymers with phenols, olefinic unsaturated dicarboxylic acids or their anhydrides and condensed formaldehyde, wherein the diolefin polymer. a) a homopolymer of a diene with 4 to 10 carbon atoms and / or b) a copolymer of the aforementioned dienes with optionally minor molar amounts of one or more copolymerizable Monomer - is where the homo- or copolymer is preferably relatively low molecular weight and the phenol content is 2 to 40, preferably 3 to 30% by weight and the amount of unsaturated dicarboxylic acids or their anhydrides is 2 to 55, preferably 5 to 30% by weight, in each case on the starting polymer, make up, according to the patent. (Paten tanmel dun p, ^p 22 f> 376.5), characterized in that the molar ratio of condensed formaldehyde to the phenolic constituents is 0.2 to 3.5, preferably 0.8 to 1.8. power. . ■ 2. Process for the preparation of reaction products of diolefin polymers with phenols and olefinically unsaturated dicarboxylic acids or their anhydrides, where a) a homopolymer of a diene with 4 to 10 carbon atoms and / or b) a copolymer of the aforementioned dienes ^ with optionally subordinate molar amounts of one or more copolymerizable Monomer - · be based on 'the AuegangspolymeriaaC reacted unsaturated in a reaction stage with a phenol with 2 to 55 wt .-% dicarboxylic acids or their anhydrides preceded not implemented "phenolic moieties are removed and formaldehyde is added to Patent ....... .. (Patent application P 2 260 376.5) in ABy d, dat the MolverhXltni * of condensed in formaldehy- to the phenolic components bia 0.2 3.5 0.8 vorxugsweiae bia _; ; 5_o 9822/07 96 -10- BAD OBiaiNAL • 40. 3. The method according to claim 2, characterized in that the formaldehyde after the reaction with the unsaturated dicarboxylic acids or their anhydrides and phenol, added and reacted with the reaction product will. 4. The method according to claims 2 or 3, characterized in that ΛηΡ terpenes and / or fatty oils are added before, during or after the reaction. November 13, 1973
Dr LG / Cb 509822/0796