DE2260376A1 - 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

Reaction products of diolefin polymers with phenols and maleic anhydride and methods of making them.

The invention relates to reaction products of diolefin polymers with phenols and maleic anhydride and processes for their preparation, their main advantage consists in the fact that phenols and maleic anhydride in a single reaction step can be attached to a wide variety of homopolymers and copolymers.

It is known that under the action of strong acids or Friedel-Crafts catalysts Phenols Olefins ortho- and / or para to phenolic hydroxyl groups as well add on the hydroxyl group itself with ether formation. Diolefins can may react with both double bonds, depending on the reaction conditions. Reaction products of diolefin polymers with phenol are also known further known by the addition of maleic anhydride to unsaturated, natural ones dle, such as wood oil or linseed oil, to produce so-called maleate oils.

Likewise, maleic anhydride can be linked to terpenes, unsaturated hydrocarbon resins and polybutadiene oils are added thermally. The production of polybutadiene oil-maleic anhydride adducts is common problematic as it. Gels easily, especially if more than 3Z maleic anhydride are to be attached. Gel formation can be caused by various additives such as Hydroquinone, ionol; Copper powder, copper naphthenate or complexing agents, reduced or prevented, but this is because of the high price of chemicals and additional work steps, e.g. removing the additives, too time-consuming. Moreover the products are mostly colored dark by the additives or in their properties worsened.

It has now surprisingly been found that phenol and olefinically unsaturated Dicarboxylic acids or their anhydrides, preferably maleic anhydride, in one single Reaction stage to a) with a homopolymer of a diene 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, preferably where the homopolymer or copolymer / is relatively low molecular weight is.

can be added to products, the phenol content 2 to 40 preferably 3 to 30% by weight and the proportion of unsaturated dicarboxylic acid or their anhydride 2 to 55, preferably 5 to 30 Ceu.-Z, based on the starting polymer, matters. These products can +) z. B. obtained when the polymers with / phenol and olefinically unsaturated dicarboxylic acids or their anhydrides, preferably Maleic anhydride, e.g. Usually the specified amounts, - optionally in the presence of at most 5% by weight, based on the starting polymer, of a Friedel-Crafts catalyst or a mineral acid such as phosphoric acid, hydrochloric acid, preferably sulfuric acid or sulfonic acids # up to the polymer # - and then unreacted phenol fractions and any catalyst used is removed. The reaction can also take place in the presence a solvent. For example, the unreacted phenol removed together with any solvents present. This is how it works unsaturated acid or its anhydride and phenol -also relatively high Quantities of a wide variety of diolefin polymers in a technically simple process to accumulate. Partial gel formation or that of the known methods Most of the time, complete gelation does not occur. There is no need even those usual with the previous thermal addition of maleic anhydride Additions.

The invention also relates to the aforementioned reaction products of diolefin polymers with phenols and olefinically unsaturated dicarboxylic acids or their anhydrides, preferably maleic anhydride.

excess Under "relatively low molecular weight" are Polymers with an average molecular weight of up to 15,000, preferably from 600 to 10,000. When the products have the properties of hard resins should have or are hard resins, one will generally use polymers assume an average molecular weight of up to 5000, if softer products are desired, starting polymers with an average molecular weight of up to 1400 preferred.

In the reaction products of the invention are the radicals of the phenols bonded in the o- and / or p-position to carbon atoms of the polymers.

In addition, some of the phenolic hydroxyls can appear ethereal C atoms of the polymer must be bound, as demonstrated, for example, by IR analysis became.

In particular, the products obtained from low molecular weight polymers, depending on the amount attached - that is, in the case of both small and large amounts - phenol or unsaturated traces or their anhydrides, in particular maleic anhydride, are sometimes still unsaturated and, as a result, still 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 ester-like bonds, for example by adding the double bonds to the carboxyl groups are possible. Remaining double bonds in the polymers can also be consumed by cyclization reactions.

As diolefin polymers, in addition to polybutadiene 1,4 and -1,2, Polyisoprene also polymers made from cycloaliphatic dienes with 5 to 10 carbon atoms, such as cyclopentadiene, methylcyclopentadiene, dicyclopentadiene, cyclohexadiene, cycloheptadiene or the like in question. The copolymerizable monomers are preferably simple olefinically unsaturated.

For example, styrene, α-methylstyrene, the various Vinyl toluenes, acrylic acid, methacrylic acid or their derivatives, such as esters, amides, Nitriles, also vinyl pyridine, allyl compounds such as diallyl phthalate, unsaturated but it is sometimes also possible to use polymers with a higher molecular weight, e.g. to use up to 100,000.

Compounds from petroleum fractions, e.g. Mixtures of unsaturated hydrocarbons, especially those that contain predominantly aliphatic hydrocarbons with 5 or 9 carbon atoms, e.g. piperylene or indene, or the like.

Monomers are often monolefinically unsaturated hydrocarbons with a boiling range from 20 to 1900 <: preferred.

Preferred copolymers are those made of C5 and / or C9 sclinites, -wherein the latter can also contain dicyclopentadiene -butadiene-dicyclopentadiene copolymer, Styrene-dicyclopentadiene copolymer, butadiene-cyclopentadiene-vinyltoluene copolymer, Dicyclopentadiene-isoprene copolymer. Butadiene-styrene copolymer, isoprene-styrene copolymer i.a.

Optionally contain the polymers or the reaction products additionally at least one unsaturated terpene, such as resin acids, e.g.

Rosin, pinene, dipentene or the like.

Suitable phenols are mono- or polyvalent, mono- or polynuclear substituted or unsubstituted phenols such as phenol, alkylphenol, e.g.

Cresols, xylenols, putvl- or nonvlphenol, chlorophenols, styrolized Phenols, resorcinol, naphthol, diphenylolmethane, diphenylolpropane and novolaks, as well also esterified or etherified phenols, such as anisole or other phenol derivatives, such as phenol carboxylic acids. The conversion is expediently carried out with an excess of Phenol, based on the weight of the polymer.

But it can also be used in deficit.

In addition to or instead of maleic anhydride, maleic acid, Fumaric acid or itaconic acid can be used.

The quantitative ratio of phenol to the anhydride of the unsaturated dicarboxylic acid #, preferably maleic anhydride, in the starting mixture is advantageously between 1: 29 and 20: 1, preferably between 1: 9 and 9: 1, in particular 7: 3 to 3: 7.

The catalyst used can, for example, by precipitation and / change can be removed by neutralizing and / or washing out. never separating the catalyst can also be done by neutralization and subsequent filtration or washing out, If sulfuric acid or sulfonic acids are used, the separation can also take place in a manner known per se by reducing to SO2 by the Polvmerisat.

Suitable catalysts are e.g. Friedel-Crafts catalysts, for example Metal compounds, such as aluminum or zinc chloride or tin tetrachloride, further Boron fluoride or its complex compounds, such as boron fluoride etherate or boron fluoride phenol, Mineral acids such as phosphoric acids, hydrochloric acid, preferably sulfuric acid or Sulphonic acids, / phenolsulphonic acid, para-toluenesulphonic acid or xylenesulphic acid. Of the The catalyst is generally in a proportion of at least 0.2, preferably up to 2 weight, based on the polymerizate, present during the implementation.

This relatively low proportion of catalyst has the advantages that the catalyst can be removed more easily and that the manufacture of the products brings fewer corrosion problems with it than when using higher amounts of catalyst.

The reaction of phenols and maleic anhydride with the polymer Seed can be done in different ways, e.g. in solution or in the melt, in general at temperatures of 20 to 220 C, preferably 40 to 1500C, in particular up to 120 ° C. The polymer can be mixed with the phenol and maleic anhydride mix or melt together and then add the catalyst. Also can Phenol, the olefinically unsaturated acid or its anhydride, especially maleic anhydride, and the catalyst are presented, whereupon the polydiolefin, especially liquid Products, to be added. After completion of the reaction under suitable temperature control any excess phenol, e.g. by distillation below normal or below removed under reduced pressure.

According to a particular embodiment, formaldehyde can be added to the reaction mixture be added before or during the reaction, which is then condensed in. Even in this case it can be used both in the presence and in the absence of catalysts to be worked. The molar ratio of the phenol incorporated to the formaldehyde incorporated can e.g. be 1: (0? 2 to 0.8).

The inventive method has the advantages that light-colored products in good yield and with significantly higher proportions of phenol and maleic anhydride than by known processes, according to which phenol or maleic anhydride only is added, and that surprisingly no gel formation occurs. Concomitantly used catalyst can without difficulty from the Separate reaction mixture. If the amount of catalyst is very small, he can also remain in the products if the small amount at the intended Application of the products does not have a disruptive effect.

The reaction products also have the advantage that their content of Phenol or unsaturated traces or their anhydrides, especially their maleic anhydride content can vary over a wide range.

You can also be high in phenol and maleic anhydride at the same time is determined by IR spectrographic analysis, but the above Numbers are always calculated in relation to the starting polymer.

Their viscosity can vary within a very wide range. never Products can, for example, be liquid, low or high viscosity or solid.

In general, the viscosity decreases with increasing phenol content and unsaturated dicarboxylic acids or acid anhydrides, especially maleic anhydride, to. The hydroxyl and acid numbers can fluctuate over a wide range. By If a certain polarity is set, the solubilities can be converted into polar ones and non-polar solvents. ^ tit increasing hydroxyl numbers indicate the Products are increasingly compatible with other phenolic resins. Next are them Products according to the invention are much more stable against air oxidation as well as against thermal stress than the known phenol or maleic anhydride adducts. In addition, they have improved solubility and compatibilities with a wide variety liarzgruppen on. The scunelt points of the products according to the invention can also be used can be varied depending on the phenol, formaldehyde and dicarboxylic acid or anhydride content. For example, the melting points of the products can be up to about 2400C can be increased.

Some of the reaction products according to the invention can still be unsaturated and have iodine numbers of silver 100. As a result, they are even more Addition and / or polymerization and / or cyclization reactions accessible.

The products according to the invention are elastic, soluble in solvents, such as aliphatic or aromatic hydrocarbons, in chlorinated hydrocarbons, such as Trichlorethylene, carbon tetrachloride, chlorobenzene, also in acetic acid ester and Chloroform or the like. The solubilities are determined by the built-in phenolic and amount of maleic anhydride adjustable. The products according to the invention represent E.g. good binders for lacquers, adhesives and printing inks, but can do Modification, e.g. B. Esterification of those formed by the llydrolysis of maleic anhydride Carboxyl groups with polyhydric alcohols or even more through salt formation Areas of application are made accessible to coverings made from the products show good gloss, good adhesive strength, good flexural strength and especially products with a higher phenol content, it is resistant to yellowing after firing. Especially suitable the lower viscosity products, e.g. those with a phenol content of 3 to 20 weight: and a maleic anhydride content of 5 to 25, preferably up to 20% by weight, especially for paints. Products with a phenol content from 10 to 30, preferably up to 25, weight and a maleic anhydride content from 15 to 30 percentages by weight are in each case based on the starting polymer - are particularly suitable as printing ink binders. High phenolic products, also over 30% by weight, and high maleic anhydride content are suitable for water-soluble Paints.

The products according to the invention also represent another relationship valuable products. In particular, they are due to the saponifiable Cruppen suitable for the production of water-soluble binders. You can continue both during their formation are also modified by subsequent reaction, e.g. with terpenes or with fatty oils. The phenolic hydroxyl group can also be used esterified (e.g. with acetic anhydride) or etherified (e.g. by reaction with Alkylene oxides such as epichlorohydrin). There are also implementations of the excess Phenol with formaldehyde or hardening with flexamethylenetetramine or with resoles possible. Substitutions, e.g. with Arvl or alkyl and / or aralkyl radicals, such as Stvrol, methyl, ethyl, Propyl or isononyl radicals, or with unsaturated radicals such as alkenyl radicals, e.g. the nonenyl radical or the like, also with halogen atoms, such as chlorine or bromine, be performed.

I) ie obtained by reaction with formaldehyde or with epichlorohydrin Products can be hardened in the usual way, e.g. with amines or acid anhydrides. Mixed adducts with terpenes, especially natural resin acids, are particularly suitable for the above-mentioned areas of application.

In the following examples, the viscosity has been used unless otherwise indicated, each measured in 50% toluene solution at 20 ° C.

Examples 1) To a mixture of 240 g of cis-1,4-polybutadiene oil, 480 ps phenol and 40 g maleic anhydride are 0.4 g 100% phenolsulfonic acid at 50 ° C given. The reaction mixture immediately turns dark.

After the mixture has been kept at 90 ° C. for one hour, is im Heated continuously up to 180 ° C over the course of 3 hours and the mixture for 7 hours leave at this temperature. During this time the reaction mixture brightens on. The unreacted phenol is distilled off with heating up to 220 ° C. Residual phenol is removed under reduced pressure (60 mm Hg). You get 318 g of a light yellow. tough plastic resin with a viscosity of 177 cl, that contains about 40 g maleic anhydride and 38 g phenol bound. Products of this Art after stoving paint films give good adhesion and flexural strength exhibit.

2) 0.3 g of 100% phenolsulfonic acid are at 90 ° C a mixture of 100 g of 1,2-polybutadiene solution, 300 g of phenol and 17 g of maleic anhydride were added. That The reaction mixture turns dark in color. It is kept at 90 ° C. for 1 hour. heats <lann continuously within 2 hours up to 180 ° C and leaves 7 hours at this Temperature. To remove the excess phenol by distillation, the mixture is heated to 220.degree.

To remove the remaining phenol, it is finally reduced under reduced pressure Pressure (60 mm Hg) worked. 138 g of a yellow, clear and hard Ilarzes are obtained with a melting point of 162 ° C and a viscosity of 251 @ cP, the 17 g of maleic anhydride and 21 g of phenol bound are contained.

3) A mixture of 120 g of cis-1,4-polybutadiene oil, 240 g of phenol and 40 g of maleic anhydride are added at 50 ° C. to 0.2 g of 100% strength phenolsulfonic acid. In the course of 4 hours, the mixture is heated to 180 ° C., which is previously dark colored reaction mixture brightens up again. The mixture is kept there for 3 hours Temperature and then distilled at 2200C first under normal pressure and finally the unreacted phenol under reduced pressure (60 mm). It result 173 g of a clear, yellow-brown, crushable, hard resin of melting point 48 C, which contains 40 g of maleic anhydride and 13 g of phenol bound. Products of this Art can be diluted with water after neutralization with ammonia or amines.

4) 0.15 g of boron trifluoride-phenol are at 90 C to a mixture of 120 g of cis-1,4-polybutadiene oil, 240 g of phenol and 20 g of maleic anhydride are added, whereby this is discolored slightly dark. It is left at 90 ° C. for 10 minutes and heated then continuously within +) 75 minutes up to 180 ° C. While you have four If it is kept at this temperature for hours, a weak stream of carbon dioxide is passed over it. Then the unreacted phenol is distilled at 2200 C under normal pressure and finally under reduced pressure (En mm). 141 g of a yellow, highly viscous resin. Products of this type are suitable as adhesive resins for polychloroprene and polyurethane adhesives.

5) To 100 g of a liquid polyisoprene dissolved in 200 g of phenol, 8 g of maleic anhydride are added at 70.degree. Then 1 g of 100% strength is added at 900 Phenolsulfonic acid too. The reaction mixture changes color with an exothermic reaction dark. One holds 1 hour at 1200C, then heats.

in the course of 3 hours up to 1800C continuously, holds 3 Hours at this temperature and finally the excess phenol is distilled at 2200C, towards the end of the distillation under reduced pressure (60 mm). Man obtained 118 g of a clear amber-colored resin with a melting point of 83 ° C and one Viscosity of 25 cP. The product contains 8 g maleic anhydride and 10 g phenol bound.

) the mixture 6) In a mixture heated to 1600C 250 g of cis-polyisoprene are introduced from 300 g of phenol and 5 g of maleic anhydride.

Then 2.5 g of concentrated sulfuric acid are left in the course of 5 hours drip. The polyisoprene gradually goes into solution. Under continuous The converted phenol is heated up to 260 ° C. towards the end of the distillation reduced pressure (60 mm) distilled off. 266 g of a maleinized are obtained Cyclo rubber in the form of a clear, light yellow resin with a melting point of 130 ° C and a viscosity of 3460 cP. content of maleic anhydride: 5 g, of phenol II g. The products are suitable for the production of printing inks.

7) In 30n g of phenol heated to 1600C, 1,3 R zinc chloride, then 15 g of maleic anhydride and, ultimately, 250 g of ci-polyisonrene protrude. The reaction mixture turns dark after a short time. After <read Polyisnpren Has gone into solution in the course of 4 hours, the zinc chloride is added by adding precipitated from 2.7 p soda and separated by filtration. The filtrate becomes the excess phenol by distillation at 220-260 ° C, towards the end of the distillation removed under reduced pressure (60 mm). A maleinized Cyclokautscluk is obtained as an amber-colored resin in a yield of 283 g with a melting point of 148 ° C and a viscosity of 592 cP which is suitable for printing inks. Maleic anhydride content 15 g, of phenol 18 g.

8) 400 g of phenol are heated to 160 ° C. Then 15 g maleic anhydride and then 250 g of an isoprene-styrene copolymer fed. After heating to 170 ° C., 2 g of 65% strength phenolsulfonic acid are obtained within 4 hours added dropwise. It is then covered for 3 hours at this temperature and then increased up to 260 ° C.

Excess phenol distills ah. Remaining amounts of phenol are removed under reduced pressure. 274 g of a pale yellow hard one are obtained Resin with a melting point of 175 ° C and a viscosity of 289 cP. salary of maleic anhydride: 15 g, of phenol 9 g.

9) To a mixture of 120 g of phenol, 5 g of maleic anhydride and 50 g of a liquid copolymer of isoprene and vinyl toluene in a weight ratio 40:60 - 1 g of 100X phenolsulphonic acid is added at 900C. Immediately darkening the reaction is exothermic. After cooling, it is lighted for 1 hour at 90 ° C., heated to 110 ° C and holds for 2 hours at this temperature. You heat up within 5 hours continuously up to 180 ° C and left for 3 hours at this temperature. The excess Phenol is removed by heating to 220 ° C., finally under reduced pressure (60 mm). 61 R of a yellow-orange, clear resin with a melting point of 100 ° C. remain and a viscosity of 101 cP.

Maleic anhydride content: 5 R, phenol 6 p.

10) To a mixture of 120 g of phenol, 5 g of maleic anhydride and 50 g of a liquid copolymer of isoprene, styrene and e (-methylstyrene in a weight ratio of 60:20:20, 1 g of 100% strength phenol sulfonic acid is added at 90 ° C. An exothermic reaction takes place under dark coloring. One stops after their completion 1 hour at this temperature and 2 hours at 110 ° C. Then in the course of Heated continuously to 1800 C for 5 hours and at this temperature for 3 hours let go. The unreacted phenol is at 2200C, finally under reduced Pressure (60 mm) distilled off. 63 g of an orange-yellow, clear resin are obtained a melting point of 61 0C and a viscosity of 35 cP, content of maleic anhydride: 5 g, of phenol 8 g.

Instead of the above-mentioned polymerizate, there is also one rich use those made from rutadiene, Stvrol and @ -Methylstyril, which is also a product with good properties is obtained.

11) To a mixture of 200 g of phenol, 20 g of maleic anhydride and 100 g of a copolymer of I) icyclopentadiene and styrene in a weight ratio 70:30 are given 0.5 g of 100% phenolsulfonic acid at 90 C. Under darkening the reaction mixture reacts strongly exothermic. Tni course of 90 minutes will be continuous heated up to 1800C and left at this temperature for 3 hours. nas reaction the mixture brightens up considerably. The excess phenol will will at 220 ° C., finally under reduced pressure (60 mm), distilled off. You get a light brown, clear resin with a melting point of 104 ° C and a viscosity of 76 cP in a yield of 136 g. The product contains 20 g of maleic anhydride and 16 g phenol bound. It is suitable as an adhesive resin.

12) To a mixture of 200 g of phenol, 30 g of maleic anhydride and 100 g of a copolymer of 90 g of dicyclopentadiene and 10 g of pinene are used in 90 ° C 1.5 R 100% phenolsulfonic acid effective. Colored with a strongly exothermic reaction the reaction mixture turns dark.

It is cooled from 130 ° C. to 110 ° C. and left there for 4 hours Temperature. In the course of 2 hours is then heated up to 180 ° C and 2 hours held at this temperature. Then the excess phenol at 2200C, against Removed at the end of the distillation under reduced pressure (60 mm). The result is 166 g of a red-brown resin with a melting point of 165 ° C and a viscosity from -3340 cP. The product contains 30 g maleic anhydride and 36 g phenol bound. It is suitable as a printing resin.

13) To a mixture of 200 g of phenol, 2n g of maleic anhydride and 100 g of a copolymer of 90 g of dicyclopentadiene and 10 g of rosin are used given at 90 ° C. 1.5 g of 100% strength phenolsulfonic acid.

The reaction is strongly exothermic with an intense dark color.

It is left at 1200C for 1 hour and then continuously heated to 1800C in the course of 1 hour. It is left for 3 hours at 180 ° C. and distilled then the unreacted phenol portion at 220 ° C initially under normal pressure and towards the end of the distillation under reduced pressure (60 mm). One obtains 149 g of a clear brown resin with a melting point of 167 ° C. and a viscosity of 1110 cP. The product contains 20 g maleic anhydride and 29 g phenol bound. It is suitable as a resin for printing inks.

14) 200 g of a copolymer of 30% pinene and 70% of a hydrocarbon fraction, consisting of 15% isoprene, 20% piperylene, 25% dicyclopentadiene, 5Z rutadiene and alternating Shares in n and Isopentenes and cyclopentenes as well as isoamylenes composed, are mixed with 100 g of phenol. Then 30 g of maleic anhydride are added and after heating to 90 ° C. 1.5 g of ionic phenolsulfonic acid. Under darkening strongly exothermic reaction takes place, so that 1800C are reached. It is left for 3 hours at this temperature, the reaction mixture lightens. By heating at 2600C the unreacted fractions are reduced towards the end of the distillation distilled off under reduced pressure (60 mm). 177 g of a brown, clear one are obtained Resin with a melting point of 600C and a viscosity of 13 cP.

15) 200 g of a copolymer of 10% pinene and 90% of a hydrocarbon fraction, which consists of 2.7 t styrene, 5.424-methylstyrene, 9.2% vinyl toluene, 14.6% dicyclopentadiene and 21.4% indene and also aromatic and saturated hydrocarbons contains are added to 100 g of phenol. Then 30 g of maleic anhydride are added and after heating to 90 ° C. 1.5 g of 100% strength phenolsulfonic acid. Under darkening if an exothermic reaction takes place, the mixture is kept at 1200C for 75 minutes, then heated continuously in the course of 1 hour to 1880 ° C., left at this temperature for 4 hours and then distilled the unsettled fractions at 2600C, initially under normal pressure and then under reduced pressure (60 mm). There remain 173 g of a brown, clear resin with a melting point of 550C and a viscosity of 13 cP.

16) To a mixture of 100 g of phenol and 30 g of maleic anhydride 2 g of 100% phenol sulfonic acid are added. After heating to 800C, the 140 g of thermally prepolymerized dicyclopentadiene were added over the course of 1 hour. It is then heated continuously up to 180 ° C. over the course of 4 hours and Leave at this temperature for 4 hours. After increasing the temperature to 2500C residual phenol is removed under reduced pressure (60 mm). One obtains 226 g of a yellow-brown resin with a melting point of 1000 ° C. and a viscosity of 62 cP. Maleic anhydride content 35 g, phenol 56 g. The product is available as an adhesive resin suitable.

17) 300 grams of polymerized dicyclopentadiene are dissolved in 140 grams of phenol melted. The mixture is heated to 110.degree. Then you get 12 R Paraformaldehvd and 45 R maleic anhydride. It is heated up to 1800C in the course of 2 hours and lightens for 2 hours at this temperature. Then within 30 minutes it will be up heated to 2500C and finally unreacted phenol under reduced pressure (60 mm) distilled off. 375 g of an amber-colored resin are obtained with a Melting point of 180 ° C and a viscosity of 460 cP. Maleic anhydride content 35 g, phenol 40 g. As a resin, the product is ideally suited for toluene gravure printing.

18) A mixture of 140 g phenol, 12 g paraformaldehyde, 45 g maleic anhydride and 70 g of acrylic acid is heated to 145 ° C. Then you leave 300 R dicyclopentadiene add dropwise over 3 hours. Then hold on the backflun for 5 hours and heat finally to 250 C. Remaining, unreacted proportions are reduced under reduced Pressure (o0 mm) removed. There result 339 g of a yellow-brown resin with a Melting point of 93-950C and a viscosity of 254 cP. Maleic anhydride content 45 8. Phenol 75 g.

Claims (11)

P a t e n t a n sp r ii c h e 1. Reaction products of diolefin polymers with phenols and olefinic unsaturated dicarboxylic acids or their anhydrides, characterized in that the Diolefin polymer a) a Romopolymerisat of a diene with 4 to 10 carbon atoms and / or b) a copolymer of the aforementioned dienes - with, if appropriate, subordinate Molar amounts of one or more copolymerizable monomers - is, preferably where the homo- or mixed polymer is / re atively low molecular weight and the phenol content 2 to -40, preferably 3 to 30 weight and the proportion of unsaturated dicarboxylic acids or their anhydrides 2 to 55, preferably 5 to 30, by weight, in each case based on on the starting polymer. 2. Products according to claim 1, characterized in that dR the copolymerizable Monomerically unsaturated aromatic hydrocarbons with a boiling range of 20 to 1900C and / or mixtures of unsaturated aliphatic hydrocarbons with are an average of 5 carbon atoms. 3. Products according to claim I or 2, characterized in that formaldehyde is condensed. 4. Products according to claim 1 to 3, characterized in that they additionally contain at least one unsaturated terpene. 5. Products according to claims 1 to 4, characterized in that the Diene is butadiene, isoprene or dicyclopentadiene. 6. Products according to Claims 1 to 5, characterized in that the anhydride of the olefinically unsaturated nicarboxylic acids maleic anhydride list. (7) Process for the preparation of reaction products of diolefin polymers with phenols and maleic anhydride according to Aniprilchen 1 to 6, characterized in that 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 monomers -in a reaction stage with Phenol and with 2 to 55% by weight maleic anhydride, based on the starting polymer, are reacted, whereupon unreacted phenol fractions are removed. 8. The method according to claim 7, characterized in that the implementation in the presence of a maximum of 5 weightz, based on the starting polymer, one Friedel-Crafts catalyst or a mineral acid is carried out. 9. The method according to claim 7 or 8, characterized in that the Reaction is carried out in the presence of a solvent. 10. The method according to claims 7 to 9, characterized in that Formaldehyde is added before or during the reaction, 11. Use of the conversion products according to claims 1 to 6 for the production of binders for printing inks, adhesives and water-soluble paints.