DE2358722C2 - Reaction products of diolefin polymers with phenols and olefinically unsaturated dicarboxylic acids and their use - Google Patents

Description

• a) ein Homopolymerisat eines Diens der Gruppe
  
  • a₁) Butadien,
  • a₂) Isopren und
  • a₃) cycloaliphatische Diene mit 5 bis 10 Kohlenstoffatomen, oder
• b) ein Mischpolymerisat aus Butadien-Dicyclopentadien bzw. Dicyclopentadien-Isopren, oder
• c) ein Mischpolymerisat der unter a) genannten Diene mit untergeordneten Molmengen mindestens eines copolymerisierbaren Monomeren der Gruppen
  • c₁) Styrol, α-Methylstyrol und Vinyltoluole, Allylverbindungen und Kohlenwasserstoff- Fraktionen in Form von Gemischen ungesättigter Kohlenwasserstoffe, die überwiegend aliphatische Kohlenwasserstoffe mit 5 bzw. 9 Kohlenstoffatomen enthalten, oder
  • c₂) Acryl- oder Methacrylsäure bzw. deren Ester, Amide oder Nitrile,
• d) als Phenol ein unsubstituiertes oder durch eine Alkylgruppe oder Chlor substituiertes Phenol aus der Gruppe Phenol, Resorcin, Naphthol, Diphenylolmethan, Diphenylolpropan und styrolisiertes Phenol, und
• e) als olefinisch ungesättigte Dicarbonsäure bzw. deren Anhydrid Maleinsäure, Maleinsäureanhydrid, Fumarsäure oder Itaconsäure eingesetzt wurden,

das Ausgangs-Diolefinhomo- oder -mischpolymerisat ein mittleres Molekulargewicht bis zu 15 000 besaß und die Reaktionsbedingungen so gewählt wurden, daß der Anteil des eingebauten Phenols 2 bis 40 Gew.-% und der Anteil der eingebauten ungesättigten Dicarbonsäure bzw. des Maleinsäureanhydrids 2 bis 55 Gew.-%, jeweils bezogen auf das Ausgangs-Diolefinpolymerisat ausmacht.The subject of the main patent 22 60 376 are reaction products obtained by reacting diolefin polymers with a phenol and an olefinically unsaturated dicarboxylic acid or its anhydride using conventional reaction conditions, as well as salts of such reaction products obtained in a conventional manner, where the diolefin polymers,

• a) a homopolymer of a diene of the group
  
  • a ₁ ) butadiene,
  • a ₂ ) Isoprene and
  • a ₃ ) cycloaliphatic dienes having 5 to 10 carbon atoms, or
• b) a copolymer of butadiene-dicyclopentadiene or dicyclopentadiene-isoprene, or
• c) a copolymer of the dienes mentioned under a) with minor molar amounts of at least one copolymerizable monomer of the groups
  • c ₁ ) styrene, α-methylstyrene and vinyltoluenes, allyl compounds and hydrocarbon fractions in the form of mixtures of unsaturated hydrocarbons containing predominantly aliphatic hydrocarbons having 5 or 9 carbon atoms, or
  • c ₂ ) acrylic or methacrylic acid or their esters, amides or nitriles,
• (d) as phenol, an unsubstituted or alkyl or chlorine-substituted phenol selected from the group consisting of phenol, resorcinol, naphthol, diphenylolmethane, diphenylolpropane and styrenated phenol, and
• e) maleic acid, maleic anhydride, fumaric acid or itaconic acid were used as the olefinically unsaturated dicarboxylic acid or its anhydride,

the starting diolefin homopolymer or copolymer had an average molecular weight of up to 15,000 and the reaction conditions were chosen so that the proportion of incorporated phenol was 2 to 40% by weight and the proportion of incorporated unsaturated dicarboxylic acid or maleic anhydride was 2 to 55% by weight, in each case based on the starting diolefin polymer.

Preferably, the proportion of incorporated phenol is 3 to 30 wt.% and that of unsaturated dicarboxylic acid or maleic anhydride is 5 to 30 wt.%.

The polymers used as starting materials preferably have an average molecular weight of 600 to 10,000. If the products are to have the properties of hard resins or are hard resins, polymers with an average molecular weight of up to 5,000 are generally used, the minimum value being, for example, about 500. If softer products are desired, starting polymers with an average molecular weight of up to 1,400 are preferred.

Although the conversion products already proposed have proven to be effective, it has sometimes been desirable to further modify them for specific applications.

The main patent also covers the use of the proposed reaction products as binders for printing inks, adhesives and varnishes, e.g. water-soluble paints.

In a further development of the invention of the main patent, the reaction products are modified by incorporating or using olefinically unsaturated monocarboxylic acids with 3 to 22, preferably up to 18 carbon atoms or their anhydrides instead of or together with the unsaturated dicarboxylic acids or the maleic anhydride. The invention also relates to the use of the aforementioned reaction products for producing binders for printing inks, adhesives and varnishes, in particular water-soluble paints. The reaction products according to the invention are primarily characterized by particularly light intrinsic colors and the light color of their solutions.

Suitable unsaturated monocarboxylic acids are, for example, acrylic acid, methacrylic acid, phenylacrylic acid, crotonic acid, isocrotonic acid, vinylacetic acid, angelic acid, tiglic acid, sorbic acid, undecylenic acid, fatty acids of drying or semi-drying oils, such as oleic acid, ricinoleic acid fatty acid (i.e. the fatty acid obtained from dehydrated castor oil), elaidic acid, eleostearic acid, erucic and brassidic acid, or uniform or mixed anhydrides thereof, each alone or in admixture.

The olefinically unsaturated monocarboxylic acids can be present in a mixture with the unsaturated dicarboxylic acids or the maleic anhydride, whereby the mutual weight ratio can be 1:9 to 9:1, preferably 3:7 to 7:3. It is also possible to use the monocarboxylic acids in the absence of dicarboxylic acid units, whereby the monocarboxylic acids can also be present in a mixture with one another. The desired melting points and viscosities of the products can be set by selecting the proportions or the type of carboxylic acids.

The diolefin polymers, unsaturated dicarboxylic acids or their anhydrides and phenols used as starting materials are the same as those described in the main patent. This also applies to the mutual proportions of the individual reaction partners.

The products according to the invention can be manufactured analogously to those of the main patent, but with the advantage that the reactions, including the volatilization of unreacted portions of the reaction components, can be carried out under gentle conditions, i.e. at lower temperatures than previously. This largely prevents any further thermal polymerization of the starting polymers, which would cause an increase in melt and solution viscosity. The products according to the invention are therefore essentially light. This results in a largely uniform molecular weight. As a result, there is increased reproducibility and the desired characteristics and properties are guaranteed. In addition, the reaction time is shortened. The olefinically unsaturated monocarboxylic acids can be reacted with the unsaturated dicarboxylic acids or the maleic anhydride before, during or after the reaction. Furthermore, the various embodiments and variations of the process described in the main patent can also be combined with the present invention, for example. B. the use of catalysts, the reaction conditions, for example temperature control, the sequence of the reactants and the solvents used. Any catalyst used can be separated from the reaction mixture without difficulty. If the amount of catalyst is very small, it can also remain in the products if the small amount does not interfere with the intended use of the products.

The reaction products have the further advantage that their content of phenol or of unsaturated acids or their anhydrides, in particular their maleic anhydride content, can vary within a wide range. They can also simultaneously have a high phenol and carboxylic acid content, which is determined by IR spectrographic analysis, although the above figures are always calculated in relation to the starting polymer.

The viscosity of the reaction products according to the invention can vary within a very wide range. The products can be liquid, low or high viscosity or even solid.

The reaction products according to the invention can still be partially unsaturated and have iodine numbers of more than 100. As a result, they are still accessible to further addition and/or polymerization and/or cyclization reactions.

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, and also acetic esters, chloroform or the like. The solubilities can be largely adjusted by the incorporated proportions of phenol and the unsaturated dicarboxylic acids or maleic anhydride and monocarboxylic acid. The products according to the invention are, for example, good binders for varnishes, adhesives and printing inks, but can be made accessible to other areas of application by modification, e.g. esterification of the carboxyl groups formed by hydrolysis of anhydrides with mono- and/or polyhydric alcohols or by salt formation. Coatings made from the products display good gloss, good adhesive strength, good flexural strength, abrasion resistance, excellent compatibility with pigments and, in particular, products with a higher phenol content, resistance to yellowing when baked. The low-viscosity products are particularly suitable, e.g. B. those with a phenol content of 3 to 20 wt.% and a carboxylic acid content of 5 to 35, preferably up to 25 wt.%, especially for paints. Products with a phenol content of 5 to 30 wt.%, preferably up to 25 wt.% and a carboxylic acid content of 5 to 30 wt.% - percentages are always based on the starting polymer - are particularly suitable as printing ink binders.

Products with high phenol content, even over 30% by weight, and high carboxylic acid content are suitable for water-soluble paints.

In general, the viscosity increases with increasing content of phenols and the unsaturated dicarboxylic acids or maleic anhydride and/or monocarboxylic acids. The hydroxyl and acid numbers can therefore vary within a wide range. By setting a certain polarity, the solubilities in polar and non-polar solvents can be controlled. With increasing hydroxyl numbers, the products show increasing compatibility with other phenolic resins. Furthermore, the products according to the invention are significantly more stable against air oxidation and also against thermal stress than the known phenol or maleic anhydride adducts. In addition, they have improved solubility and compatibility with the various resin groups. Furthermore, the melting points of the products according to the invention can be varied depending on the phenol and dicarboxylic acid or maleic anhydride and/or monocarboxylic acid content. For example, the melting points of the products can be varied as desired, for example by the presence of unsaturated monocarboxylic acids up to about 240°C.

The products according to the invention can be further modified both during their formation and by subsequent reaction, for example with terpene compounds such as rosin and/or with fatty oils, i.e. the addition of these substances can take place before, during or after the reaction. The products can therefore additionally contain at least one unsaturated terpene compound, such as those described in the main patent, preferably rosin. The phenolic hydroxyl group can also be etherified (for example by reaction with alkylene oxides such as epichlorohydrin).

In addition, substitutions with the radicals specified in claim 1, e.g. alkyl radicals such as methyl, ethyl, propyl or isononyl radicals, chlorine or styrene, can be carried out at still free positions on the phenol nucleus.

The products obtained by reaction with epichlorohydrin can be cured in the usual way, for example 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, unless otherwise stated, the viscosity was measured in 50% toluene solution at 20°C.

Examples

• 1. 500 g of polycyclopentadiene (molecular weight 600-900) are dissolved in a mixture of 25 g of phenol and 50 g of acrylic acid at high temperature. After holding at 100°C for 1 hour, the mixture is heated over a period of 6 hours, initially under reflux and then to 230°C while distilling off the volatile components. Towards the end of the reaction, the mixture is worked under reduced pressure (approx. 150 to 200 mm) for 15 to 20 minutes. 513 g (= 90%) of a yellow-brown resin with a melting point of 110 to 112°C and a viscosity of 32 cP are obtained.
• 2. 500 g of a cyclopentadiene polymer (molecular weight 600-1000) are melted in 200 g of phenol and the mixture is heated to 100°C. Then 50 g of acrylic acid are added and the mixture is heated over the course of 6 hours, first under reflux to 200°C, then to 230°C while distilling off excess phenol. Finally, the mixture is worked under reduced pressure (60 mm). 539 g (= 73%) of a light yellow resin with a melting point of 115°C and a viscosity of 23 cP are obtained. The hydroxyl number is 20 and the acid number is 10.
• 3. 500 g of a cyclopentadiene polymer (molecular weight 500-1000) are dissolved in 100 g of phenol; then 60 g of malic anhydride and 10 g of acrylic acid are added at 100°C. The mixture is heated to 200°C under reflux for 7 hours and then to 230°C while distilling. Finally, the mixture is worked under reduced pressure (60 mm). 564 g (= 84%) of a light brown resin with a melting point of 126°C and a viscosity of 41 cP remain.
• 4. 500 g of cyclopentadiene polymer (molecular weight 600-1000) are dissolved in 100 g of phenol. 60 g of acrylic acid and 10 g of maleic anhydride are then added at 120°C. The mixture is then heated to 200°C under reflux for 7 hours and then to 230°C while distilling. Finally, the mixture is worked under reduced pressure (60 mm). This gives 547 g (= 82%) of a light yellow resin with a melting point of 122°C and a viscosity of 38 cP. The hydroxyl number is 8 and the acid number is 16.
• 5. 1 g of 65% aqueous phenolsulfonic acid is added to a mixture of 700 g of cis-1,4-polybutadiene oil (molecular weight 1400), 400 g of phenol and 80 g of maleic anhydride at 50°C. The mixture is then heated to 100°C over the course of one hour, during which the reaction mixture turns dark. 90 g of acrylic acid are then slowly added from a dropping funnel. After heating to 120°C, the temperature is maintained for one hour and then increased continuously over the course of 4 hours to 250°C. At a temperature of 140-160°C the reaction mixture lightens again. Finally, unreacted components are distilled off under reduced pressure (60 mm). 1150 g (= 90.5%) of an amber-colored resin are obtained.
• Infrared analysis shows that about 30% of the added phenol is bound in an ether-like manner. The rest is ortho- and para-substituted in equal parts.
• 6. 500 g of a viscous polyisoprene (molecular weight 2000-3000) are dissolved in 600 g of phenol while heating. Then 30 g of maleic anhydride are added at 70°C and the mixture is heated to 90°C. After adding 2 g of 65% aqueous phenolsulfonic acid, the reaction mixture turns dark. 60 g of acrylic acid are then slowly added. The mixture is then kept at 120°C for 1 hour and then at 180°C for 3 hours. The reaction mixture becomes lighter in color. Unreacted phenol is distilled off at 220°C and further unreacted components at 240°C under reduced pressure (60 mm). 970 g (= 81.5%) of a light yellow resin remain.
• 7. 600 g of a copolymer (molecular weight approx. 600) made of 10% α- pinene and 90% of a hydrocarbon fraction, which is composed of 2.7% styrene, 5.4% α- methylstyrene, 9.2% vinyltoluene, 14.6% dicyclopentadiene and 21.4% indene and also contains aromatic and saturated hydrocarbons, are melted with 300 g of a technical cresol mixture. After adding 60 g of maleic anhydride and 40 g of acrylic acid, 3 g of 65% aqueous phenolsulfonic acid are added at 90°C. An exothermic reaction takes place with darkening of the color. The mixture is left at 120°C for one hour, then heated continuously to 180°C over the course of 2 hours and kept at this temperature for 3 hours. By partially distilling off unreacted reaction components the mixture becomes lighter. Excess phenol is removed at 250-260°C, first under normal pressure and then under reduced pressure (60 mm). 540 g (= 54%) of a yellow-brown resin are obtained.

Claims (5)

1. Reaction products obtained by reacting diolefin polymers with a phenol and an olefinically unsaturated dicarboxylic acid or its anhydride using conventional reaction conditions, as well as salts of such reaction products obtained in a conventional manner, where the diolefin polymers are
a) a homopolymer of a diene of the group a ₁ ) butadiene, a ₂ ) Isoprene and a ₃ ) cycloaliphatic dienes having 5 to 10 carbon atoms, or b) a copolymer of butadiene-dicyclopentadiene or dicyclopentadiene-isoprene, or c) a copolymer of the dienes mentioned under a) with minor molar amounts of at least one copolymerizable monomer of the groups (c ₁ ) styrene, a -methylstyrene and vinyltoluenes, allyl compounds and hydrocarbon fractions in the form of mixtures of unsaturated hydrocarbons containing predominantly aliphatic hydrocarbons with 5 or 9 carbon atoms, or c ₂ ) acrylic or methacrylic acid or their esters, amides or nitriles, (d) as phenol, an unsubstituted or alkyl or chlorine-substituted phenol selected from the group consisting of phenol, resorcinol, naphthol, diphenylolmethane, diphenylolpropane and styrenated phenol, and e) maleic acid, maleic anhydride, fumaric acid or itaconic acid were used as the olefinically unsaturated dicarboxylic acid or its anhydride,
the starting diolefin homopolymer or copolymer had an average molecular weight of up to 15,000 and the reaction conditions were chosen so that the proportion of incorporated phenol was 2 to 40% by weight and the proportion of incorporated unsaturated dicarboxylic acid or maleic anhydride was 2 to 55% by weight, each based on the starting diolefin polymer, according to patent P 22 60 376.5, characterized in that instead of the unsaturated dicarboxylic acids or maleic anhydride, they contain olefinically unsaturated monocarboxylic acids having 3 to 22 carbon atoms or their anhydrides, each individually or as a mixture. 2. Reaction products according to claim 1, characterized in that they contain acrylic acid or methacrylic acid as olefinically unsaturated monocarboxylic acids. 3. Reaction products according to claim 1 or 2, characterized in that they contain a mixture of unsaturated dicarboxylic acids or their anhydrides and the olefinically unsaturated monocarboxylic acids in a weight ratio of 1:9 to 9:1, preferably 3:7 to 7:3. 4. Use of the reaction products according to one or more of claims 1 to 3 for the preparation of binders for printing inks, adhesives and varnishes.