DE2357762C2 - - Google Patents

Description

The main patent 22 65 553 relates to reaction products or their salts obtained by the reaction of
Diolefin polymers with a phenol and an olefinically unsaturated dicarboxylic acid or its anhydride and
Formaldehyde - optionally α ) in the presence of at most 5% by weight of a mineral acid or a Friedel-Crafts catalyst and / or β ) an unsaturated terpene or a fatty oil -, as diolefin polymers

• a) a homopolymer of a diene from 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 which predominantly contain aliphatic hydrocarbons with 5 or 9 carbon atoms, or
  • c ₂ ) acrylic or methacrylic acid or its esters, amides or nitriles,
• d) as phenol, the phenol itself, which may be due to Alkyl is substituted, or resorcinol, naphthol, Diphenylolmethane, Diphenylolpropan or styrolized Phenol or chlorophenols and
• e) as olefinic unsaturated dicarboxylic acid or their Anhydride maleic acid, maleic anhydride, fumaric acid or itaconic acid have been used,

wherein the starting diolefin homopolymer or copolymer has an average molecular weight of 600 to 15,000, the Proportion of the built-in phenol 2 to 40 wt .-% and Proportion of the unsaturated dicarboxylic acid or of maleic anhydride 2 to 5 wt .-%, each based on the starting diolefin polymer, and before or during the reaction formaldehyde in such quantities has been added that the molar ratio of incorporated Phenol to built-in formaldehyde is 1: (0.2 to 0.8).

According to the main patent, the implementation products are as Binder component for printing inks, adhesives and Paints used. The products obtained have been well proven, but it was desirable that their Possibility to expand still further.

In further training of the subject of the main patent it has now been found that high quality products can then be found receives when the molar ratio of the in the products condensed formaldehyde to the phenolic Components (0.8-3.5): 1, preferably up to 1.8: 1. The proportion of the phenol incorporated is preferably 3 to 30 % By weight and the proportion of built-in unsaturated Dicarboxylic acid or maleic anhydride 5 to 30% by weight, each based on the starting polymer.  

Contrary to the opinion of experts, according to which formaldehyde of phenolic resins in general only in a proportion of up to can be incorporated to about 2 moles per mole of phenol according to the teaching of the present invention for the first time Possibility created with a phenolic resin essential phenol content, which up to 40% built-in Phenol can contain such high proportions of formaldehyde per mole of phenol. It can be sent to the phenolic components not bound formaldehyde Shares react in another way. For example can the reactive groups, e.g. B. in the form of Methylol groups of the products according to the invention, too Reactions with those serving as starting material Diolefin polymers and / or unsaturated terpenes, like rosin.

Mineral oil resins and Phenol formaldehyde resin in the presence of unsaturated Carboxylic acids, such as maleic anhydride, with one another implemented and the products obtained from it as Binder used for printing inks and paints. After that, it is necessary to first use a phenolic resin with the desired specific characteristics, that is only implemented in the second stage. Because with that Starting phenolic resin the reactive sites on the phenolic cores are largely occupied by the condensation Phenolic resin in this reaction practically only with the Methylol groups react. As a result, the  Phenol cores do not adhere to the double bond of the starting Mineral oil resin can be added.

Another advantage of the invention over the prior art Technology is that the products are in a stew processes can be produced. That way you can also products with an increased content of built-in phenol getting produced. This is possible because Formaldehyde condensed to those phenol nuclei that have first been added to the diene polymer. Under Mediation of the methylol resulting from the formaldehyde groups can now be added additional phenol condense. This increases the number of Hydroxyl groups and the free nucleus where further implementations can be made. About that In addition, the solubility of the products in various solvents as well as the compatibility with a number of other resins or combinations of resins change, thereby broadening the scope of the invention appropriate products is possible.

In the reaction products according to the invention, the Residues of the phenols in the o- and / or p-position Carbon atoms of the polymers bound. In addition some of the phenolic hydroxyls can be ethereal C atoms of the polymer are bound, as by IR Analysis has been demonstrated.

In particular those made from low molecular weight polymers received products are depending on the amount stored - d. H. both small and large quantities - Phenol or maleic anhydride sometimes still partially unsaturated and as a result further additions and / or polymerization reactions accessible. The Maleic anhydride does not add to the Phenol addition consumed double bonds in  in different ways, such as by Diels-Alder reaction and / or also in the form of substituted alkenyl succinic acids. Also ester-like bonds, e.g. B. by adding the Double bonds to the carboxyl groups are possible. Remaining double bonds of the polymers can also are consumed by cyclization reactions.

The products of the invention can be analogous to those of Main patent received. Different possible variants and Embodiments, e.g. B. implementation in Presence of catalysts and / or solvents which Selection of the reaction conditions, the order and the like, are possible as under the main patent. You can also the formaldehyde after the reaction of Polymer with the unsaturated dicarboxylic acids or Add maleic anhydride and phenol and with the Implement the reaction product.

The diene homo- and / or copolymers that copolymerizable monomers that are olefinic unsaturated dicarboxylic acids or maleic anhydride and the suitable phenols and catalysts and their Quantities or mutual proportions are with the exception of the claimed molar ratio of phenol: Formaldehyde as in the main patent.

Also according to the present invention has a proportion low catalyst content the advantages that the Catalyst can be removed more easily and that the manufacture of products with fewer corrosion problems than when using higher amounts of catalyst.

The reaction products according to the invention have the advantages that they are bright products, in good yield and with much higher proportions of phenol and maleic acid anhydride than by known methods, according to which only  Phenol or only maleic anhydride is added, obtained and that surprisingly no yellowing he follows. The catalyst used can be used without Separate difficulties from the reaction mixture. Provided the amount of catalyst was very small, he can also in the Products remain when the small amount is with the intended use of the products does not interfere.

The reaction products have the further advantage that you Content of phenol or unsaturated dicarboxylic acids, especially their maleic anhydride content, in one wide range can fluctuate. You can also at the same time a high phenol and maleic anhydride content is determined by IR spectrographic analysis, have, however, the numerical data of claim 1 are always calculated in relation to the starting polymer.

Their viscosity can be in a very wide range vary. The products can e.g. B. liquid, low or be highly viscous or solid.

Generally the viscosity decreases with increasing content on phenols and unsaturated dicarboxylic acids or Maleic anhydride too. So the hydroxyl and Acid numbers fluctuate in wide ranges. By A certain polarity can be set Solubilities in polar and non-polar solvents Taxes. With increasing hydroxyl numbers the Products become increasingly compatible with others Phenolic resins. The products according to the invention are furthermore much more stable against air oxidation as well as against thermal stress than the known phenol or Maleic anhydride adducts. They also point out improved solubilities and tolerances with the most diverse resin groups. They can continue Melting points of the products according to the invention depending on  Phenol, formaldehyde and dicarboxylic acid or Anhydride content can be varied. For example, the Melting points of the products up to about as desired 240 ° C can be increased.

Some of the reaction products according to the invention still be unsaturated and have iodine numbers of over 100. As a result, they are still further 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, further in acetic acid ester and chloroform or the like. The solubilities are due to the built-in phenol and Amount of maleic anhydride adjustable. The invention Products represent e.g. B. good binders.

The use of the is also within the scope of the invention Implementation products as a binder component for Printing inks, adhesives and varnishes. The invention Implementation products can, however, by modification, e.g. B. Esterification by hydrolysis of maleic anhydride carboxyl groups formed with polyhydric alcohols or through salt formation, still further areas of application be made accessible. Made from the products Coatings show good gloss, good adhesive strength, good Flexural strength, abrasion resistance, excellent Compatibility with pigments and, especially products with higher phenol content, yellowing resistance at Branding. The lower viscous are particularly suitable Products, e.g. B. 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 up to 30% by weight - percentages are in each case based on the Starting polymer - are particularly useful as a printing ink pad medium suitable. Products with high phenol content, too over 30 wt .-% and high maleic anhydride are suitable for water-soluble paints.

The products according to the invention also represent other valuable products. In particular they are due to the saponifiable groups for production water-soluble binder suitable. You can continue both during their formation and through subsequent ones Reaction have been modified, e.g. B. with terpenes and / or with fatty oils, d. H. the addition of these substances can before, during or after the reaction. The products can thus according to an embodiment of the invention additionally contain at least one unsaturated terpene. The terpenes mentioned in the main patent are but preferably rosin, in question. That too is Hardening with hexamethylenetetramine or a reaction with Resoles possible.

In free areas of the phenol core, the substituents specified in claim 1 present be. Mixed adducts with terpenes, in particular Natural resin acids are particularly suitable for that fields of application mentioned above.

In the following examples, the viscosity when not otherwise specified, each in 50% toluene solution measured at 20 ° C.

Examples

• 1. 900 g polycyclopentadiene (molecular weight 600-900) are in a mixture of 143 g of p-tert-butylphenol and 90 g of xylene dissolved in the heat. Then it goes to 110 ° C heated. Now add 108 g of maleic anhydride and then 30 g of paraformaldehyde. Then you heat in the course of 3 hours up to 180 ° C and holds the mixture 30 minutes at this temperature. Within another Hour is heated up to 250 ° C, being lighter distill off volatile components. Towards the end of the reaction is worked under reduced pressure (60-80 mm). Man receives a yellow-brown resin with a melting point of 151 ° C and a viscosity of 156 cP. The yield is 1112 g = 94%. The acid number is 37. That Molar ratio of phenol to formaldehyde is 1: 0.95.
• 2.300 g polycyclopentadiene (molecular weight 600-900) and 30 g of rosin are mixed in a mixture of 30 g Xylene and 10 g phenol dissolved in the heat. At 120 ° C then 45 g of maleic anhydride and 6 g are added Paraformaldehyde too. The ratio of phenol to Formaldehyde is 1: 1.8. Over the course of 5 to 6 hours heated to 250 ° C. Now you hold the reaction mixture for a short time under reduced pressure (60 mm). Man receives 357 g = 98% of a yellow resin with the melting point 188 to 194 ° C and the viscosity of 148 cP.
• 3.300 g polycylopentadiene (molecular weight 600-900) are in a mixture of 30 g of xylene and 5 g of phenol the heat is released. Then you give 36 g at 120 ° C Maleic anhydride and 30 g acrylic acid and then 6 g of paraformaldehyde. The ratio of phenol to Formaldehyde is 1: 3.4. Then you heat in the course of 5 hours continuously up to 250 ° C and works at this temperature for 20 minutes under reduced pressure. 338 g = 90% of a yellow resin of Melting point 220 ° C and a viscosity of 597 cP.

Claims (3)

1. Further development of the reaction products or their salts, obtained by reacting diolefin polymers with a phenol and an olefinically unsaturated dicarboxylic acid or their anhydride and formaldehyde - optionally α ) in the presence of at most 5% by weight of a mineral acid or a Friedel-Crafts catalyst and / or β ) of an unsaturated terpene or a fatty oil -, as the diolefin polymer

• a) a homopolymer of a diene from 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
  • c₁) styrene, α- methylstyrene and vinyltoluenes, allyl compounds and hydrocarbon fractions in the form of mixtures of unsaturated hydrocarbons which contain predominantly aliphatic hydrocarbons with 5 or 9 carbon atoms, or
  • c₂) acrylic or methacrylic acid or its esters, amides or nitriles,
• d) as phenol the phenol itself, which is optionally substituted by alkyl, or resorcinol, naphthol, diphenylolmethane, diphenylolpropane or styrenated phenol or chlorophenols and
• e) maleic acid, maleic anhydride, fumaric acid or itaconic acid have been used as olefinically unsaturated dicarboxylic acid or its anhydride,

the starting diolefin homopolymer or copolymer having an average molecular weight of 600 to 15,000, the proportion of the phenol incorporated 2 to 40% by weight and the proportion of the unsaturated dicarboxylic acid or maleic anhydride incorporated 2 to 55% by weight, in each case based on the starting diolefin polymer, and before or during the reaction formaldehyde has been added in such amounts that the molar ratio of phenol to formaldehyde incorporated is 1: (0.2 to 0.8), according to patent 22 65 553 , characterized in that the molar ratio of condensed formaldehyde to the phenolic constituents instead of (0.2 to 0.8): 1 now (0.8 to 3.5): 1, preferably (0.8 to 1.8): 1. 2. Use of the reaction products according to claim 1 as Binder component for printing inks, adhesives and Paints.