WO2018167310A1 - Procédé de fonctionnalisation de polymères d'acrylate en absence de solvant et polymères d'acrylate modifiés pouvant être obtenus par ce procédé - Google Patents

Procédé de fonctionnalisation de polymères d'acrylate en absence de solvant et polymères d'acrylate modifiés pouvant être obtenus par ce procédé Download PDF

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Publication number
WO2018167310A1
WO2018167310A1 PCT/EP2018/056758 EP2018056758W WO2018167310A1 WO 2018167310 A1 WO2018167310 A1 WO 2018167310A1 EP 2018056758 W EP2018056758 W EP 2018056758W WO 2018167310 A1 WO2018167310 A1 WO 2018167310A1
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WO
WIPO (PCT)
Prior art keywords
acrylate
acrylate polymers
functionalizing
reaction
solvent
Prior art date
Application number
PCT/EP2018/056758
Other languages
German (de)
English (en)
Inventor
Walter Degelmann
Original Assignee
Lohmann Gmbh & Co. Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lohmann Gmbh & Co. Kg filed Critical Lohmann Gmbh & Co. Kg
Priority to EP18711940.9A priority Critical patent/EP3596139A1/fr
Publication of WO2018167310A1 publication Critical patent/WO2018167310A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently

Definitions

  • the present invention relates to a process for functionalizing acrylate polymers in the molten state.
  • Acrylate polymers that is, homo- and copolymers of acrylic acid, methacrylic acid, and various esters of these acids, are well known in the art and are widely used in a wide variety of applications. Important monomers in this context are, for example: methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, ferric acid.
  • Important comonomers in the production of acrylate polymers include acrylonitrile, methacrylonitrile, ethylene, styrene, 1, 3-butadiene, 1, 2-butadiene, vinyl acetate, vinyl propionate, vinyl chloride and vinylidene chloride.
  • polyfunctional acrylate monomers which can be used in the preparation of acrylate monomers; Examples which may be mentioned here are di- and triacrylates (eg ethylene glycol diacrylate, trimethylolpropane triacrylate), hydroxy-substituted acrylates (eg 2-hydroxyethyl acetate), ethers (eg ethyl diglycol acrylate), amines (eg dimethylaminoethyl acrylate, tert-butylaminoethyl methacrylate), epoxy-derivatized acrylates (eg glycidyl acrylate, Glycidyl methacrylate) and sulfonic acids (eg 2-sulfoethyl methacrylate).
  • di- and triacrylates eg ethylene glycol diacrylate, trimethylolpropane triacrylate
  • hydroxy-substituted acrylates eg 2-hydroxyethyl acetate
  • ethers eg
  • acrylate polymers can be specifically influenced by polymer-analogous reactions and / or crosslinking reactions (with the finished acrylate polymers as starting materials for further functionalization reactions).
  • Acrylate polymers obtained with the participation of polyfunctional comonomers are of particular interest when it comes to carrying out crosslinking reactions on the polymers.
  • crosslinking reactions are known using second components (which react with the functional groups present) or else radiation curing reactions.
  • Crosslinking reactions with secondary components usually take place in solutions. Such reaction systems usually allow a good mixing of the reactants and a good temperature control of the reactions. However, it can be problematic to remove the solvent from the finished reaction product. Crosslinking increases the molecular weight of the polymers, and thus increases their ability to retain small molecules (such as solvents) in the molecular structure. This is undesirable for many technical applications, since the properties of the polymer can change with the presence of such solvent residues and, in particular during use (by evaporation), uncontrolled and undesired property changes can occur. Even under environmental aspects such a behavior may be problematic. In addition, thicker layers of solvent can generally produce only limited. The drying process is increasingly cost-intensive or high residual contents of solvent remain in the end product.
  • European Patent Application No. 1 234 851 discloses a crosslinkable rubber composition of a nitrile group-containing rubber further containing monomer units of an ethylenically unsaturated dicarboxylic acid monoalkylester monomer, wherein a polyamine can serve as a crosslinking agent and a basic crosslinking accelerator is used.
  • the dicarboxylic acid monoalkyl ester monomer units which differ structurally from the polyacrylate units of the present invention, serve as reactive groups for linking via the crosslinking agent.
  • acrylate polymers Homopolymer and copolymers of acrylic acid and / or methacrylic acid and their esters are understood as "acrylate polymers" in the sense of the invention, in which case the radicals forming the ester group can not bear any further functionality (ie represent hydrocarbon radicals) or be functionalized. Essentially all acrylic and methacrylic acid esters known in the art as constituents of acrylate polymers are suitable.
  • the acrylate polymer may further be selected from homo- and copolymers of methyl, ethyl, butyl, 2-ethylhexyl, cyclohexyl, dodecyl, 2-hydroxyethyl or 2-dimethylaminoethyl ester of acrylic or methacrylic acid and copolymers of these monomers become.
  • the copolymers may also have other comonomers, which do not originate from the group of acrylate monomers.
  • the acrylate polymers to be functionalized according to the invention may also have further comonomer constituents, which themselves do not have to represent acrylic acid or methacrylic acid derivatives. Essentially all monomers which are suitable as comonomers for acrylate polymers in the prior art are suitable here. Examples of suitable comonomers include acrylonitrile, methacrylonitrile, styrene, 1, 3-butadiene, 1, 2-butadiene, vinyl acetate, vinyl propionate, vinyl chloride and vinylidene chloride.
  • the acrylate polymers may contain between 0 and up to 100 mol%, preferably between 0 and 20 mol%, more preferably between 0 and 10 mol% of free carboxy groups.
  • the acrylate polymers of the present invention preferably contain no ethylenic dicarboxylic acids or their monoalkyl or dialkyl esters as comonomers.
  • Such acrylate polymers according to the invention in the absence of solvents (ie, in the melt) and in a temperature range between 50 ° C and 350 ° C, preferably between 100 ° C and 200 ° C, optionally in the presence of a catalyst, with a functionalizing agent implemented.
  • Functionalizing agents in the context of the invention are organic compounds having at least one primary (-NH 2 ) or secondary (-NH) amino function or amino group.
  • This primary or secondary amino group reacts in the course of the reaction with an ester function of the acrylate polymer to form an amide function (carboxylic acid amide).
  • the reaction thus leads to the replacement of a side chain on the polyacrylate backbone, wherein a new side chain (from an amide function) is introduced in each case for each original side chain (from an ester function) which is removed from the macromolecule.
  • the functionalizing agent is an organic compound other than the said primary or secondary amino functionality has no further functionality, thus easy replacement of an ester takes place against an amide side chain.
  • the functionalizing agent is an organic compound having at least one additional functionality to the primary or secondary amino function per molecule.
  • the inventive method allows the targeted introduction of further functionalities in the acrylate polymer.
  • the functionalities to be introduced into the acrylate polymer in this way are manifold. At best, a limitation can result from an undesired interaction of the functionalities involved or from the resulting undesirable reactions.
  • the functionalizing agent is an organic di- or polyamine having at least two or more primary and / or secondary amino groups per molecule. The functionalization in this case represents a crosslinking of the acrylate polymer.
  • the process according to the invention can be carried out in a batch process or in a continuous process, for example in a heatable extruder
  • the reaction can in principle be carried out in all apparatuses suitable for carrying out reactions in the molten state
  • the reaction can be carried out continuously or batchwise and under normal pressure as well as elevated / reduced pressure Suitable apparatuses are, for example, continuous single- and multi-shaft kneaders such as kneading autoclaves, Buss kneaders or twin-screw extruders
  • the reaction can also be carried out in a stirred autoclave having intensive mixing but low shear melt mixing means, which is particularly useful when relatively volatile compounds are used.
  • a particularly preferred method for carrying out the process is the continuous melt extrusion in single or twin screw extruders, because in this method a particularly intensive mixing is possible.
  • the reaction can therefore be carried out with tough melts, which can be carried out at low reaction temperatures.
  • An optimal mixture without high shear also ensures a very uniform mixing of the reaction mixture.
  • additives such as dyes are evenly distributed in the polymer.
  • the residence time in the heated zone is limited to an optimum, in order to avoid an unnecessary temperature load on the reaction mixture.
  • the method includes the steps of contacting the acrylate polymer in a molten state with the functionalizing agent, optionally in the presence of a catalyst, mixing the components, and maintaining a reaction temperature in the mixture in the range between 50 ° C and 350 ° C ° C, preferably 100 ° C and 200 ° C, for a sufficient time for the implementation of the components period.
  • Suitable catalysts are in principle all compounds which are known to the person skilled in the art as suitable catalysts for the reaction of a carboxylic acid ester into a carboxylic acid amide (see, for example, F. Körte (ed.), Methodicum Chimicum, Volume 6: CN compounds, me, Stuttgart 1974, Chapter 17, or R. Larock (ed.), Comprehensive Organic Transformations, 2nd Ed., Wiley-VCH, New York 1999, Chapter "Interconversion of Nitriles, Carboxylic Acids and Derivatives"
  • those of their own physical properties are suitable to be used under the process conditions described above.
  • Particularly suitable catalysts according to the invention are Brönstedt acids, in particular organic acids, and in particular carboxylic acids, preference being given to those carboxylic acids which are not volatile under the process conditions.
  • a suitable embodiment here represent, for example, hydrocarbon resins with carboxy functionality or a plurality of carboxyl functionalities per molecule.
  • the catalyst can in this case be used in ranges between 0.5 and 10% by weight, preferably between 0.5 and 5% by weight, based on the weight of the reactants used (acrylate polymer and functionalizing agent). Even larger or smaller weight ratios can - if necessary, be realized depending on the reaction conditions and reactants.
  • Suitable acrylate polymers are in particular polymers having a molecular weight in the range between 10,000 g / mol and 2,000,000 g / mol, preferably between 10,000 g / mol and 200,000 g / mol, in question.
  • acrylate polymers outside of these ranges can also be functionalized by the process of the present invention, provided the corresponding acrylate polymers are in molten state at the temperatures of the process.
  • the acrylate polymer is solid at room temperature.
  • functionalizing agents it is possible to use both aliphatic and aromatic primary or secondary amines. These amines may contain one or more other functional groups characterized by being stable in the presence of a corresponding amino function.
  • the functionalizing agents are usually used in a molar proportion of 0.1 to 100 mol%, based on the content of carboxy or carboxylic ester functions in the acrylate polymer used.
  • the functionalizing agents are aliphatic or aromatic, primary or secondary amines. In a preferred embodiment, they are aliphatic or aromatic, primary or secondary diamines. In a further preferred embodiment, these are aliphatic or aromatic, primary or secondary polyamines.
  • acrylate polymers By means of the process according to the invention, it is possible to functionalize acrylate polymers over a wide range, i.e. to introduce into the macromolecule those functional groups which can not be introduced by the copolymerization of a corresponding comonomer.
  • Such functionalizations include both polymer-analogous reactions (ie, reactions in which the molecular weight of the macromolecule does not change significantly) and crosslinking reactions (in which the molecular weight increases), as well as the combination of macromolecules with correspondingly functionalized solids (approximately corresponding functionalized silica, silicates or other inorganic or organic solids suitable for surface functionalization, carbon blacks, fullerenes, etc.
  • Functionalization reactions are introduced on corresponding surfaces, which can then react with acrylate polymers. This can be used, for example, to improve the adhesion of acrylate polymers to the surfaces of such workpieces.
  • the invention also relates to the structurally modified acrylate polymers obtained by the process.
  • Example 1 Reaction of acResin® DS 3500 with Jeffamine® M-2070: Increasing the water solubility by introducing a hydrophilic side chain
  • acResin® DS 3500 (BASF) is a polybutyl acrylate with a molecular weight of approx. 50,000 g / mol.
  • Existing carboxyl groups can be determined by titration with KOH; the consumption is 52 mg KOH per g of polymer. According to the manufacturer, the product is miscible with water to less than 10%.
  • the process according to the invention leads to an exchange of the butyl ester for polyetheramide side chains, which change its properties (water miscibility / solubility) with increasing concentration in the macromolecule.
  • Example 2 Reaction of Acronal® 4F with meta-xylenediamine: Cross-linking of a Polvacrylate by Crosslinking Starting Materials: Acronal® 4F (BASF) is a polybutyl acrylate with a molecular weight of 40,000 g / mol (without titratable acid groups).
  • BASF is a polybutyl acrylate with a molecular weight of 40,000 g / mol (without titratable acid groups).
  • Meia-xylylenediamine is a primary amine with two amino functions per molecule.
  • Foral® AX (Eastman) is a fully hydrogenated, acidic hydrocarbon resin used as a catalyst.
  • Foral®NC is a partially neutralized hydrocarbon resin (acid number 120-138), which is used as a catalyst.
  • the determined weights show the occurrence of a conversion to the amide;
  • the fairly long times may also be related to the delayed diffusion from the approach and are likely to be independent of the actual reaction. Improvement can be Smaller and more volatile groups take place, also in the sense of a generally accelerated progress of the action (also vacuum as an aid).

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de fonctionnalisation de polymères d'acrylate au moyen d'un agent fonctionnalisant à des températures comprises entre 50 °C et 350 °C, ledit agent présentant au moins un groupe amino primaire ou secondaire, ledit groupe amino étant transformé en fonction amide par réaction avec un groupe carboxyle des polymères d'acrylate et la réaction ayant lieu en absence de solvant. L'invention concerne en outre des polymères d'acrylate modifiés pouvant être obtenus par ce procédé.
PCT/EP2018/056758 2017-03-17 2018-03-16 Procédé de fonctionnalisation de polymères d'acrylate en absence de solvant et polymères d'acrylate modifiés pouvant être obtenus par ce procédé WO2018167310A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP18711940.9A EP3596139A1 (fr) 2017-03-17 2018-03-16 Procédé de fonctionnalisation de polymères d'acrylate en absence de solvant et polymères d'acrylate modifiés pouvant être obtenus par ce procédé

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017105755.2 2017-03-17
DE102017105755.2A DE102017105755A1 (de) 2017-03-17 2017-03-17 Funktionalisierte Acrylate (aus der Schmelze)

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Publication Number Publication Date
WO2018167310A1 true WO2018167310A1 (fr) 2018-09-20

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PCT/EP2018/056758 WO2018167310A1 (fr) 2017-03-17 2018-03-16 Procédé de fonctionnalisation de polymères d'acrylate en absence de solvant et polymères d'acrylate modifiés pouvant être obtenus par ce procédé

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EP (1) EP3596139A1 (fr)
DE (1) DE102017105755A1 (fr)
WO (1) WO2018167310A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328367A (en) * 1965-04-29 1967-06-27 Du Pont Copolymers
EP0722994A1 (fr) * 1994-12-21 1996-07-24 Lexmark International, Inc. Composition d'encre aqueuse pour l'impression par jet
EP0879860A2 (fr) * 1997-05-24 1998-11-25 Byk-Chemie GmbH Agent dispersant pour pigments ou charges à base de polyacrylates
EP1234851A1 (fr) 1999-08-20 2002-08-28 Zeon Corporation Composition de caoutchouc reticulable et objet reticule
EP1627023B1 (fr) 2003-05-19 2008-05-14 Tesa AG Procede de production d'une matiere adhesive de contact a base d'acrylate sans solvant et reticulable par ultraviolets

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328367A (en) * 1965-04-29 1967-06-27 Du Pont Copolymers
EP0722994A1 (fr) * 1994-12-21 1996-07-24 Lexmark International, Inc. Composition d'encre aqueuse pour l'impression par jet
EP0879860A2 (fr) * 1997-05-24 1998-11-25 Byk-Chemie GmbH Agent dispersant pour pigments ou charges à base de polyacrylates
EP1234851A1 (fr) 1999-08-20 2002-08-28 Zeon Corporation Composition de caoutchouc reticulable et objet reticule
EP1627023B1 (fr) 2003-05-19 2008-05-14 Tesa AG Procede de production d'une matiere adhesive de contact a base d'acrylate sans solvant et reticulable par ultraviolets

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
F. KORTE: "Methodicum Chimicum, Band 6: C-N-Verbindungen", vol. 6, 1974, THIEME, article "Kapitel 17"
R. LAROCK: "Comprehensive Organic Transformations, 2. Auflage", 1999, WILEY-VCH, article "Interconversion of Nitriles, Carboxylic Acids and Derivatives"

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EP3596139A1 (fr) 2020-01-22
DE102017105755A1 (de) 2018-09-20

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