EP2638091A1 - Condensation products of aminofunctional polymers - Google Patents

Condensation products of aminofunctional polymers

Info

Publication number
EP2638091A1
EP2638091A1 EP11781537.3A EP11781537A EP2638091A1 EP 2638091 A1 EP2638091 A1 EP 2638091A1 EP 11781537 A EP11781537 A EP 11781537A EP 2638091 A1 EP2638091 A1 EP 2638091A1
Authority
EP
European Patent Office
Prior art keywords
condensation product
phenol
epoxy resin
hydroxymethyl
condensation products
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP11781537.3A
Other languages
German (de)
French (fr)
Inventor
Jürgen Finter
Ulrich Gerber
Edis Kasemi
Andreas Kramer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sika Technology AG
Original Assignee
Sika Technology AG
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 Sika Technology AG filed Critical Sika Technology AG
Priority to EP11781537.3A priority Critical patent/EP2638091A1/en
Publication of EP2638091A1 publication Critical patent/EP2638091A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/44—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and containing rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C08G59/623—Aminophenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the present invention relates to novel Mannich-analogous condensation products and to a novel process for their preparation. Another object of the present invention is the use of these condensation products as accelerators in the curing of one- and two-component epoxy adhesives. State of the art
  • An epoxy resin consists of polyether polymers which, depending on the reaction conditions, with the addition of suitable hardeners, give a thermosetting plastic of high strength and chemical resistance. If epoxy resin and hardener are mixed, the curing of the originally viscous mixture usually takes place within a few minutes to a few hours, depending on the composition and temperature.
  • curing agents for epoxy resins are different systems available commercially, such as hardeners based on amine, amide and anhydride basis (for example, under the name Epikure ® from Hexion Specialty Chemicals) or hardener based on polyether (for example under the name Jeffamine ® from Huntsman).
  • Mannich bases of primary amines, formaldehyde and phenols can also be used as hardeners or accelerators (cf, inter alia, EP 0 253 339 A).
  • WO 00/15687 also describes a Mannich base accelerator which is prepared by transamination of a Mannich base with an amine.
  • Mannich bases are made using formaldehyde.
  • Formaldehyde is among other things responsible for the development of allergies, skin, respiratory and eye irritation. Accordingly, there is a need to provide Mannich analog condensation products which can be prepared while avoiding formaldehyde.
  • EP 1 475 41 1 A discloses a two-stage production process for Preparation of Mannich bases based on m-cresol or 3,5-xylenol and polyamines, in which a tertiary amine is preferably used.
  • a two-stage production process of Mannich bases is disclosed in EP 1 475 412 A, these being obtained from phenols such as m-cresol, 3,5-xylenol or resorcinol with polyamines, preferably using tertiary amines.
  • Such two-stage processes are associated with additional expense and make the production of Mannich bases more expensive.
  • the present invention has the object to provide alternative accelerators for epoxy resins or curing agents for epoxy resins and polyurethanes, which preferably do not have the disadvantages present.
  • the present invention has the object of providing accelerators for epoxy resins or curing agents for epoxy resins and polyurethanes which do not contain free phenol.
  • the present invention has the object to provide accelerators for epoxy resins or curing agents for epoxy resins and polyurethanes which contain no formaldehyde.
  • the present invention has the particular object of providing accelerators for epoxy resins or hardeners for epoxy resins and polyurethanes which have no oligomeric by-products.
  • R 1 is hydrogen or -CH 3 ;
  • R 2 is hydrogen or -CH 2 OH
  • R 3 is hydrogen or -CH 3 , and at least one polyoxyalkylenediamine is built up.
  • condensation products of the invention are suitable as accelerators for epoxy resins and as curing agents for epoxy resins or polyurethanes.
  • condensation products according to the invention are suitable for accelerating the curing of epoxy resin adhesives, for improving the adhesion of epoxy resin adhesives and / or peel strength of epoxy resin adhesives, which due to the use of special phenolic and amine components, the disadvantages known from the prior art are substantially avoided.
  • the condensation product according to the invention comprises no free phenol and no oligomeric by-products. Since, in contrast to conventional Mannich base synthesis in the context of the present invention, the use of formaldehyde is dispensed with, the condensation products according to the invention are also free of formaldehyde.
  • the condensation products according to the invention are accessible from readily available and inexpensive raw materials via a simple production process, which is described below and is also the subject of the present invention.
  • the condensation products of the invention are characterized in particular by an excellent curing behavior of epoxy resin adhesives.
  • the present invention relates to a condensation product which is prepared from at least one (hydroxymethyl) phenol as component (A) and at least one polyoxyalkylenediamine as component (B).
  • a (hydroxymethyl) phenol is understood as meaning an aromatic phenol which carries at least one methylol substituent in the ortho, meta or para position relative to the phenolic OH group.
  • Such phenols are commercially available.
  • the phenols may preferably carry one or two methylol groups. Preferably, the phenols carry only one methylol group. Suitable examples are 2- (hydroxymethyl) phenol (salicyl alcohol), 3- (hydroxymethyl) phenol, 4- (hydroxymethyl) phenol and 2,6-di (hydroxymethyl) -4-methyl-phenol. Particularly preferred are 2- (hydroxymethyl) phenol (salicyl alcohol), 3- (hydroxymethyl) phenol, 4- (hydroxymethyl) phenol.
  • the (hydroxymethyl) phenol used in the condensation product according to the invention is a phenol substituted in the ortho position with a methylol group, which optionally has further substituents, and corresponds to the general formula (I)
  • R 1 is hydrogen or -CH 3 ;
  • R 2 is hydrogen or -CH 2 OH
  • R 3 is hydrogen or -CH 3 .
  • R 2 is hydrogen.
  • Condensation products produced from this are distinguished by improved curing acceleration in epoxy resin compositions.
  • mixtures of such (hydroxymethyl) phenols can also be used in the context of the present invention for the preparation of the condensation products according to the invention.
  • the condensation product according to the invention is further synthesized from at least one polyoxyalkylenediamine.
  • a polyoxyalkylene diamine is understood as meaning a compound which terminally has in each case two primary amine functions which are linked to one another by a polyoxyalkylene backbone.
  • the polyoxyalkylene diamine used in the condensation product according to the invention preferably has units based on propylene oxide or ethylene oxide and propylene oxide. Further, it is preferable that the polyoxyalkylene diamine has a molecular weight in a range of 220 to 10,000 g / mol.
  • the polyoxyalkyldiamine has the general structure (II)
  • X1 stands for a value from 2 to 70.
  • Corresponding polyoxyalkylene diamines are available commercially from Huntsman under the trade names Jeffamine ® D-230, D-400, D-2000 and D-4000 with varying proportions of propylene glycol units.
  • the polyoxyalkylene diamine has the general structure (III):
  • indices x2, y2 and z2 have the following meaning:
  • o y2 equals 2 to 40
  • condensation products of (hydroxymethyl) phenols and polyoxyalkylenediamines according to the invention can be prepared from the phenolic compounds and polyoxyalkylenediamines described above by condensation reaction.
  • the preparation of these condensation products is possible by conventional condensation methods.
  • the condensation products are preferably prepared by the process described below:
  • Another aspect of the present invention is a novel process for the preparation of condensation products of the invention.
  • This process for the preparation of the invention is characterized in that at least one (hydroxymethyl) phenol is reacted with at least one polyoxyalkylenediamine.
  • the method according to the invention comprises the following method steps:
  • the reaction in the process according to the invention, in particular the process step (ii) described above, is preferably carried out for a period of 1 to 10 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours.
  • the process according to the invention is carried out under inert conditions, in particular in the presence of an inert gas.
  • the at least one (hydroxymethyl) phenol is reacted with the at least one polyoxyalkylenediamine in a stoichiometric ratio of 1 to 30, preferably 1 to 10, particularly preferably 1 to 1.
  • the present invention further relates to a condensation product obtainable by the method described above.
  • the condensation product according to the invention is particularly suitable as a curing agent for an amine-reactive substance which has at least two amine-reactive functional groups.
  • Suitable amine-reactive functional groups are, in particular, glycidyl ether and / or isocyanate groups.
  • the amine-reactive substance which has at least two amine-reactive functional groups is a diglycidyl ether. In particular, it is a diglycidyl ether of bisphenol-A, bisphenol-F or bisphenol-A / F.
  • Such diglycidyl ethers are available, for example, as Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or DER TM 331 or DER TM 330 (Dow) or Epikote 828 (Hexion).
  • the present invention therefore relates in particular to the use of at least one condensation product according to the invention or at least one condensation product obtainable in accordance with the process described above in epoxy resin systems, for example in the context of epoxy resin adhesives and coatings based on epoxy resins.
  • the condensation products of the invention are used to accelerate the curing of epoxy resin adhesives, to improve the adhesion of epoxy resin adhesives and / or peel strength of epoxy resin adhesives.
  • the condensation product according to the invention can be used as such or in a composition.
  • condensation products according to the invention and the condensation products of the invention resulting from the process according to the invention are used in particular in hardener components of two-component epoxy systems.
  • the condensation products according to the invention can be used here directly or as constituents of the hardener component.
  • the condensation products according to the invention are particularly preferably used as hardeners in two-component epoxy resin adhesives.
  • the present invention also relates to a two-component composition which consists of a first component K1 and a second component K2.
  • the first component K1 comprises at least one amine-reactive compound having at least two functional groups which can react with amines.
  • the second component K2 comprises at least one condensation product according to the invention.
  • both components K1 and K2 may comprise further ingredients known to the person skilled in the art.
  • Such further ingredients are in particular fillers, plasticizers, solvents, catalysts and / or additives.
  • Particularly suitable fillers are Russian, chalks, in particular coated chalks, sands, silicates, light fillers, such as ceramic or glass spheres, in particular ceramic or glass hollow spheres, pyrogenic silicic acids, fly ash.
  • Particularly preferred solvents are solvents which are not classified as VOC "volatile organic compounds.” Particularly preferred are higher-boiling hydrocarbons.
  • phthalates and adipates in particular di-acetyl phthalate (DIDP) and dioctyl adipate (DOA), are suitable as plasticizers.
  • DIDP di-acetyl phthalate
  • DOA dioctyl adipate
  • Such two-component compositions can be widely used.
  • Particularly preferred is their use as an adhesive or sealant, in particular as a structural adhesive. It has been found that the properties which can be achieved by means of the condensation products according to the invention are particularly desirable, in particular in the adhesive area.
  • the adhesive After mixing components K1 and K2 of the described two-component composition, the adhesive is applied to a substrate surface and joined to another surface of the substrate.
  • the cured composition acts as an adhesive layer capable of transferring forces between the two substrate surfaces of the formed composite.
  • the two-component composition is particularly well suited as a structural adhesive in building construction and civil engineering as well as in industry.
  • a two-part composition especially a two-part epoxy resin composition, i. in which component K1 comprises a diglycidyl ether can be used as an adhesive for the bonding of fiber-reinforced composites.
  • An illustrative example of this is the bonding of carbon fiber fins in reinforcing structures such as bridges.
  • inventive two-component compositions in particular a two-component epoxy resin composition, can be used as a plastic matrix for the production of fiber-reinforced composites.
  • carbon or glass fibers can be embedded in a two-component composition and, in the cured state, can be used as a fiber composite, for example in the form of a lamella.
  • fiber fabrics or fabrics can be applied to a building by means of a two-component composition, in particular by means of a two-component epoxy resin composition, and together with the building form a fiber-reinforced composite.
  • the viscosity of the condensation product according to the invention depends strongly on the phenolic compound used as well as on the polyamine used.
  • Particularly suitable condensation product according to the invention have a viscosity at 25 ° C. of less than 10,000 mPas.
  • Preferred condensation products of the invention have viscosities in the range between 200 and 7000 mPas.
  • condensation products of the invention have no oligomeric compounds.
  • the present invention will be explained in more detail with reference to the following examples. Examples
  • the condensation products B to E were prepared in an analogous manner.
  • the application (2) according to the invention shows a rapid increase in viscosity, which is attributable to the progressive hardening of bisphenol A diglycidyl ether (BADGE). This increase in viscosity is less pronounced in (1) and (3).
  • BADGE bisphenol A diglycidyl ether
  • the present application experiment thus shows that the viscosity of bisphenol A diglycidyl ether in the presence of the condensation product according to the invention increases more than with the comparison substances (the presence of Jeffamine ® D-400 alone or in the presence of Jeffamine ® D-400 and salicyl alcohol).
  • a device Mettler DSC822 8 was used for this purpose. 10-20 mg of the compositions were each weighed into an aluminum pan. After the sample in the DSC at a heating rate of 10 K / min was heated from 25 ° C to 200 ° C, the sample was cooled to 25 ° C and then heated at a heating rate of 10 K / min to 100 ° C.
  • the glass transition temperature (Tg) was determined by DSC software from the measured DSC curve and listed in Table 2.
  • the resulting cured epoxy resin comprises in the case of the use of the inventive condensation product A as a curing agent (Sample 2) a similar glass transition temperature to such a D-400 epoxy resin cured with Jeffamine ® (Sample 1) on; however, the cure is much faster.
  • the condensation products according to the invention are outstandingly suitable for accelerating the curing of epoxy resins. It can be dispensed with the use of phenol as the starting material, which is due to the toxicity of free phenol advantage.
  • the use of formaldehyde can also be dispensed with in the context of the synthesis of the condensation products according to the invention.
  • the condensation product of the invention can be used as a formaldehyde-free accelerator for the curing of epoxy resins.
  • a blending of the condensation products according to the invention with conventional polyamines for adjusting the viscosity is not required.
  • condensation product B for example, 1 g of condensation product B was mixed with 5:37 g Jeff- amine ® T-403rd
  • This mixture was then mixed aequimolar (with respect to the reactive H groups) with bisphenol A diglycidyl ether (eg, 13.63 g of bisphenol A diglycidyl ether in the case of condensation product B) and measured in GELNORM RVN.
  • bisphenol A diglycidyl ether eg, 13.63 g of bisphenol A diglycidyl ether in the case of condensation product B
  • GELNORM RVN As a comparative measurement, a sample was used consisting solely of starting amine (Jeffamine ® T-403, resp., Jeffamine ® D-400) which was quantity which is equimolar mixed (with respect to the reactive H groups) with bisphenol-A diglycidyl ether. The results are shown in FIGS. 2 and 3.
  • Figure 2 shows the increase in viscosity as a function of the reaction time for the condensation products B (KP-B) and C (KP-C) as compared to a sample consisting solely of starting amine (Jeff-T403).
  • 3 shows the increase in viscosity as a function of the reaction time for the condensation products D (KP-D) and E (KP-E) in comparison to a sample consisting solely of starting amine (Jeff-D400).

Abstract

The invention relates to a condensation product of at least one (hydroxy-methyl)phenol and at least one polyoxyalkylene diamine, to a method for producing same, and to the use thereof in curing epoxy resin systems.

Description

KONDENSATIONSPRODUKTE AUS AMINOFUNKTIONELLEN POLYMEREN  CONDENSATION PRODUCTS FROM AMINO FUNCTIONAL POLYMERS
Beschreibung Die vorliegende Erfindung betrifft neuartige Mannich-analoge Kondensationsprodukte sowie ein neues Verfahren zur deren Herstellung. Weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung dieser Kondensationsprodukte als Beschleuniger in der Härtung von Ein- und Zweikomponenten-Epoxidharz-Klebstoffen. Stand der Technik Description: The present invention relates to novel Mannich-analogous condensation products and to a novel process for their preparation. Another object of the present invention is the use of these condensation products as accelerators in the curing of one- and two-component epoxy adhesives. State of the art
Ein Epoxidharz besteht aus Polyetherpolymeren, die je nach Reaktionsführung unter Zugabe geeigneter Härter einen duroplastischen Kunststoff von hoher Festigkeit und chemischer Beständigkeit ergeben. Werden Epoxidharz und Härter gemischt, erfolgt je nach Zusammensetzung und Temperatur üblicherweise innerhalb von wenigen Minuten bis einigen Stunden die Aushärtung des ursprünglich viskosen Gemisches. Als Härter für Epoxidharze sind unterschiedliche Systeme kommerziell erhältlich, wie beispielsweise Härter auf Amin-, Amid- und Anhydridbasis (beispielsweise unter der Bezeichnung Epikure® von Hexion Speciality Chemicals) oder Härter auf Basis von Polyetheraminen (beispielsweise unter der Bezeichnung Jeffamine® von Huntsman). An epoxy resin consists of polyether polymers which, depending on the reaction conditions, with the addition of suitable hardeners, give a thermosetting plastic of high strength and chemical resistance. If epoxy resin and hardener are mixed, the curing of the originally viscous mixture usually takes place within a few minutes to a few hours, depending on the composition and temperature. As curing agents for epoxy resins are different systems available commercially, such as hardeners based on amine, amide and anhydride basis (for example, under the name Epikure ® from Hexion Specialty Chemicals) or hardener based on polyether (for example under the name Jeffamine ® from Huntsman).
Als Härter bzw. Beschleuniger können auch Mannichbasen aus primären Aminen, Formaldehyd und Phenolen eingesetzt werden (vgl. u.a EP 0 253 339 A). Ferner beschreibt auch die WO 00/15687 einen Mannichbasen-Beschleuniger, welcher durch Transaminierung einer Mannichbase mit einem Amin hergestellt wird. Mannich bases of primary amines, formaldehyde and phenols can also be used as hardeners or accelerators (cf, inter alia, EP 0 253 339 A). Furthermore, WO 00/15687 also describes a Mannich base accelerator which is prepared by transamination of a Mannich base with an amine.
Ein Nachteil entsprechender herkömmlicher Mannichbasen liegt in der Verwendung von Phenol als Ausgangsmaterial, da die erhaltenen Mannichbasen häufig noch nicht umgesetztes Phenol umfassen. Aufgrund der Toxizität von freiem Phenol sind auf Phenol basierende Mannichbasen für viele Anwendungsbereiche daher nicht einsetzbar. Deshalb sind große Bestrebung getätigt worden, Phenol-freie Mannichbasen herzustellen. So wurden beispielsweise Mannichbasen auf Basis von Nonylphenol oder p-tert.-Butylphenol oder Cardanol entwickelt (vgl. US 6,262, 148). Auch entspre- chende kommerzielle Produkte, wie Aradur 3442 von Huntsman Advanced Materials Inc., sind bekannt. A disadvantage of corresponding conventional Mannich bases is the use of phenol as starting material, since the resulting Mannich bases often comprise unreacted phenol. Because of the toxicity of free phenol, phenol-based Mannich bases are therefore unusable for many applications. Therefore, great efforts have been made to produce phenol-free Mannich bases. Thus, for example, Mannich bases based on nonylphenol or p-tert-butylphenol or cardanol have been developed (compare US 6,262,148). Also corresponding Commercial products such as Aradur 3442 from Huntsman Advanced Materials Inc. are known.
Ein weiterer Nachteil bei der Verwendung von herkömmlichen Mannichbasen besteht darin, dass diese unter Verwendung von Formaldehyd hergestellt werden. Formaldehyd wird unter anderem für die Entstehung von Allergien, Haut-, Atemwegs- und Augenreizungen verantwortlich gemacht. Demgemäß besteht Bedarf an der Bereitstellung von Mannich-analogen Kondensationsprodukten, welche unter Vermeidung von Formaldehyd herstellbar sind. Another disadvantage of using conventional Mannich bases is that they are made using formaldehyde. Formaldehyde is among other things responsible for the development of allergies, skin, respiratory and eye irritation. Accordingly, there is a need to provide Mannich analog condensation products which can be prepared while avoiding formaldehyde.
Ein weiterer großer Nachteil bekannter herkömmlicher Mannich-Härter ist die hohe Viskosität, die bei deren Herstellung aufgrund der Bildung von Oligomeren und Nebenprodukten entsteht. So bilden sich durch die Umsetzung von Phenolen mit Formaldehyd in einer herkömmlichen Mannichbasensynthese unter basischen Bedin- gungen hochmolekulare und verhältnismäßig hochviskose Resole aus. Wenn diese hochmolekularen und verhältnismäßigen hochviskosen Resole beispielsweise mit polymeren Polyaminen, die per se ebenfalls eine höhere Viskosität aufweisen, zu herkömmlichen Mannichbasen umgesetzt werden sollen, gelingt dieses aufgrund der hohen Viskosität der resultierenden Reaktionsmischung im Allgemeinen nicht. Daher sind herkömmliche Mannichbasen aus Phenolen, Formaldehyd und polymeren Polyaminen im Allgemeinen nicht zugänglich. Another major disadvantage of known conventional Mannich hardeners is the high viscosity that results from their production due to the formation of oligomers and by-products. Thus, by reacting phenols with formaldehyde in a conventional Mannich base synthesis under basic conditions form high molecular weight and relatively high viscosity Resole. If these high molecular weight and relatively high-viscosity resoles, for example, with polymeric polyamines, which also have a higher viscosity per se, to be converted to conventional Mannich bases, this is not possible due to the high viscosity of the resulting reaction mixture in general. Therefore, conventional Mannich bases of phenols, formaldehyde and polymeric polyamines are generally not accessible.
Bei der Herstellung von herkömmlichen Mannichbasen-Härtern wird üblicherweise mit einem großen Überschuss an Amin gearbeitet, um das Molekulargewicht und so die Viskosität niedrig zu halten. Daher werden im Allgemeinen herkömmliche Mannichbasen-Härter in Abmischung mit üblichen Polyaminen eingesetzt. Die Zumischung zusätzlicher Polyamine wirkt sich jedoch meist negativ auf die Eigenschaften der ausgehärteten Epoxidharz-Zusammensetzung aus. Darüber hinaus sind die Verfahren zur Herstellung bekannter Mannichbasen sehr aufwändig und schwierig zu führen, insbesondere dann, wenn die Ausbildung von hochmolekularen Kondensationsprodukten möglichst verhindert werden soll. So offenbart beispielsweise die EP 1 475 41 1 A ein zweistufiges Herstellverfahren zur Herstellung von Mannichbasen basierend auf m-Kresol oder 3,5-Xylenol und Polya- minen, bei dem vorzugsweise ein tertiäres Amin verwendet wird. Ebenso wird ein zweistufiges Herstellverfahren von Mannichbasen in der EP 1 475 412 A offenbart, wobei diese aus Phenolen wie m-Kresol, 3,5-Xylenol oder Resorcin mit Polyaminen vorzugsweise unter Verwendung von tertiären Aminen gewonnen werden. Derartige zweistufige Verfahren sind mit zusätzlichem Aufwand verbunden und verteuern die Herstellung der Mannichbasen. In the production of conventional Mannich base hardeners, a large excess of amine is usually used in order to keep the molecular weight and thus the viscosity low. Therefore, conventional Mannich base hardeners are generally used in admixture with conventional polyamines. The addition of additional polyamines, however, usually has a negative effect on the properties of the cured epoxy resin composition. In addition, the processes for preparing known Mannich bases are very complicated and difficult to perform, especially if the formation of high molecular weight condensation products should be prevented as much as possible. For example, EP 1 475 41 1 A discloses a two-stage production process for Preparation of Mannich bases based on m-cresol or 3,5-xylenol and polyamines, in which a tertiary amine is preferably used. Likewise, a two-stage production process of Mannich bases is disclosed in EP 1 475 412 A, these being obtained from phenols such as m-cresol, 3,5-xylenol or resorcinol with polyamines, preferably using tertiary amines. Such two-stage processes are associated with additional expense and make the production of Mannich bases more expensive.
Ausgehend von diesem Stand der Technik stellt sich die vorliegende Erfindung die Aufgabe, alternative Beschleuniger für Epoxidharze oder Härter für Epoxidharze und Polyurethane bereitzustellen, welche die vorliegenden Nachteile vorzugsweise nicht aufweisen. Starting from this prior art, the present invention has the object to provide alternative accelerators for epoxy resins or curing agents for epoxy resins and polyurethanes, which preferably do not have the disadvantages present.
Insbesondere stellt sich die vorliegende Erfindung die Aufgabe, Beschleuniger für Epoxidharze oder Härter für Epoxidharze und Polyurethane bereitzustellen, welche kein freies Phenol enthalten. In particular, the present invention has the object of providing accelerators for epoxy resins or curing agents for epoxy resins and polyurethanes which do not contain free phenol.
Ferner stellt sich die vorliegende Erfindung die Aufgabe, Beschleuniger für Epoxidharze oder Härter für Epoxidharze und Polyurethane bereitzustellen, welche kein Formaldehyd enthalten. Furthermore, the present invention has the object to provide accelerators for epoxy resins or curing agents for epoxy resins and polyurethanes which contain no formaldehyde.
Bei der Herstellung entsprechender Beschleuniger sollte daher vorzugsweise auf die Verwendung von Phenolen und Formaldehyd verzichtet werden. Des Weiteren stellt sich die vorliegende Erfindung insbesondere die Aufgabe, Beschleuniger für Epoxidharze oder Härter für Epoxidharze und Polyurethane bereitzustellen, welche keine oligomeren Nebenprodukte aufweisen. In the production of appropriate accelerators should therefore preferably be dispensed with the use of phenols and formaldehyde. Furthermore, the present invention has the particular object of providing accelerators for epoxy resins or hardeners for epoxy resins and polyurethanes which have no oligomeric by-products.
, Daher sollten die Beschleuniger auf einfache Weise ohne die Bildung von unerwünschten hochmolekularen Kondensationsprodukten erhältlich sein. Darstellung der Erfindung Therefore, the accelerators should be readily available without the formation of undesirable high molecular weight condensation products. Presentation of the invention
Gelöst werden diese Aufgaben durch ein Kondensationsprodukt, welches These tasks are solved by a condensation product, which
destens einem (Hydroxymethyl)phenol der allgemeinen Formel (I) at least one (hydroxymethyl) phenol of the general formula (I)
in welcher: in which:
R1 gleich Wasserstoff oder -C H 3 ist; R 1 is hydrogen or -CH 3 ;
R2 gleich Wasserstoff oder -C H2O H ist; und R 2 is hydrogen or -CH 2 OH; and
R3 gleich Wasserstoff oder -C H 3 ist, und mindestens einem Polyoxyalkylendiamin aufgebaut wird. R 3 is hydrogen or -CH 3 , and at least one polyoxyalkylenediamine is built up.
Die erfindungsgemäßen Kondensationsprodukte eignen sich als Beschleuniger für Epoxidharze sowie als Härter für Epoxidharze oder Polyurethane. The condensation products of the invention are suitable as accelerators for epoxy resins and as curing agents for epoxy resins or polyurethanes.
Insbesondere eignen sich diese erfindungsgemäßen Kondensationsprodukte zur Beschleunigung der Aushärtung von Epoxidharzklebstoffen, zur Verbesserung der Haftung von Epoxidharzklebstoffen und/oder Schälfestigkeit von Epoxidharzklebstoffen, wobei aufgrund der Verwendung spezieller Phenol- und Aminkomponenten die aus dem Stand der Technik bekannten Nachteile im Wesentlichen vermieden werden. Insbesondere umfasst das erfindungsgemäße Kondensationsprodukt kein freies Phenol und keine oligomeren Nebenprodukte. Da im Gegensatz zu der herkömmlichen Mannichbasensynthese im Rahmen der vorliegenden Erfindung auf die Verwendung von Formaldehyd verzichtet wird, sind die erfindungsgemäß resultierenden Kondensationsprodukte auch frei von Formaldehyd. Die erfindungsgemäßen Kondensationsprodukte sind aus einfach zugänglichen und kostengünstigen Rohstoffen über ein einfaches Herstellungsverfahren, welches weiter unten beschrieben wird und ebenfalls Gegenstand der vorliegenden Erfindung ist, zugänglich. Die erfindungsgemäßen Kondensationsprodukte zeichnen sich insbe- sondere durch ein exzellentes Härtungsverhalten von Epoxidharz-Klebstoffen aus. In particular, these condensation products according to the invention are suitable for accelerating the curing of epoxy resin adhesives, for improving the adhesion of epoxy resin adhesives and / or peel strength of epoxy resin adhesives, which due to the use of special phenolic and amine components, the disadvantages known from the prior art are substantially avoided. In particular, the condensation product according to the invention comprises no free phenol and no oligomeric by-products. Since, in contrast to conventional Mannich base synthesis in the context of the present invention, the use of formaldehyde is dispensed with, the condensation products according to the invention are also free of formaldehyde. The condensation products according to the invention are accessible from readily available and inexpensive raw materials via a simple production process, which is described below and is also the subject of the present invention. The condensation products of the invention are characterized in particular by an excellent curing behavior of epoxy resin adhesives.
Im Folgenden werden bevorzugte Ausgestaltungen des erfindungsgemäßen Kondensationsprodukts näher beschrieben. Die vorliegende Erfindung betrifft ein Kondensationsprodukt, welches aus mindestens einem (Hydoxymethyl)phenol als Komponente (A) und mindestens einem Poly- oxyalkylendiamin als Komponente (B) hergestellt wird. In the following, preferred embodiments of the condensation product according to the invention are described in more detail. The present invention relates to a condensation product which is prepared from at least one (hydroxymethyl) phenol as component (A) and at least one polyoxyalkylenediamine as component (B).
Komponente (A) - (Hydoxymethyl)phenol Component (A) - (Hydoxymethyl) phenol
Unter einem (Hydroxymethyl)phenol wird im Rahmen der vorliegenden Erfindung ein aromatisches Phenol verstanden, welches in ortho-, meta- oder para-Position zur phenolischen OH-Gruppe mindestens einen Methylolsubstituenten trägt. Solche Phenole sind kommerziell erhältlich. In the context of the present invention, a (hydroxymethyl) phenol is understood as meaning an aromatic phenol which carries at least one methylol substituent in the ortho, meta or para position relative to the phenolic OH group. Such phenols are commercially available.
Im Rahmen der vorliegenden Erfindung können die Phenole vorzugsweise eine oder zwei Methylolgruppe tragen. Vorzugsweise tragen die Phenole nur eine Methylolgruppe. Geeignete Beispiele sind 2-(Hydroxymethyl)phenol (Salicylalkohol), 3- (Hydroxymethyl)phenol, 4-(Hydroxymethyl)phenol sowie 2,6-Di(hydroxymethyl)-4- methyl-phenol. Besonders bevorzugt sind 2-(Hydroxymethyl)phenol (Salicylalkohol), 3-(Hydroxymethyl)phenol, 4-(Hydroxymethyl)phenol. In the context of the present invention, the phenols may preferably carry one or two methylol groups. Preferably, the phenols carry only one methylol group. Suitable examples are 2- (hydroxymethyl) phenol (salicyl alcohol), 3- (hydroxymethyl) phenol, 4- (hydroxymethyl) phenol and 2,6-di (hydroxymethyl) -4-methyl-phenol. Particularly preferred are 2- (hydroxymethyl) phenol (salicyl alcohol), 3- (hydroxymethyl) phenol, 4- (hydroxymethyl) phenol.
Das in dem erfindungsgemäßen Kondensationsprodukt verwendete (Hydroxy- methyl)phenol ist ein mit einer Methylolgruppe in ortho-Position substituiertes Phenol, welches gegebenenfalls weitere Substituenten aufweist, und entspricht der allgemeinen Formel (I) The (hydroxymethyl) phenol used in the condensation product according to the invention is a phenol substituted in the ortho position with a methylol group, which optionally has further substituents, and corresponds to the general formula (I)
in welcher: in which:
R1 gleich Wasserstoff oder -C H 3 ist; R 1 is hydrogen or -CH 3 ;
R2 gleich Wasserstoff oder -C H2O H ist; und R 2 is hydrogen or -CH 2 OH; and
R3 gleich Wasserstoff oder -C H 3 ist. R 3 is hydrogen or -CH 3 .
Vorzugsweise ist R2 gleich Wasserstoff. Daraus hergestellte Kondensationsprodukte zeichnen sich durch eine verbesserte Aushärtungsbeschleunigung in Epoxidharzzusammensetzungen aus. Selbstverständlich können im Rahmen der vorliegenden Erfindungen zur Herstellung der erfindungsgemäßen Kondensationsprodukte auch Mischungen solcher (Hydroxymethyl)phenole verwendet werden. Preferably, R 2 is hydrogen. Condensation products produced from this are distinguished by improved curing acceleration in epoxy resin compositions. Of course, mixtures of such (hydroxymethyl) phenols can also be used in the context of the present invention for the preparation of the condensation products according to the invention.
Die Auswahl der eingesetzten (Hydroxymethyl)phenole beeinflusst stark die Eigenschaften der resultierenden Kondensationsprodukte und damit der unter Verwendung dieser Kondensationsprodukte als Härter bzw. Beschleuniger resultierenden Epoxid- Systeme. The selection of the (hydroxymethyl) phenols used greatly influences the properties of the resulting condensation products and thus the epoxy systems resulting from the use of these condensation products as hardeners or accelerators.
Komponente (B) - Polyoxyalkylendiamin Das erfindungsgemäße Kondensationsprodukt wird ferner aus mindestens einem Polyoxyalkylendiamin aufgebaut. Im Rahmen der vorliegenden Erfindung wird unter einem Polyoxyalkylendiamin eine Verbindung verstanden, welche terminal jeweils zwei primäre Aminfunktionen aufweist, die durch ein Polyoxyalkylen-Rückgrat miteinander verbunden sind. Das in dem erfindungsgemäßen Kondensationsprodukt verwendete Polyoxyalkylendiamin weist dabei vorzugsweise Einheiten auf Basis von Propylenoxid oder Ethy- lenoxid und Propylenoxid auf. Des Weiteren ist es bevorzugt, wenn das Polyoxyalkylendiamin ein Molekulargewicht in einem Bereich von 220 bis 10.000 g/mol aufweist. Component (B) - Polyoxyalkylenediamine The condensation product according to the invention is further synthesized from at least one polyoxyalkylenediamine. In the context of the present invention, a polyoxyalkylene diamine is understood as meaning a compound which terminally has in each case two primary amine functions which are linked to one another by a polyoxyalkylene backbone. The polyoxyalkylene diamine used in the condensation product according to the invention preferably has units based on propylene oxide or ethylene oxide and propylene oxide. Further, it is preferable that the polyoxyalkylene diamine has a molecular weight in a range of 220 to 10,000 g / mol.
In einer ersten Ausgestaltung der vorliegenden Erfindung weist das Polyoxyalkyl diamin die allgemeine Struktur (II) In a first embodiment of the present invention, the polyoxyalkyldiamine has the general structure (II)
auf, in welcher X1 für einen Wert von 2 bis 70 steht. in which X1 stands for a value from 2 to 70.
Entsprechende Polyoxyalkylendiamine sind kommerziell erhältlich von Huntsman unter den Bezeichnungen Jeffamine® D-230, D-400, D-2000 und D-4000 mit unterschiedlichen Anteilen an Propylenglykoleinheiten. Corresponding polyoxyalkylene diamines are available commercially from Huntsman under the trade names Jeffamine ® D-230, D-400, D-2000 and D-4000 with varying proportions of propylene glycol units.
In einer weiteren Ausgestaltung der vorliegenden Erfindung weist das Polyoxyalkylendiamin die allgemeine Struktur (III) auf : In a further embodiment of the present invention, the polyoxyalkylene diamine has the general structure (III):
(III) (III)
in welcher die Indizes x2, y2 und z2 die folgende Bedeutung aufweisen: in which the indices x2, y2 and z2 have the following meaning:
o y2 gleich 2 bis 40 und  o y2 equals 2 to 40 and
o x2 + z2 gleich 1 bis 7.  o x2 + z2 equals 1 to 7.
Entsprechende Polyoxyalkylendeamine sind kommerziell erhältlich von Huntsman unter den Bezeichnungen Jeffamine® HK-51 1 (y2 = 2; x2 + z2 = ~ 1 ,2); ED-600 (y2 = ~ 9; x2 + z2 = ~ 3,6); ED-900 (y2 = ~ 12,5; x2 + z2 = ~ 6,0) und ED-2003 (y2 = ~ 39; x2 + z2 = ~ 6,0). Corresponding Polyoxyalkylendeamine are commercially available from Huntsman under the trade names Jeffamine ® HK-51 1 (y2 = 2; x2 + z2 = ~ 1, 2); ED-600 (y2 = ~ 9, x2 + z2 = ~ 3.6); ED-900 (y2 = ~ 12.5, x2 + z2 = ~ 6.0) and ED-2003 (y2 = ~ 39; x2 + z2 = ~ 6.0).
Die erfindungsgemäßen Kondensationsprodukte aus (Hydroxymethyl)phenolen und Polyoxyalkylendiaminen lassen sich aus den zuvor beschriebenen phenolischen Verbindungen und Polyoxyalkylendiaminen durch Kondensationsreaktion herstellen. Die Herstellung dieser Kondensationsprodukte ist nach üblichen Kondensationsverfahren möglich. Bevorzugt werden jedoch die Kondensationsprodukte nach dem im folgenden beschriebenen Verfahren hergestellt: The condensation products of (hydroxymethyl) phenols and polyoxyalkylenediamines according to the invention can be prepared from the phenolic compounds and polyoxyalkylenediamines described above by condensation reaction. The preparation of these condensation products is possible by conventional condensation methods. However, the condensation products are preferably prepared by the process described below:
So stellt ein weiterer Aspekt der vorliegenden Erfindung ein neues Verfahren für die Herstellung von erfindungsgemäßen Kondensationsprodukten dar. Dieses erfindungsgemäße Verfahren zur Herstellung zeichnet sich dadurch aus, dass mindestens ein (Hydroxymethyl)phenol mit mindestens einem Polyoxyalkylendiamin umgesetzt wird. Thus, another aspect of the present invention is a novel process for the preparation of condensation products of the invention. This process for the preparation of the invention is characterized in that at least one (hydroxymethyl) phenol is reacted with at least one polyoxyalkylenediamine.
Als (Hydroxymethyl)phenol kann eine wie oben beschriebene (Hydroxymethyl)- phenolverbindung verwendet werden. Insoweit wird auf die obigen Ausführungen verwiesen. Als Polyoxyalkylendiamin kann eine wie oben beschriebene Polyoxyalkylendiamin- verbindung verwendet werden. Insoweit wird ebenfalls auf die obigen Ausführungen verwiesen. In einer bevorzugten Ausführungsform umfasst das erfindungsgemäße Verfahren die folgenden Verfahrensschritte: As (hydroxymethyl) phenol, a (hydroxymethyl) phenol compound as described above can be used. In that regard, reference is made to the above statements. As the polyoxyalkylene diamine, a polyoxyalkylene diamine compound as described above can be used. In that regard, reference is also made to the above statements. In a preferred embodiment, the method according to the invention comprises the following method steps:
(i) Vorlegen von mindestens einem (Hydroxymethyl)phenol und von mindestens einem Polyoxyalkylendiamin bei einer Temperatur von 15 bis 100 °C, bevorzugt 20 bis 90 °C, besonders bevorzugt 20 bis 70 °C, in einem Reaktionsgefäß; (I) presenting at least one (hydroxymethyl) phenol and at least one polyoxyalkylenediamine at a temperature of 15 to 100 ° C, preferably 20 to 90 ° C, particularly preferably 20 to 70 ° C, in a reaction vessel;
Erhöhen der Temperatur auf 120 bis 190 °C, bevorzugt 120 bis 180 °C, besonders bevorzugt 120 bis 170 °C. Die Umsetzung in dem erfindungsgemäße Verfahren, insbesondere der zuvor beschriebene Verfahrensschritt (ii), wird vorzugsweise für einen Zeitraum von 1 bis 10 Stunden, bevorzugt 1 bis 8 Stunden, besonders bevorzugt 2 bis 5 Stunden, durchgeführt. Des Weiteren ist es bevorzugt, wenn das erfindungsgemäße Verfahren unter inerten Bedingungen, insbesondere in Gegenwart eines Inertgases, durchgeführt wird.  Raising the temperature to 120 to 190 ° C, preferably 120 to 180 ° C, more preferably 120 to 170 ° C. The reaction in the process according to the invention, in particular the process step (ii) described above, is preferably carried out for a period of 1 to 10 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours. Furthermore, it is preferred if the process according to the invention is carried out under inert conditions, in particular in the presence of an inert gas.
Vorteilhafterweise wird das mindestens eine (Hydroxymethyl)phenol mit dem mindestens einen Polyoxyalkylendiamin in einem stöchiometrischen Verhältnis von 1 zu 30, bevorzugt 1 zu 10, besonders bevorzugt 1 zu 1 , umgesetzt. Advantageously, the at least one (hydroxymethyl) phenol is reacted with the at least one polyoxyalkylenediamine in a stoichiometric ratio of 1 to 30, preferably 1 to 10, particularly preferably 1 to 1.
Die vorliegende Erfindung betrifft ferner ein Kondensationsprodukt, welches durch das zuvor beschriebene Verfahren erhältlich ist. Das erfindungsgemäße Kondensationsprodukt eignet sich insbesondere als Härter für eine Amin-reaktive Substanz, welche mindestens zwei Amin-reaktive funktionelle Gruppen aufweist. Als derartige Amin-reaktive funktionelle Gruppen kommen insbesondere Glycidylether- und/oder Isocyanat-Gruppen in Betracht. In einer Ausführungsform der vorliegenden Erfindung ist die Amin-reaktive Substanz, welche mindestens zwei Amin-reaktive funktionelle Gruppen aufweist, ein Diglycidy- lether. Insbesondere ist es ein Diglycidylether von Bisphenol-A, Bisphenol-F oder Bisphenol-A/F. Solche Diglycidylether sind beispielsweise als Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) oder D.E.R.™ 331 oder D.E.R.™ 330 (Dow) oder Epikote 828 (Hexion) erhältlich. The present invention further relates to a condensation product obtainable by the method described above. The condensation product according to the invention is particularly suitable as a curing agent for an amine-reactive substance which has at least two amine-reactive functional groups. Suitable amine-reactive functional groups are, in particular, glycidyl ether and / or isocyanate groups. In one embodiment of the present invention, the amine-reactive substance which has at least two amine-reactive functional groups is a diglycidyl ether. In particular, it is a diglycidyl ether of bisphenol-A, bisphenol-F or bisphenol-A / F. Such diglycidyl ethers are available, for example, as Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or DER ™ 331 or DER ™ 330 (Dow) or Epikote 828 (Hexion).
Durch Mischen der Amin-reaktiven Substanz, welche mindestens zwei Amin-reaktive funktionelle Gruppen aufweist, mit dem erfindungsgemässen Kondensationsprodukt tritt eine Reaktion der Amingruppen des Kondensationsprodukts mit den Amin- reaktiven funktionellen Gruppen der Amin-reaktiven Substanz auf und es erfolgt eine Aushärtung. By mixing the amine-reactive substance which has at least two amine-reactive functional groups with the condensation product according to the invention, a reaction of the amine groups of the condensation product with the amine-reactive functional groups of the amine-reactive substance occurs and curing takes place.
Daher betrifft die vorliegende Erfindung insbesondere die Verwendung von mindes- tens einem erfindungsgemäßen Kondensationsprodukt oder mindestens einem gemäß dem oben beschriebenen Verfahren erhältlichen Kondensationsprodukt in Epoxidharzsystemen, beispielsweise im Rahmen von Epoxidharzklebstoffen und Be- schichtungen auf Basis von Epoxidharzen. Insbesondere werden die erfindungsgemäßen Kondensationsprodukte zur Beschleunigung der Aushärtung von Epoxidharzklebstoffen, zur Verbesserung der Haftung von Epoxidharzklebstoffen und/oder Schälfestigkeit von Epoxidharzklebstoffen verwendet. Das erfindungsgemäße Kondensationsprodukt kann als solches oder in einer Zusammensetzung eingesetzt werden.  The present invention therefore relates in particular to the use of at least one condensation product according to the invention or at least one condensation product obtainable in accordance with the process described above in epoxy resin systems, for example in the context of epoxy resin adhesives and coatings based on epoxy resins. In particular, the condensation products of the invention are used to accelerate the curing of epoxy resin adhesives, to improve the adhesion of epoxy resin adhesives and / or peel strength of epoxy resin adhesives. The condensation product according to the invention can be used as such or in a composition.
Die erfindungsgemäßen Kondensationsprodukte sowie die aus dem erfindungsgemäßen Verfahren resultierenden erfindungsgemäßen Kondensationsprodukte finden insbesondere Einsatz in Härterkomponenten von zweikomponentigen Epoxidsyste- men. Die erfindungsgemäßen Kondensationsprodukte können hier direkt oder als Bestandteile der Härterkomponente eingesetzt werden. Besonders bevorzugt werden die erfindungsgemäßen Kondensationsprodukte eingesetzt als Härter in zweikomponentigen Epoxidharz-Klebstoffen. The condensation products according to the invention and the condensation products of the invention resulting from the process according to the invention are used in particular in hardener components of two-component epoxy systems. The condensation products according to the invention can be used here directly or as constituents of the hardener component. The condensation products according to the invention are particularly preferably used as hardeners in two-component epoxy resin adhesives.
Die mit diesen erfindungsgemäßen Kondensationsprodukten gehärteten zweikompo- nentigen Epoxidsysteme und die daraus erhaltenen Produkte weisen sehr vorteilhafte Eigenschaften auf. The two-component epoxy systems cured with these condensation products according to the invention and the products obtained therefrom have very advantageous properties.
Wenn das erfindungsgemäße Kondensationsprodukt zur Aushärtung von Am inreaktiven Systemen eingesetzt wird, betrifft die vorliegende Erfindung auch eine zweikomponentige Zusammensetzung, welche aus einer ersten Komponente K1 und einer zweiten Komponente K2 besteht. Die erste Komponente K1 umfasst mindestens eine Amin-reaktive Verbindung mit mindestens zwei funktionellen Gruppen, welche mit Aminen reagieren können. Die zweite Komponente K2 umfasst mindestens ein erfindungsgemäßes Kondensationsprodukt. Als Amin-reaktive Verbindungen, welche mindestens zwei funktionelle Gruppen aufweisen, die mit Aminen reagieren können, sind bereits vorgängig beschrieben worden. When the condensation product according to the invention is used for the curing of amineactive systems, the present invention also relates to a two-component composition which consists of a first component K1 and a second component K2. The first component K1 comprises at least one amine-reactive compound having at least two functional groups which can react with amines. The second component K2 comprises at least one condensation product according to the invention. As amine-reactive compounds which have at least two functional groups which can react with amines have already been described above.
Beide Komponenten K1 und K2 können bei Bedarf weitere dem Fachmann bekannte Inhaltsstoffe umfassen. Derartige weitere Inhaltsstoffe sind insbesondere Füllstoffe, Weichmacher, Lösungsmittel, Katalysatoren und/oder Additive. If required, both components K1 and K2 may comprise further ingredients known to the person skilled in the art. Such further ingredients are in particular fillers, plasticizers, solvents, catalysts and / or additives.
Als Füllstoffe gelten insbesondere Russe, Kreiden, insbesondere beschichtete Kreiden, Sande, Silikate, Leichtfüllstoffe, wie Keramik- oder Glaskugeln, insbesondere Keramik- oder Glashohlkugeln, pyrogene Kieselsäuren, Flugasche, als bevorzugt. Particularly suitable fillers are Russian, chalks, in particular coated chalks, sands, silicates, light fillers, such as ceramic or glass spheres, in particular ceramic or glass hollow spheres, pyrogenic silicic acids, fly ash.
Als Lösungsmittel werden insbesondere derartige Lösungsmittel bevorzugt, welche nicht als VOC„volatile organic Compounds" eingestuft werden. Besonders bevorzugt werden höher siedende Kohlenwasserstoffe. Particularly preferred solvents are solvents which are not classified as VOC "volatile organic compounds." Particularly preferred are higher-boiling hydrocarbons.
Als Weichmacher sind insbesondere Phthalate und Adipate, insbesondere Diisode- cylphthalat (DIDP) und Dioctyladipat (DOA). Derartige zweikomponentige Zusammensetzungen lassen sich breit einsetzen. Insbesondere bevorzugt ist deren Verwendung als Klebstoff oder Dichtstoff, insbesondere als struktureller Klebstoff. Es hat sich nämlich gezeigt, dass die mittels den er- findungsgemässen Kondensationsprodukten erzielbaren Eigenschaften insbesonde- re im Klebstoffbereich besonders erwünscht sind. In particular, phthalates and adipates, in particular di-acetyl phthalate (DIDP) and dioctyl adipate (DOA), are suitable as plasticizers. Such two-component compositions can be widely used. Particularly preferred is their use as an adhesive or sealant, in particular as a structural adhesive. It has been found that the properties which can be achieved by means of the condensation products according to the invention are particularly desirable, in particular in the adhesive area.
Nach dem Mischen der Komponenten K1 und K2 der beschriebenen zweikomponen- tigen Zusammensetzung wird der Klebstoff auf eine Substratoberfläche appliziert und mit einer weiteren Substartoberfläche gefügt. Die ausgehärtete Zusammensetzung wirkt als Klebschicht, welche befähigt ist, Kräfte zwischen den zwei Substratoberflächen des gebildeten Verbundkörpers zu übertragen. After mixing components K1 and K2 of the described two-component composition, the adhesive is applied to a substrate surface and joined to another surface of the substrate. The cured composition acts as an adhesive layer capable of transferring forces between the two substrate surfaces of the formed composite.
Die zweikomponentige Zusammensetzung eignet sich aufgrund ihrer Eigenschaften speziell gut als struktureller Klebstoff im Hoch- und Tiefbau, sowie in der Industrie. Beispielsweise kann eine derartige zweikomponentige Zusammensetzung, insbesondere eine zweikomponentige Epoxidharz-Zusammensetzung, d.h. in welcher die Komponente K1 einen Diglycidylether umfasst, als Klebstoff für das Verkleben von faserverstärkten Composites eingesetzt werden. Ein illustrierendes Beispiel hierfür ist das Verkleben von Kohlenfaser-Lamellen beim Verstärken von Bauwerken, wie Brücken. Due to its properties, the two-component composition is particularly well suited as a structural adhesive in building construction and civil engineering as well as in industry. For example, such a two-part composition, especially a two-part epoxy resin composition, i. in which component K1 comprises a diglycidyl ether can be used as an adhesive for the bonding of fiber-reinforced composites. An illustrative example of this is the bonding of carbon fiber fins in reinforcing structures such as bridges.
Weiterhin können erfindungsgemässe zweikomponentige Zusammensetzungen, insbesondere eine zweikomponentige Epoxidharz-Zusammensetzung, als Kunststoffmatrix für die Herstellung von faserverstärkten Composites eingesetzt werden. So lassen sich beispielsweise Kohlen- oder Glasfasern in eine zweikomponentige Zu- sammensetzung einbetten und können im ausgehärteten Zustand als Faser- Composite, beispielsweise in Form einer Lamelle, zum Einsatz kommen. Furthermore, inventive two-component compositions, in particular a two-component epoxy resin composition, can be used as a plastic matrix for the production of fiber-reinforced composites. For example, carbon or glass fibers can be embedded in a two-component composition and, in the cured state, can be used as a fiber composite, for example in the form of a lamella.
Ebenso können beispielsweise Fasergewebe oder -gelege mittels einer zweikompo- nentigen Zusammensetzung, insbesondere mittels einer zweikomponentigen Epo- xidharz-Zusammensetzung, auf ein Bauwerk appliziert werden, und dort mit dem Bauwerk zusammen ein faserverstärktes Composite bilden. Die Viskosität des erfindungsgemäßen Kondensationsprodukts hängt dabei jeweils stark von der eingesetzten phenolischen Verbindung sowie vom eingesetzten Poly- amin ab. Besonders geeignete erfindungsgemäße Kondensationsprodukts weisen eine Viskosität bei 25 °C kleiner als 10000 mPas auf. Bevorzugte erfindungsgemäße Kondensationsprodukte weisen Viskositäten im Bereich zwischen 200 und 7000 mPas auf. Likewise, for example, fiber fabrics or fabrics can be applied to a building by means of a two-component composition, in particular by means of a two-component epoxy resin composition, and together with the building form a fiber-reinforced composite. The viscosity of the condensation product according to the invention depends strongly on the phenolic compound used as well as on the polyamine used. Particularly suitable condensation product according to the invention have a viscosity at 25 ° C. of less than 10,000 mPas. Preferred condensation products of the invention have viscosities in the range between 200 and 7000 mPas.
Dem Fachmann ist klar, dass bei dieser Art von Umsetzung in geringem Masse auch noch nicht reagierte Bestandteile im Endprodukt vorhanden sein können. It is clear to the person skilled in the art that, in the case of this type of reaction, unreacted constituents may also be present to a lesser extent in the end product.
Die erfindungsgemäßen Kondensationsprodukte weisen keine oligomeren Verbindungen auf. Die vorliegende Erfindung wird anhand der nachfolgenden Beispiele näher erläutert. Beispiele The condensation products of the invention have no oligomeric compounds. The present invention will be explained in more detail with reference to the following examples. Examples
Die im Folgenden genannten Beispiele dienen zur Veranschaulichung der Erfindung. The following examples serve to illustrate the invention.
1. Herstellungsverfahren 1. Manufacturing process
Im Folgenden wird ein Verfahren zur Herstellung erfindungsgemäßer Kondensationsprodukte näher beschrieben: In the following, a process for the production of condensation products according to the invention is described in more detail:
Kondensationsprodukt A Condensation product A
Ein 500 ml-Rundgefäß wird mit 20 g (0,0473 mol) Jeffamine® D-400 und 14 g (0,946 mol) Salicylalkohol befüllt und unter Stickstoff am Rotationsverdampfer erwärmt. Nachdem eine homogene Mischung erhalten wurde (ungefähr 50 °C) wird ein Vaku- um angelegt (~ 20 mbar). Anschließend wird die Temperatur auf 165 °C erhöht. Die Reaktion wird nach 5 Stunden beendet, um ein braunes relativ viskoses Material („Kondensationsprodukt A") zu erhalten. Eine LC-MS-Analyse zeigt, dass das Produkt ungefähr 45 % Produkt an dem erfindungsgemäßen zweikernigen aromatischen Kondensationsprodukt, 45 % einkerniges aromatisches Addukt und 10 % nichtrea- giertes Jeffamine® D-400 umfasst. A 500 mL round vessel is charged with 20 g (0.0473 mol) of Jeffamine ® D-400 and 14 g (0.946 mol) of salicyl filled and heated under nitrogen on a rotary evaporator. After a homogeneous mixture is obtained (about 50 ° C), a vacuum is applied (~20 mbar). Then the temperature is raised to 165 ° C. The reaction is terminated after 5 hours to give a brown relatively viscous material ("condensation product A"). LC-MS analysis shows that the product is about 45% product on the binuclear aromatic Condensation product, 45% mononuclear aromatic adduct and 10% nichtrea- giertes Jeffamine ® D-400 comprises.
Die Kondensationsprodukte B bis E wurden auf analoge Art und Weise hergestellt.  The condensation products B to E were prepared in an analogous manner.
Tabelle 1 , Herstellung Kondensationsprodukte A bis E, *= molare Verhältnisse von Salicylalkohol, resp. Bis(hydroxymethyl)cresol zu Jeffamin D-400, resp. Jeffamin T- 403. Table 1, Preparation of condensation products A to E, * = molar ratios of salicylic alcohol, respectively. Bis (hydroxymethyl) cresol to Jeffamin D-400, resp. Jeffamine T-403.
2. Anwendungsbeispiele 2. Application examples
Es wurden die in Tabelle 2 aufgeführten Proben hergestellt The samples listed in Table 2 were prepared
In einem ersten Anwendungsversuch wird die zeitliche (t) Entwicklung der Viskosität (η) mit GELNORM-RVN bei Raumtemperatur untersucht. Die Viskosität wird dabei in Prozenten des maximalen Drehmoments angegeben. Die Ergebnisse sind in der Figur 1 dargestellt, in welcher (1 ) für die Probe 1 (Vergleichsbeispiel), (2) für die Probe 2 (erfindungsgemäßes Beispiel) und (3) für die Probe 3 (Vergleichsbeispiel) steht. Man beobachtet eine signifikante Beschleunigung der Härtung mit dem erfindungsgemäßen Kondensationsprodukt A aus Jeffamine® D-400 und Salicylalkohol im Ver- gleich zu einer alleinigen Verwendung von Jeffamine D-400 oder zur Verwendung von Jeffamine® D-400 in der Gegenwart von ungebundenem Salicylalkohol. In a first application experiment the temporal (t) development of the viscosity (η) with GELNORM-RVN at room temperature is investigated. The viscosity is specified as a percentage of the maximum torque. The results are shown in FIG. 1, in which (1) stands for sample 1 (comparative example), (2) for sample 2 (example according to the invention) and (3) for sample 3 (comparative example). A significant acceleration of curing with the inventive condensation product A from Jeffamine ® D-400 and is observed in comparison salicyl equal to a sole use of Jeffamine D-400 or for use of Jeffamine ® D-400 in the presence of unbound salicyl.
Die Ergebnisse sind in der Figur 1 dargestellt, in welcher (1 ) für die Probe 1 (Ver- gleichsbeispiel), (2) für die Probe 2 (erfindungsgemäßes Beispiel) und (3) für die Probe 3 (Vergleichsbeispiel) steht. The results are shown in FIG. 1, in which (1) stands for sample 1 (comparative example), (2) for sample 2 (example according to the invention) and (3) for sample 3 (comparative example).
Wie der Figur 1 zu entnehmen ist, zeigt die erfindungsgemäße Anwendung (2) eine schnelle Viskositätszunahme, welche auf die fortschreitende Härtung von Bisphenol- A-diglycidylether (BADGE) zurückzuführen ist. Dieser Viskositätsanstieg ist bei (1 ) und (3) geringer ausgeprägt. As can be seen from FIG. 1, the application (2) according to the invention shows a rapid increase in viscosity, which is attributable to the progressive hardening of bisphenol A diglycidyl ether (BADGE). This increase in viscosity is less pronounced in (1) and (3).
Der vorliegende Anwendungsversuch zeigt somit, dass die Viskosität von Bisphenol- A-diglycidylether in Gegenwart des erfindungsgemäßen Kondensationsprodukts stärker ansteigt als mit den Vergleichssubstanzen (Gegenwart von Jeffamine® D-400 alleine bzw. in Gegenwart von Jeffamine® D-400 und Salicylalkohol). The present application experiment thus shows that the viscosity of bisphenol A diglycidyl ether in the presence of the condensation product according to the invention increases more than with the comparison substances (the presence of Jeffamine ® D-400 alone or in the presence of Jeffamine ® D-400 and salicyl alcohol).
Diese Beobachtungen werden von DSC-Messungen bestätigt, welche 24 Stunden nach dem Härten bei Raumtemperaturen durchgeführt wurden. These observations are confirmed by DSC measurements made 24 hours after room temperature curing.
Es wurde hierfür ein Gerät Mettler DSC8228 verwendet. 10 - 20 mg der Zusammensetzungen wurden jeweils in einen Aluminiumtiegel eingewogen. Nachdem die Probe im DSC mit einer Heizrate von 10 K / min von 25°C auf 200°C aufgeheizt wurde, wurde die Probe auf 25°C abgekühlt und anschliessend mit einer Heizrate von 10 K/min bis 100°C aufgeheizt. Die Glasübergangstemperatur (Tg) wurde mit Hilfe der DSC-Software aus der gemessenen DSC-Kurve bestimmt und in Tabelle 2 aufgeführt. A device Mettler DSC822 8 was used for this purpose. 10-20 mg of the compositions were each weighed into an aluminum pan. After the sample in the DSC at a heating rate of 10 K / min was heated from 25 ° C to 200 ° C, the sample was cooled to 25 ° C and then heated at a heating rate of 10 K / min to 100 ° C. The glass transition temperature (Tg) was determined by DSC software from the measured DSC curve and listed in Table 2.
Das resultierende ausgehärtete Epoxidharz weist im Fall der Verwendung von dem erfindungsgemäßen Kondensationsprodukt A als Härter (Probe 2) eine ähnliche Glasübergangstemperatur auf wie ein mit Jeffamine® D-400 gehärtetes Epoxidharz (Probe 1 ) auf; allerdings verläuft die Härtung viel schneller. Wie aus dem erfindungsgemäßen Beispiel ersichtlich, eignen sich die erfindungsgemäßen Kondensationsprodukte hervorragend für die Beschleunigung der Aushärtung von Epoxidharzen. Dabei kann auf die die Verwendung von Phenol als Ausgangsmaterial verzichtet werden, was aufgrund der Toxizität von freiem Phenol von Vorteil ist. Auch auf die Verwendung von Formaldehyd kann im Rahmen der Synthese der erfindungsgemäßen Kondensationsprodukten verzichtet werden. Damit kann das erfindungsgemäße Kondensationsprodukte als Formaldehyd-freier Beschleuniger für die Aushärtung von Epoxidharzen verwendet werden. The resulting cured epoxy resin comprises in the case of the use of the inventive condensation product A as a curing agent (Sample 2) a similar glass transition temperature to such a D-400 epoxy resin cured with Jeffamine ® (Sample 1) on; however, the cure is much faster. As can be seen from the example according to the invention, the condensation products according to the invention are outstandingly suitable for accelerating the curing of epoxy resins. It can be dispensed with the use of phenol as the starting material, which is due to the toxicity of free phenol advantage. The use of formaldehyde can also be dispensed with in the context of the synthesis of the condensation products according to the invention. Thus, the condensation product of the invention can be used as a formaldehyde-free accelerator for the curing of epoxy resins.
Da im Rahmen der vorliegenden Erfindung bei der Synthese der Kondensationsprodukte auf die Verwendung von Formaldehyd verzichtet wird, kommt es auch nicht zu einer unerwünschten Bildung von Resolen, die zu einem Viskositätsanstieg bei der basischen Synthese herkömmlicher Mannichbasen führen. Damit können zur Herstellung der erfindungsgemäßen Kondensationsprodukte auch Polyamine eingesetzt werden, die per se ebenfalls eine höhere Viskosität aufweisen. Since the use of formaldehyde is dispensed with in the synthesis of the condensation products in the context of the present invention, there is also no undesired formation of resols which lead to an increase in viscosity in the basic synthesis of conventional Mannich bases. Thus, for the preparation of the condensation products according to the invention it is also possible to use polyamines which likewise have a higher viscosity per se.
Auch eine Abmischung der erfindungsgemäßen Kondensationsprodukte mit üblichen Polyaminen zur Einstellung der Viskosität ist nicht erforderlich. A blending of the condensation products according to the invention with conventional polyamines for adjusting the viscosity is not required.
In einem weiteren Anwendungsversuch wurde erneut die zeitliche (t) Entwicklung der Viskosität (η) mit GELNORM-RVN bei Raumtemperatur der Kondensationsprodukte B, C, D und E untersucht. In a further application experiment, the temporal (t) development of the viscosity (η) with GELNORM-RVN at room temperature of the condensation products B, C, D and E was again investigated.
Es wurde zuerst eine Mischung aus 0.1 Aequivalent (H-Aequivalent) des Kondensationsprodukts mit 0.9 Aequivalent Ausgangsamin hergestellt. Im Fall des Kondensationsprodukts B wurde beispielsweise 1 g Kondensationsprodukt B mit 5.37 g Jeff- amine® T-403 vermischt. It was first prepared a mixture of 0.1 equivalent (H equivalent) of the condensation product with 0.9 equivalent of starting amine. In the case of the condensation product B, for example, 1 g of condensation product B was mixed with 5:37 g Jeff- amine ® T-403rd
Diese Mischung wurde dann aequimolar (in Bezug auf die reaktiven H-Gruppen) mit Bisphenol-A-diglycidylether (e.g. 13.63 g Bisphenol-A-diglycidylether im Fall von Kondensationsprodukt B) gemischt und im GELNORM RVN gemessen. Als Vergleichsmessung diente eine Probe bestehend einzig aus Ausgangsamin (Jeffamine® T-403, resp. Jeffamine® D-400), welche aequimolar (in Bezug auf die reaktiven H-Gruppen) mit Bisphenol-A-diglycidylether gemischt wurde. Die Ergebnisse sind in den Figuren 2 und 3 dargestellt. Fig. 2 zeigt die Zunahme der Viskosität als Funktion der Reaktionszeit für die Kondensationsprodukte B (KP-B) und C (KP-C) im Vergleich zu einer Probe bestehend einzig aus Ausgangsamin (Jeff- T403). Fig. 3 zeigt die Zunahme der Viskosität als Funktion der Reaktionszeit für die Kondensationsprodukte D (KP-D) und E (KP-E) im Vergleich zu einer Probe beste- hend einzig aus Ausgangsamin (Jeff-D400). This mixture was then mixed aequimolar (with respect to the reactive H groups) with bisphenol A diglycidyl ether (eg, 13.63 g of bisphenol A diglycidyl ether in the case of condensation product B) and measured in GELNORM RVN. As a comparative measurement, a sample was used consisting solely of starting amine (Jeffamine ® T-403, resp., Jeffamine ® D-400) which was quantity which is equimolar mixed (with respect to the reactive H groups) with bisphenol-A diglycidyl ether. The results are shown in FIGS. 2 and 3. Figure 2 shows the increase in viscosity as a function of the reaction time for the condensation products B (KP-B) and C (KP-C) as compared to a sample consisting solely of starting amine (Jeff-T403). 3 shows the increase in viscosity as a function of the reaction time for the condensation products D (KP-D) and E (KP-E) in comparison to a sample consisting solely of starting amine (Jeff-D400).
Aus den Ergebnissen der Figuren 2 und 3 ist ersichtlich, dass bei Kondensationsprodukten aus einem (Hydroxymethyl)phenol der allgemeinen Formel (I) in welcher R2 gleich Wasserstoff ist, die Härtung schneller verläuft. From the results of Figures 2 and 3 it can be seen that in condensation products of a (hydroxymethyl) phenol of the general formula (I) in which R 2 is hydrogen, the curing proceeds faster.

Claims

Patentansprüche: claims:
1 . Kondensationsprodukt aus mindestens einem (Hydroxymethyl)phenol der allgemeinen Formel (I) 1 . Condensation product of at least one (hydroxymethyl) phenol of the general formula (I)
in welcher: in which:
R1 gleich Wasserstoff oder -C H 3 ist; R 1 is hydrogen or -CH 3 ;
R2 gleich Wasserstoff oder -C H2O H ist; und R 2 is hydrogen or -CH 2 OH; and
R3 gleich Wasserstoff oder -C H 3 ist, und mindestens einem Polyoxyalkylendiamin. R 3 is hydrogen or -CH 3 , and at least one polyoxyalkylene diamine.
Kondensationsprodukt nach Anspruch 1 , dadurch gekennzeichnet, dass das Polyoxyalkylendiamin Einheiten auf Basis von Ethylenoxid, Propylenoxid oder Ethylenoxid und Propylenoxid umfasst. Condensation product according to claim 1, characterized in that the polyoxyalkylene diamine comprises units based on ethylene oxide, propylene oxide or ethylene oxide and propylene oxide.
Kondensationsprodukt nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Polyoxyalkylendiamin der allgemeinen Struktur (II) entspricht: Condensation product according to claim 1 or 2, characterized in that the polyoxyalkylene diamine corresponds to the general structure (II):
(Ii) auf, in welcher X1 für einen Wert von 2 bis 70 steht. (Ii) in which X1 stands for a value from 2 to 70.
Kondensationsprodukt nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Polyoxyalkylendiamin der allgemeinen Struktur (III) entspricht: Condensation product according to claim 1 or 2, characterized in that the polyoxyalkylene diamine corresponds to the general structure (III):
in welcher die Indizes x2, y2 und z2 die folgende Bedeutung aufweisen: in which the indices x2, y2 and z2 have the following meaning:
o y2 gleich 2 bis 40 und  o y2 equals 2 to 40 and
o x2 + z2 gleich 1 bis 7.  o x2 + z2 equals 1 to 7.
Kondensationsprodukt nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Polyoxyalkylendiamin ein Molekulargewicht von 220 bis 10.000 g/mol aufweist. Condensation product according to one of claims 1 to 4, characterized in that the polyoxyalkylene diamine has a molecular weight of 220 to 10,000 g / mol.
Verfahren zur Herstellung eines Kondensationsprodukts, dadurch gekennzeichnet, dass mindestens ein (Hydroxymethyl)phenol mit mindestens einem Polyoxyalkylendiamin umgesetzt wird. A process for the preparation of a condensation product, characterized in that at least one (hydroxymethyl) phenol is reacted with at least one polyoxyalkylenediamine.
Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass ein (Hydroxy- methyl)phenol gemäß der Definition in Anspruch 1 verwendet wird. A method according to claim 6, characterized in that a (hydroxymethyl) phenol is used as defined in claim 1.
Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass ein Polyoxyalkylendiamin gemäß der Definition in einem der Ansprüche 2 bis 5 verwendet wird. A method according to claim 6 or 7, characterized in that a polyoxyalkylene diamine is used as defined in any one of claims 2 to 5.
Verfahren nach einem der Ansprüche 6 bis 8, umfassend die folgenden Verfahrensschritte: Vorlegen von mindestens einem (Hydroxymethyl)phenol und von mindestens einem Polyoxyalkylendiamin bei einer Temperatur von 15 bis 100 °C, bevorzugt 20 bis 90 °C, besonders bevorzugt 20 bis 70 °C, in einem Reaktionsgefäß; Method according to one of claims 6 to 8, comprising the following method steps: Presenting at least one (hydroxymethyl) phenol and at least one polyoxyalkylene diamine at a temperature of 15 to 100 ° C, preferably 20 to 90 ° C, more preferably 20 to 70 ° C, in a reaction vessel;
Erhöhen der Temperatur auf 120 bis 190 °C, bevorzugt 120 bis 180 °C, besonders bevorzugt 120 bis 170 °C.  Raising the temperature to 120 to 190 ° C, preferably 120 to 180 ° C, more preferably 120 to 170 ° C.
Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass das Verfahren für einen Zeitraum von 1 bis 10 Stunden, bevorzugt 1 bis 8 Stunden, besonders bevorzugt 2 bis 5 Stunden, durchgeführt wird. A method according to claim 9, characterized in that the method for a period of 1 to 10 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours, is performed.
Verfahren nach einem der Ansprüche 6 bis 10, dadurch gekennzeichnet, dass das mindestens eine (Hydroxymethyl)phenol mit dem mindestens einen Polyoxyalkylendiamin in einem stöchiometrischen Verhältnis von 1 zu 30, bevorzugt 1 zu 10, besonders bevorzugt 1 zu 1 , umgesetzt wird. Method according to one of claims 6 to 10, characterized in that the at least one (hydroxymethyl) phenol with the at least one polyoxyalkylenediamine in a stoichiometric ratio of 1 to 30, preferably 1 to 10, particularly preferably 1 to 1, is reacted.
Kondensationsprodukt, erhältlich nach einem Verfahren gemäß einem der Ansprüche 6 bis 1 1 . A condensation product obtainable by a process according to any one of claims 6 to 11.
Verwendung von mindestens einem Kondensationsprodukt gemäß einem der Ansprüche 1 bis 5 oder gemäß Anspruch 12 in Epoxidharzsystemen, insbeson dere in Epoxidharzklebstoffen und Epoxidharzbeschichtungen. Use of at least one condensation product according to one of claims 1 to 5 or according to claim 12 in epoxy resin systems, in particular in epoxy resin adhesives and epoxy resin coatings.
Verwendung nach Anspruch 13 zur Beschleunigung der Aushärtung von Epoxidharzklebstoffen, zur Verbesserung der Haftung von Epoxidharzklebstoffen und/oder Schälfestigkeit von Epoxidharzklebstoffen. Use according to claim 13 for accelerating the curing of epoxy resin adhesives, for improving the adhesion of epoxy resin adhesives and / or peel strength of epoxy resin adhesives.
Zweikomponentige Zusammensetzung, umfassend eine ersten Komponente, welche mindestens einen Amin-reaktive Verbindung mit mindestens zwei funktionellen Gruppen, welche mit Aminen reagieren können, umfasst, und eine zweite Komponente, welche mindestens eine Kondensationsprodukt gemäss einem der Ansprüche 1 bis 5 oder gemäß Anspruch 12 umfasst. A two-component composition comprising a first component comprising at least one amine-reactive compound having at least two functional groups capable of reacting with amines, and a second component comprising at least one condensation product according to any one of claims 1 to 5 or claim 12 ,
EP11781537.3A 2010-11-11 2011-11-10 Condensation products of aminofunctional polymers Withdrawn EP2638091A1 (en)

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EP10190823A EP2452963A1 (en) 2010-11-11 2010-11-11 Condensation products of aminofunctional polymers
EP11781537.3A EP2638091A1 (en) 2010-11-11 2011-11-10 Condensation products of aminofunctional polymers
PCT/EP2011/069838 WO2012062853A1 (en) 2010-11-11 2011-11-10 Condensation products of aminofunctional polymers

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US9157015B2 (en) 2015-10-13
EP2452963A1 (en) 2012-05-16
US9586889B2 (en) 2017-03-07
CN103201306B (en) 2016-11-02
JP6117700B2 (en) 2017-04-19
JP2013542304A (en) 2013-11-21
JP2017106021A (en) 2017-06-15
US20160016888A1 (en) 2016-01-21
CN103201306A (en) 2013-07-10
WO2012062853A1 (en) 2012-05-18
US20130225723A1 (en) 2013-08-29

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