EP2638091A1 - Produits de condensation composés de polymères aminofonctionnels - Google Patents

Produits de condensation composés de polymères aminofonctionnels

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Withdrawn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)
English (en)
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/fr
Publication of EP2638091A1 publication Critical patent/EP2638091A1/fr
Withdrawn legal-status Critical Current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).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne un produit de condensation composé d'au moins un (hydroxy-méthyl)phénol et d'au moins une polyoxyalkylène-diamine, un procédé de préparation de ce produit et son utilisation dans le durcissage de systèmes de résines époxy.
EP11781537.3A 2010-11-11 2011-11-10 Produits de condensation composés de polymères aminofonctionnels Withdrawn EP2638091A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11781537.3A EP2638091A1 (fr) 2010-11-11 2011-11-10 Produits de condensation composés de polymères aminofonctionnels

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10190823A EP2452963A1 (fr) 2010-11-11 2010-11-11 Produits de condensation constitués de polymères aminofonctionnels
EP11781537.3A EP2638091A1 (fr) 2010-11-11 2011-11-10 Produits de condensation composés de polymères aminofonctionnels
PCT/EP2011/069838 WO2012062853A1 (fr) 2010-11-11 2011-11-10 Produits de condensation composés de polymères aminofonctionnels

Publications (1)

Publication Number Publication Date
EP2638091A1 true EP2638091A1 (fr) 2013-09-18

Family

ID=43759992

Family Applications (2)

Application Number Title Priority Date Filing Date
EP10190823A Withdrawn EP2452963A1 (fr) 2010-11-11 2010-11-11 Produits de condensation constitués de polymères aminofonctionnels
EP11781537.3A Withdrawn EP2638091A1 (fr) 2010-11-11 2011-11-10 Produits de condensation composés de polymères aminofonctionnels

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP10190823A Withdrawn EP2452963A1 (fr) 2010-11-11 2010-11-11 Produits de condensation constitués de polymères aminofonctionnels

Country Status (5)

Country Link
US (2) US9157015B2 (fr)
EP (2) EP2452963A1 (fr)
JP (2) JP6117700B2 (fr)
CN (1) CN103201306B (fr)
WO (1) WO2012062853A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3585475B1 (fr) 2017-02-24 2024-04-03 Nalu Medical, Inc. Appareil avec stimulateurs implantés séquentiellement

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2356151A (en) * 1941-04-09 1944-08-22 Resinous Prod & Chemical Co Polyphenylol alkane resins
US3148150A (en) * 1960-05-12 1964-09-08 Petrolite Corp Process for preventing, reducing and removing hard-water scale employing methylol pheol derivatives
US3462393A (en) * 1967-05-05 1969-08-19 Dow Chemical Co Epoxy resin with diamine of polyoxypropylene glycol and method of cure
CH513112A (de) * 1968-11-13 1971-09-30 Reichhold Albert Chemie Ag Verfahren zur Herstellung von substituierten Phenolen
US4454059A (en) * 1976-11-12 1984-06-12 The Lubrizol Corporation Nitrogenous dispersants, lubricants and concentrates containing said nitrogenous dispersants
JPS5491598A (en) * 1977-12-27 1979-07-20 Texaco Development Corp Hardener for epoxy resin and rapidly hardening method of said epoxy resin
US4164520A (en) 1977-12-27 1979-08-14 Texaco Development Corporation Accelerated cure of epoxy resins
DE2928554A1 (de) 1979-07-14 1981-01-29 Bayer Ag Verfahren zur herstellung eines gemisches aus 2- und 4-hydroxybenzylalkohol
US4681965A (en) * 1985-08-08 1987-07-21 Texaco Inc. Phosphorus containing aromatic amino polyols
US4714750A (en) * 1986-06-25 1987-12-22 Texaco Inc. Synthesis of products from polyoxyalkylene amines and 2,6-di-t-butylphenol for use as epoxy accelerators and curing agents
DE3624314A1 (de) 1986-07-18 1988-01-28 Hoechst Ag Verwendung von epoxidharz/haerter-mischungen zur herstellung von beschichtungen mit erhoehter zwischenschichthaftung
US4786683A (en) * 1987-05-26 1988-11-22 The Firestone Tire & Rubber Company Phenolic resin and polyether treated guayule resin
US5098986A (en) * 1990-11-19 1992-03-24 Texaco Chemical Company Paired alkyl phenol Mannich condensates
EP0487188A1 (fr) * 1990-11-19 1992-05-27 Texaco Chemical Company Condensats de Mannich alkylphénoliques
US5120817A (en) * 1991-02-27 1992-06-09 Texaco Chemical Company Epoxy resin compositions
JP3327038B2 (ja) * 1995-03-16 2002-09-24 大日本インキ化学工業株式会社 エポキシ樹脂組成物
US6262148B1 (en) 1998-07-01 2001-07-17 Vantico Inc. Phenalkamine curing agents and epoxy resin compositions containing the same
DK1114076T3 (da) 1998-09-14 2003-07-07 Vantico Ag Acceleratorer til hærdbare systemer
JP2001106783A (ja) * 1999-10-01 2001-04-17 Arakawa Chem Ind Co Ltd フェノール樹脂組成物およびエポキシ樹脂用硬化剤
JP2001213938A (ja) * 2000-01-31 2001-08-07 Nippon Paint Co Ltd アミノポリエーテル変性エポキシおよびこれを含有するカチオン電着塗料組成物
JP4050905B2 (ja) * 2002-01-24 2008-02-20 旭化成ケミカルズ株式会社 フェノール類のメチレン化物の製造方法
EP1475411A1 (fr) 2003-05-05 2004-11-10 Sika Technology AG Bases de Mannich et préparation de bases de Mannich
EP1475412A1 (fr) 2003-05-05 2004-11-10 Sika Technology AG Compositions de résines époxydes contenant une base de Mannich pour les applications à température élevée
US7125916B2 (en) * 2003-10-14 2006-10-24 National Chung-Hsing University Method for producing nanosilica plates
JP5148812B2 (ja) * 2004-06-29 2013-02-20 新日鉄住金化学株式会社 ビスフェノール類の製造方法
US20090099312A1 (en) * 2007-10-15 2009-04-16 Carl Duane Weber Amine terminated tougheners for epoxy resin based adhesives and materials

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2012062853A1 *

Also Published As

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

Similar Documents

Publication Publication Date Title
EP2997069B1 (fr) Composition de résine époxy pour produits semi-finis fibres-matrice
DE102009028019A1 (de) Härtbare Zusammensetzungen auf Basis von Epoxidharzen und hetero-poly-cyclischen Polyaminen
EP2837645A1 (fr) Utilisation de 2,5-bisaminométhylfurane comme durcisseur pour résines époxy
WO2004099312A1 (fr) Compositions de resine epoxy contenant des bases de mannich, appropriees pour des applications a haute temperature
EP2825580B1 (fr) Nouveaux catalyseurs de polymères réactifs pour systèmes de résine époxy 2k
EP1716195A1 (fr) Kit a plusieurs composants utilise a des fins de fixation et son utilisation
DE202013012362U1 (de) Epoxybasierte Masse für Befestigungszwecke, deren Verwendung und die Verwendung bestimmter Komponenten
WO2006117339A1 (fr) Base de mannich a base de resorcine
WO2017009220A1 (fr) Utilisation d'oligo-n,n-bis-(3-aminopropyl)méthylamine en tant que durcisseur pour des résines époxydes
EP2953991B1 (fr) Composition durcissable avec une grande résistance à la rupture
EP3770200A1 (fr) Composition de résine époxy pour des applications de revêtement résistant aux produits chimiques
EP2948493A2 (fr) 2,2',6,6'-tétraméthyl-4,4'-méthylène-bis(cyclohexylamine) servant de durcisseur pour des résines époxydes
DE3151592A1 (de) Haertbare kunstharzmischungen und mittel fuer haertbare kunstharzmischungen auf basis von praepolymeren polyaetherurethanharnstoffaminen und epoxidharzen
EP1978048A1 (fr) Durcisseur pour résine époxy, procédé de durcissement d'une résine époxy tout comme utilisation du durcisseur
WO2015022186A1 (fr) Utilisation de polypropylèneimine en tant que durcisseur pour résines époxydes
EP2638091A1 (fr) Produits de condensation composés de polymères aminofonctionnels
DE2604739A1 (de) Polymerisierbare harzmasse
EP0131802B1 (fr) Procédé de préparation de revêtements à base d'un mélange contenant une résine époxyde et un durcisseur
EP3571182B1 (fr) N,n -diaminopropyl-2-méthyl-cyclohexane-1,3-diamine et n,n'-diaminopropyl-4-méthyl-cyclohexane-1,3-diamine et leur utilisation comme durcisseurs de resines epoxydes
WO2009124680A1 (fr) Mélanges de polyisocyanates
WO2020187855A1 (fr) Composition de polyuréthane à deux composants
EP3320014B1 (fr) Compositions durcissables
WO2015158684A1 (fr) Mélange de polyamine cyanoalkylée et d'accélérateur comme durcisseur latent pour résines époxy
EP3381963A1 (fr) Durcisseur pour résine époxyde
EP2818491A1 (fr) Composition durcissable avec une grande résistance à la rupture

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130611

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20171026

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20191010

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20200221