WO1999028365A1 - Additifs de composes monoepoxy aromatiques et de norbornanediamine - Google Patents

Additifs de composes monoepoxy aromatiques et de norbornanediamine Download PDF

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Publication number
WO1999028365A1
WO1999028365A1 PCT/EP1998/007463 EP9807463W WO9928365A1 WO 1999028365 A1 WO1999028365 A1 WO 1999028365A1 EP 9807463 W EP9807463 W EP 9807463W WO 9928365 A1 WO9928365 A1 WO 9928365A1
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WO
WIPO (PCT)
Prior art keywords
general formula
adduct
compound
adducts
diglycidyl ether
Prior art date
Application number
PCT/EP1998/007463
Other languages
English (en)
Inventor
Wolfgang Scherzer
Jörg Volle
Original Assignee
Ciba Spezialitätenchemie Bergkamen Gmbh
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 Ciba Spezialitätenchemie Bergkamen Gmbh filed Critical Ciba Spezialitätenchemie Bergkamen Gmbh
Publication of WO1999028365A1 publication Critical patent/WO1999028365A1/fr

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Classifications

    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines

Definitions

  • Curable mixtures based on amine hardeners and epoxy resins are widely used in the industry for coating and improving metallic and mineral substrates.
  • the amine hardeners used are, in particular, aliphatic, cycloaliphatic or aromatic amines as well as, optionally, imidazo- line group-containing polyaminoamides and adducts thereof.
  • binder systems are rapidly cured after being applied to the substrates to make them e.g. quickly passable or recoatable.
  • Essential criteria are high early water resistance of the still unhardened film (e.g. by drop formation at high relative atmospheric humidity) as well as low viscosity of the binder system to ensure its processability even at low temperatures.
  • Mannich bases i.e reaction products of amines and formaldehyde with a phenolic component
  • hardeners for epoxy resins which develop a hardness that is to some extent satisfactory at low temperatures.
  • JP Hei 7-507900 JP Hei 7-5117899 or USP 4,269,742.
  • the disadvantage of the systems proposed therein is on the one hand their high viscosity and, on the other hand, the bad UV resistance of the cured coatings owing to the phenolic components present in these systems.
  • EP 0 288 975 describes adducts of monoepoxy compounds and specific diamines which can be used at very low temperatures. However, these compounds also need to be accelerated with salicylic acid, phenol, alkylphenol or with a Mannich base. These accelerators in turn also produce bad UV resistance.
  • WO 96/34032 describes adducts of cycloaliphatic di- or polyglycidyl ethers with norbomanediamine, if required using in addition acrylates or methacrylates. Although these products have to some extent good UV resistance, the development of the hardness of these systems (measured in accordance with Shore D) is far too low even at room temperature; the surface properties of the cured films are insufficient for many applications and the viscosities of the amine adducts are very high in spite of a high diluent proportion of about 45 %.
  • the object of this invention is therefore to overcome these disadvantages and to provide hardeners for binder systems which, at high UV resistance and low viscosity, provide the cured systems with a rapid complete cure and with uniformly good surface properties both at room temperature and under unfavourable curing conditions, such as at low temperatures and/or high relative atmospheric humidity.
  • this invention relates to adducts containing free active hydrogen bound to amino nitrogen atoms, which are obtainable by reacting
  • Ri , R3, R5 are each independently of one another H or an unbranched or branched alkyl radical containing 1 to 10 carbon atoms,
  • R2, R4 are H
  • RQ is a radical of formula 2 y7 .
  • V7 using at most 2 mol of the compound of the general formula (2) per mol of the compound of the general formula (1). It is preferred, however, to use a molar ratio of 1 :1.
  • novel adducts are prepared by known processes by placing the diamines in a vessel and adding the aromatic monoepoxy compounds dropwise, with stirring, at 60 to 80 °C and then stirring this mixture for about 1 hour (h) at that temperature until the adduct formation is complete.
  • isolated adducts are also used, which are prepared with an excess of norbor- nanediamine (NBDA).
  • NBDA norbor- nanediamine
  • the 1.5- to 10-fold, preferably the 4- to 6-fold, molar amount of amine is placed in a vessel and the aromatic monoepoxy compound is added dropwise, with stirring, conveniently at 60 to 80 °C. Excess amine is then removed by distillation under vacuum.
  • this invention thus relates to a process for the preparation of the adducts according to claim 1 , which process comprises
  • the reaction temperature is not critical and may thus be varied but is conveniently from 60 to
  • This invention also relates to curable mixtures consisting of
  • the novel adducts are preferably adjusted with the components (C) to (E) to a user-friendly mixture ratio of 50 parts of hardener (adducts I) per 100 parts of resin (component II).
  • the mixture ratios can also vary from 30 to 100 parts of hardener/100 g of resin.
  • the diluent proportion should not exceed 40 %, based on the hardener, since this would result in too great a drop in the mechanical data.
  • the ratio between reactive groups of the adducts according to (I) and, optionally, the amines according to (D) and the epoxy groups (II) and, optionally, the higher- or monofunctional glycidyl ethers according to (E) is preferably adjusted about equivalently.
  • the preferred aliphatic or cycloaliphatic amines of (D) are isopho- ronediamine, bisaminomethylcyclohexane and/or 2,4,4(2,2,4)-trimethylhexamethylenedi-1 ,6- amine.
  • the mono- or higher-functional glycidyl ethers (E) according to claim 4 are preferably ethylhexyl glycidyl ether, hexanediol diglycidyl ether, butanediol digly- cidyl ether, cyclohexanedimethylol diglycidyl ether, diethylene glycol diglycidyl ether, poly- oxypropylene diglycidyl ether and glycidyl ether based on bisphenol A, bisphenol F and novolaks.
  • the epoxy compounds (component II) additionally used in accordance with this invention are commercially available products containing at least one epoxy group per molecule and are derived from mono- and/or polyvalent and/or polynuclear phenols, in particular bisphenols, and from novolaks, such as diglycidyl ethers of bisphenol A and bisphenol F.
  • binders for synthetic resin mortar standard pebbles and sands are additionally used in the grain size distributions and amounts customarily used in this field.
  • NBDA norbomanediamine
  • 320 g of benzyl alcohol 450 g of norbomanediamine (NBDA) and 320 g of benzyl alcohol are placed in a reaction vessel. After heating this mixture to 60 to 80 °C, 230 g of cresyl glycidyl ether (epoxy value: about 0.55) are added dropwise, with stirring, over 30 min, keeping the temperature within this range by cooling. To ensure complete adduct formation, stirring is continued for 60 min at 60 °C to 80 °C.
  • NBDA norbomanediamine
  • Viscosity 210 mPa.s /25 °C; H equivalent: about 95
  • Viscosity 230 mPa.s /25 °C; H equivalent: about 95
  • Viscosity 455 mPa.s /25 °C; H equivalent: about -95
  • Viscosiy 160 mPa.s /25 °C; H equivalent: about -95
  • Example 1 450 g of NBDA, 150 g of phenyl glycidyl ether (epoxy value: about 0.58), 80 g of hexanediol diglycidyl ether and 320 g of benzyl alcohol are reacted according to Example 1.
  • Viscosity 320 mPa.s /25 °C; H equivalent: about -95
  • Viscosity 270 mPa-s /25 °C; H equivalent: about -95
  • Viscosity 400 mPa.s /25 °C; NH equivalent: about 95
  • Viscosity 360 mPa.s /25 °C; NH equivalent: about 95
  • Viscosity 310 mPa-s /25 °C; H equivalent: about 95
  • Viscosity 290 mPa-s /25 °C; H equivalent: about 95
  • 530 g of the adduct of Example 13 are homogenised with 200 g of IPD and 270 g of benzyl alcohol at about 60 °C.
  • Viscosity 280 mPa-s /25 °C; NH equivalent: about 95
  • 320 g of the adduct of Example 13 are homogenised with 300 g of IPD and 380 g of benzyl alcohol at about 60 °C.
  • Viscosity 160 mPa-s /25 °C; NH equivalent: about 95
  • 530 g of the adduct of Example 13 are homogenised with 181 g of NBDA and 289 g of benzyl alcohol at about 60 °C.
  • Viscosity 185 mPa-s /25 °C; NH equivalent: about 95
  • Viscosity 60 mPa-s /25 °C; NH equivalent: 95
  • Viscosity 385 mPa.s /25 °C; NH equivalent: 95
  • Measurement is carried out using a Haake rotary viscometer RV20 in accordance with the instructions of the producer.
  • the calculated amounts of epoxy resins and amine hardener are weighed into a mixing vessel and are vigorously mixed with a spatula for about 2 min without working in any excess air. Local inhomogeneities show as streaks and are to be avoided.
  • a 500 ⁇ m film transfer frame, of Erichsen, is placed on a glass plate which has been cleaned first with acetone and then dried, and this frame is then filled with about 15 g of the reactive mixture and drawn evenly over the free area.
  • the freshly coated glass plates are immediately laid out into the corresponding climatic chambers, typically at relative atmospheric humidity (r.h.) at 23 °C/r. h. about 95 %. at 10 °C/r. h. about 80 % at 5 °C/r. h. > 70 %.
  • the glass plates After curing for 24 hours, the glass plates are taken back to the test laboratory for assessment of their surface.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

Cette invention a trait à des additifs renfermant une liaison hydrogène actif libre - atomes d'amino-azote, qu'il est possible d'obtenir en faisant réagir: 2,5(2,6)bis(aminométhyl)bicyclo(2,2,1)heptane(norbornanédiamine), correspondant à la formule (1), avec un composé époxy aromatique monofonctionnel correspondant à la formule générale (2). Dans cette formule, R1, R2, et R5 représentent, de manière indépendante, H ou un radical alkyle non ramifié ou ramifié comportant de 1 à 10 atomes de carbone, R2 et R4 représentent H et R6 représente un radical correspondant à la formule (3). On utilise deux moles au plus du composé correspondant à la formule générale (2) par mole de composé correspondant à la formule générale (1). Cette invention porte également sur la préparation de ces additifs ainsi que sur des mélanges durcissables les renfermant.
PCT/EP1998/007463 1997-11-28 1998-11-20 Additifs de composes monoepoxy aromatiques et de norbornanediamine WO1999028365A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19752954.2 1997-11-28
DE19752954 1997-11-28

Publications (1)

Publication Number Publication Date
WO1999028365A1 true WO1999028365A1 (fr) 1999-06-10

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007060091A1 (fr) * 2005-11-25 2007-05-31 Huntsman Advanced Materials (Switzerland) Gmbh Agent de durcissement pour resines epoxy
EP2752437A1 (fr) 2013-01-08 2014-07-09 Sika Technology AG Durcisseur pour produits à résine époxy pauvres en émissions
WO2014108304A2 (fr) * 2013-01-08 2014-07-17 Sika Technology Ag Durcisseurs pour produits en résine époxyde à faible taux d'émission
WO2016137791A1 (fr) * 2015-02-27 2016-09-01 3M Innovative Properties Company Adhésif structural en deux parties
US9580622B2 (en) 2013-12-16 2017-02-28 Dow Global Technologies Llc Crosslinkable composition, a method of making the same and a crosslinked composition produced therefrom
US9718990B2 (en) 2013-12-11 2017-08-01 Dow Global Technologies Llc Coating system, a method of applying the coating system and an article comprising the coating system
CN115926114A (zh) * 2021-08-05 2023-04-07 中国石油化工股份有限公司 一种室温固化低色泽改性脂环胺固化剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS544992A (en) * 1977-06-14 1979-01-16 Nippon Zeon Co Ltd Novel epoxy hardener
JPH0480228A (ja) * 1990-07-20 1992-03-13 Mitsui Toatsu Chem Inc エポキシ樹脂用硬化剤

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS544992A (en) * 1977-06-14 1979-01-16 Nippon Zeon Co Ltd Novel epoxy hardener
JPH0480228A (ja) * 1990-07-20 1992-03-13 Mitsui Toatsu Chem Inc エポキシ樹脂用硬化剤

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 7908, Derwent World Patents Index; Class A21, AN 79-14693B, XP002100663 *
DATABASE WPI Section Ch Week 9217, Derwent World Patents Index; Class A21, AN 92-138016, XP002100662 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7683154B2 (en) 2005-11-25 2010-03-23 Huntsman International Llc Epoxy resin curing agent of polyethylene polyamine-monoglycidyl ether adduct and amine compound
WO2007060091A1 (fr) * 2005-11-25 2007-05-31 Huntsman Advanced Materials (Switzerland) Gmbh Agent de durcissement pour resines epoxy
US9631047B2 (en) 2013-01-08 2017-04-25 Sika Technology Ag Curing agents for low-emission epoxy resin products
EP2752437A1 (fr) 2013-01-08 2014-07-09 Sika Technology AG Durcisseur pour produits à résine époxy pauvres en émissions
WO2014108304A2 (fr) * 2013-01-08 2014-07-17 Sika Technology Ag Durcisseurs pour produits en résine époxyde à faible taux d'émission
WO2014108304A3 (fr) * 2013-01-08 2014-12-18 Sika Technology Ag Durcisseurs pour produits en résine époxyde à faible taux d'émission
CN104870509A (zh) * 2013-01-08 2015-08-26 Sika技术股份公司 用于低排放环氧树脂产品的固化剂
US9790319B2 (en) 2013-01-08 2017-10-17 Sika Technology Ag Curing agents for low-emission epoxy resin products
US9718990B2 (en) 2013-12-11 2017-08-01 Dow Global Technologies Llc Coating system, a method of applying the coating system and an article comprising the coating system
US9580622B2 (en) 2013-12-16 2017-02-28 Dow Global Technologies Llc Crosslinkable composition, a method of making the same and a crosslinked composition produced therefrom
WO2016137791A1 (fr) * 2015-02-27 2016-09-01 3M Innovative Properties Company Adhésif structural en deux parties
US10280345B2 (en) 2015-02-27 2019-05-07 3M Innovative Properties Company Two-part structural adhesive
CN115926114A (zh) * 2021-08-05 2023-04-07 中国石油化工股份有限公司 一种室温固化低色泽改性脂环胺固化剂及其制备方法

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