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WO1999037714A1 - Phenols propoxyles et/ou alcools aromatiques propoxyles utilises comme plastifiants pour des resines epoxy et durcisseurs amines de resines epoxy - Google Patents

Phenols propoxyles et/ou alcools aromatiques propoxyles utilises comme plastifiants pour des resines epoxy et durcisseurs amines de resines epoxy Download PDF

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Publication number
WO1999037714A1
WO1999037714A1 PCT/EP1999/000280 EP9900280W WO9937714A1 WO 1999037714 A1 WO1999037714 A1 WO 1999037714A1 EP 9900280 W EP9900280 W EP 9900280W WO 9937714 A1 WO9937714 A1 WO 9937714A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
aminic
hardener
curable mixture
mixture according
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.)
Ceased
Application number
PCT/EP1999/000280
Other languages
English (en)
Inventor
Wolfgang Scherzer
Jörg Volle
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.)
CIba Spezialitaetenchemie Bergkamen GmbH
Original Assignee
CIba Spezialitaetenchemie 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 Spezialitaetenchemie Bergkamen GmbH filed Critical CIba Spezialitaetenchemie Bergkamen GmbH
Publication of WO1999037714A1 publication Critical patent/WO1999037714A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to novel plasticisers for epoxy resins and aminic epoxy resin hardeners as well as to curable mixtures in which said plasticisers are used.
  • Curable mixtures based on aminic hardeners and epoxy resins are widely used in the industry for coating and improving metallic and mineral substrates.
  • the epoxy resins used are mainly glycidyl compounds based on bisphenol A (4,4'-dihydroxy- diphenylpropane-2,2), bisphenol F (4,4'-dihydroxydiphenylmethane) or novolaks.
  • the viscosity of these glycidyl compounds is very high and is usually from 6.000 to 16.000 mPa»s. It is very difficult, however, to process epoxy resins of such high viscosity as it is virtually impossible to homogeneously mix them with the aminic hardeners designated therefor, in particular at low temperatures.
  • reactive thinners such as monoglycidyl ethers of phenols or glycidyl ethers based on mono- or difunctio- nal aliphatic or cycloaliphatic alcohols.
  • the aminic hardeners used are in particular aliphatic, cycloaliphatic, araliphatic or aromatic amines, and polyaminoamides which optionally contain imidazoline groups.
  • diluents or plasticisers are used. These must be compatible with the epoxy resin and the aminic hardener, should impart a certain flexibility to the brittle epoxy resin/hardener system and should remain homogeneous in the coating after curing.
  • Phthalates such as dioctyl phthalate, alkyl phenols such as nonylphenols and, especially, benzyl alcohol are usually used to this purpose.
  • Phthalates are, however, not very suitable, as amide formation may take place with strongly basic amines, the hardener thus being rendered useless.
  • Benzyl alcohol affords stable end products and effects a fast curing rate of the applied coating. A fast curing rate, especially also at low temperatures, is desirable in practice in order to make it possible to pass over or recoat the coating within the briefest time possible.
  • Using benzyl alcohol however, in many cases also shortens the gel time after the epoxy resin and epoxy resin hardener are mixed, so that practice-oriented processing is hardly possible any longer.
  • alkylphenols The alkylphenols furthermore usually have a fairly high viscosity and therefore have no, or only a minor, viscosity-reducing effect on the epoxy resin/hardener system.
  • alkylphenols and benzyl alcohols have the additional disadvantage that they can be used only to a limited degree in the drinking water and food sector.
  • novel plasticisers/diluents are obtainable by generally known processes by reacting the phenols/alcohols with propylene oxide in the presence of predominantly basic catalysts. These processes are described, inter alia, in "Ullmann's Enzyklopadie der ischen Chemie", Verlag Chemie GmbH, Weinheim, 4 th edition, Vol. 19, pages 31-38.
  • the molecular-weight distribution is dependent on the degree of propoxylation.
  • the compounds of the general formula (I) which are additionally used in the mixture according to this invention are the technical products having the molecular-weight distributions contingent on the process, which compounds may possibly also contain minor amounts of educt. If this is undesirable, then the reaction products may also be purified by distillation or may be split up into the individual fractionation steps. To adjust the curable and/or cured mixtures to particular technical properties, it is also possible to use mixtures of the compounds.
  • the novel plasticisers/diluents in the inventive curable mixtures bring about a markedly longer gel time while effecting, also at low temperatures, a comparable rapid development of the hardness.
  • novel diluents are very compatible with the aminic hardeners and with the epoxy resins and impart high flexibility to the cured coating without reducing the chemical resistance, and - 4-
  • the novel curable mixtures have, also at low temperatures, comparable high initial strengths, making early passability or recoatability of the coatings possible.
  • this invention relates to curable mixtures based on epoxy resins and aminic hardeners, optionally additionally using colourants, pigments, fillers, UV stabilisers, flow con- trol/plasticising agents, wherein the plasticiser/diluent used is at least one compound of the general formula (I):
  • Ri , R3, R5 are each independently of one another H or an unbranched or branched alkyl radical containing 1 to 12 carbon atoms, and
  • Preferred curable mixtures are those wherein the components of formula (I) are the propo- xylates of phenol, cresol or benzyl alcohol.
  • This invention also relates to curable mixtures consisting of
  • novel curable mixtures usefully contain 1 to 40 parts by weight, preferably 5 to 25 parts by weight, based on the sum of the mixture components (A), (B), (C) and (D), of at least one compound of the general formula (I).
  • the diluents/plasticisers used according to this invention can be added, singly or in admixture, both to the epoxy resin and to the aminic hardener. According to this invention, addition to the aminic hardener is preferred.
  • aminic hardeners (B) are: polyethylenepolyamines, for example diethylenetriamine, triethylenetetramine, tetraethylene- pentamine etc.; polypropylenepolyamines, for example dipropylenetriamine, tripropylenetetramine and the polyamines obtained by cyanoethylation of polyamines, in particular of ethylenediamine, and subsequent complete or partial hydration; aliphatic amines, for example diaminoethane, diaminopropane, neopentanediamine, diami- nobutane, hexamethylenediamine, 2,2,4(2 ) 4,4)-trimethylhexamethylenediamine-1 ,6; cycloaliphatic polyamines, for example isophoronediamine, diaminocyclohexane, norbornanediamine, 3(4),8(9)-bis(aminomethyl)tricyclo[5,2,1,0]decane, (TCD-diamine
  • Preferred examples of aminic hardeners (B) are: xylylenediamine, norbornanediamine, 1 ,3-bisaminomethylcyclohexane, 2,2,4(2,4,4)-trime- thylhexamethylenediamine-1 ,6, isophoronediamine and/or polyaminoamides which optionally contain imidazoline and which are obtainable by condensation of fatty acids with polyethylenepolyamines.
  • the prepolymers preferred according to this invention are the above amine components.
  • the epoxy compounds used for prepolymerising the cited polyamines are the known and commercially available products comprising at least one epoxy group per molecule.
  • glycidyl ethers based on mono- or polyvalent phenols, for example phenol, cresol, bisphenol A, bisphenol F, novolaks, mono- or polyvalent aliphatic alcohols containing 4 to 18 carbon atoms, for example butanol, butanediol, hexanol, hexanediol, fatty alcohols having a chain length of 8 to 18 carbon atoms, polyoxyal- kylene glycols, for example diethylene glycol, dipropylene glycol, polyoxypropylene glycol, diethylene glycol monobutyl ether.
  • the degree of adduction can be varied within wide limits and is influenced by the kind of amine compound and glycidyl compound and can furthermore be adjusted to the respective field in which the curable mixture is used.
  • amine adducts are usually prepared by placing the amine component in a vessel and homogenising it with the diluent/plasticiser.
  • the glycidyl compound is added at 60 to 80°C.
  • the mixture is stirred for about 30 min until adduction is complete. It is also possible to add the plasticiser after the adduction.
  • isolated adducts can also be used, which are prepared with an excess of the amine component, excess amine being removed by distillation after the adduction.
  • plasticiser is added after the distillation step.
  • the epoxy resins (A) used according to 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 novolaks, for example diglycidyl ethers of bisphenol A and bisphenol F.
  • glycidyl ethers based on bisphenol A, bisphenol F or novolaks with so-called reactive diluents, for example monoglycidyl ethers of phenols or glycidyl ethers based on mono- or polyvalent aliphatic or cycloaliphatic alcohols.
  • Examples of such reactive diluents are phenyl glycidyl ether, cresyl glycidyl ether, p-tertiary-butylphenyl glycidyl ether, butyl glycidyl ether, C 12 -C u alcohol glycidyl ether, butane diglycidyl ether, hexane diglycidyl ether, cyclohexanedimethyl diglycidyl ether or glycidyl ethers based on polyethylene glycols or polypropylene glycols.
  • the standard additives (C) to the novel curable mixtures, for example fillers, such as pebbles, sands, silicates, graphite, silicium dioxide, talcum, mica etc. in the grain size distributions customarily used in this field, pigments, colourants, accelerators, stabilisers, flow control/plasticising agents, non-reactive extender resins and other plasticisers and diluents.
  • fillers such as pebbles, sands, silicates, graphite, silicium dioxide, talcum, mica etc.
  • pigments, colourants, accelerators, stabilisers flow control/plasticising agents, non-reactive extender resins and other plasticisers and diluents.
  • this hardener adduct 50 Parts by weight of this hardener adduct are stirred together with 100 parts by weight of an epoxy resin (epoxy resin based on bisphenol A/bisphenol F, diluted with a glycidyl ether based on a monofunctional fatty alcohol, epoxy equivalent: -190 g/equivalent, viscosity: 950 mPa «s/25°C) at room temperature (23°C).
  • the gel time is determined at room temperature.
  • the samples for the determination of the hardness according to Shore D are stored at 23°C and at 10°C.
  • the hardness according to Shore D is determined after 1 day, 2 and 5 days and after further hardening at 60°C (48 h). The results are compiled in Table 1.
  • the preparation of the hardener component and its subsequent processing is carried out as in Example 1 , but using a phenolpropoxylate having an average degree of propoxylation of 3 mol of PO per mol of phenol as plasticiser/diluent.
  • the preparation of the hardener component and its subsequent processing is carried out as in Example 1 , but using a benzyl alcohol propoxylate having an average degree of propoxylation of 1 mol of PO per mol of benzyl alcohol as plasticiser/diluent.
  • Example 5 The preparation of the hardener component and its subsequent processing is carried out as in Example 1 , but using a nonylphenolpropoxylate having an average degree of propoxylation of 1 mol of PO per mol of nonylphenol as plasticiser/diluent. Comparison Example 5
  • the mixture of the hardener component and its subsequent processing is carried out as in
  • Example 1 but using benzyl alcohol as plasticiser/diluent.
  • Example 1 43.5 g of norbornanediamine, 15 g of epoxy resin according to Example 1 and 41.5 g of phenolpropoxylate having an average degree of propoxylation of 1 mol of PO per mol of phenol are reacted in accordance with Example 1 :
  • a hardener is prepared in analogy to Example 6, but using a phenolpropoxylate having an average degree of propoxylation of 3 mol of PO per mol of phenol as plasticiser/diluent. The subsequent processing is carried out as described in Example 1.
  • a hardener is prepared in analogy to Example 6, but using a nonylphenolpropoxylate having an average degree of propoxylation of 1 mol of PO per mol of nonylphenol as plasticiser/diluent.
  • the subsequent processing is carried out as described in Example 1.
  • a hardener is prepared in analogy to Example 6, but using a benzyl alcohol propoxylate having an average degree of propoxylation of 1 mol of PO per mol of benzyl alcohol as plasticiser/diluent.
  • the subsequent processing is carried out as described in Example 1.
  • a hardener is prepared in analogy to Example 6, but using benzyl alcohol as plasticiser/diluent. The subsequent processing is carried out as described in Example 1. - 10-
  • a hardener is prepared in analogy to Example 11 , but using a para-tertiary-butylphenolpro- poxylate having an average degree of propoxylation of 1 mol of PO per mol of para-tertiary- butylphenol as plasticiser/diluent.
  • a hardener is prepared in analogy to Example 11 , but using benzyl alcohol as plasticiser/diluent. The subsequent processing is carried out as described in Example 1.
  • Example 4 40 g of 1 ,3-bisaminomethylcyclohexane, 15 g of epoxy resin according to Example 1 and 45 g of phenolpropoxylate having an average degree of propoxylation of 1 mol of PO per mol of phenol are reacted in accordance with Example 1.
  • a hardener is prepared in analogy to Example 14, but using a nonylphenolpropoxylate having an average degree of propoxylation of 1 mol of PO per mol of nonylphenol. The subsequent processing is carried out as described in Example 1. - 11-
  • a hardener is prepared in analogy to Example 14, but using benzyl alcohol as plasticiser/diluent. The subsequent processing is carried out as described in Example 1.
  • a hardener is prepared in analogy to Example 17, but using benzyl alcohol as plasticiser/diluent. The subsequent processing is carried out as described in Example 1.
  • a hardener is prepared in analogy to Example 19, but using nonylphenol as plasticiser/diluent.

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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

L'invention concerne des mélanges durcissables, exempts de solvant et à base de résines époxy et de durcisseurs aminés, renfermant comme plastifiant/diluant au moins un composé représenté par la formule générale (I) dans laquelle R1, R3, R5 représentent chacun, indépendamment l'un de l'autre, H ou un radical alkyle ramifié ou non ramifié contenant de 1 à 12 atomes de carbone, et R2, R4 représente H, m étant compris entre 1 et 10 et n compris entre 0 et 3.
PCT/EP1999/000280 1998-01-27 1999-01-19 Phenols propoxyles et/ou alcools aromatiques propoxyles utilises comme plastifiants pour des resines epoxy et durcisseurs amines de resines epoxy Ceased WO1999037714A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19802934.9 1998-01-27
DE19802934 1998-01-27

Publications (1)

Publication Number Publication Date
WO1999037714A1 true WO1999037714A1 (fr) 1999-07-29

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PCT/EP1999/000280 Ceased WO1999037714A1 (fr) 1998-01-27 1999-01-19 Phenols propoxyles et/ou alcools aromatiques propoxyles utilises comme plastifiants pour des resines epoxy et durcisseurs amines de resines epoxy

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3208292A1 (fr) 2016-02-19 2017-08-23 Evonik Degussa GmbH Modificateur pour compositions durcissables comprenant de l'alcoxylate d'alcool benzylique
US11426762B2 (en) 2015-12-31 2022-08-30 Henkel Ag & Co. Kgaa Low bake autodeposition coatings

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1515473A (en) * 1977-03-10 1978-06-28 Ciba Geigy Ag Curable epoxy resin compositions
GB1542905A (en) * 1975-09-12 1979-03-28 Neynaber Chemie Gmbh Mouldable compositions based on thermosetting condensation resins
JPH07157700A (ja) * 1993-12-06 1995-06-20 Sakata Corp 金属印刷用インキ組成物
JPH09169854A (ja) * 1995-10-31 1997-06-30 Yuka Shell Epoxy Kk エポキシ樹脂水性分散液

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1542905A (en) * 1975-09-12 1979-03-28 Neynaber Chemie Gmbh Mouldable compositions based on thermosetting condensation resins
GB1515473A (en) * 1977-03-10 1978-06-28 Ciba Geigy Ag Curable epoxy resin compositions
JPH07157700A (ja) * 1993-12-06 1995-06-20 Sakata Corp 金属印刷用インキ組成物
JPH09169854A (ja) * 1995-10-31 1997-06-30 Yuka Shell Epoxy Kk エポキシ樹脂水性分散液

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9736, Derwent World Patents Index; Class A14, AN 97-389454, XP002104928 *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 009 31 October 1995 (1995-10-31) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11426762B2 (en) 2015-12-31 2022-08-30 Henkel Ag & Co. Kgaa Low bake autodeposition coatings
EP3208292A1 (fr) 2016-02-19 2017-08-23 Evonik Degussa GmbH Modificateur pour compositions durcissables comprenant de l'alcoxylate d'alcool benzylique

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