EP1015440A1 - Spiro composes du type polyglycidyle et leur utilisation dans des resines epoxy - Google Patents

Spiro composes du type polyglycidyle et leur utilisation dans des resines epoxy

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Publication number
EP1015440A1
EP1015440A1 EP98941293A EP98941293A EP1015440A1 EP 1015440 A1 EP1015440 A1 EP 1015440A1 EP 98941293 A EP98941293 A EP 98941293A EP 98941293 A EP98941293 A EP 98941293A EP 1015440 A1 EP1015440 A1 EP 1015440A1
Authority
EP
European Patent Office
Prior art keywords
polyglycidyl
formula
epoxy
reacting
polyglycidyl compound
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Withdrawn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
EP98941293A
Other languages
German (de)
English (en)
Inventor
Christoph Rickert
Hugh Stephen Laver
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.)
Huntsman Advanced Materials Switzerland GmbH
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding 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 Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Publication of EP1015440A1 publication Critical patent/EP1015440A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero 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
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • 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
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • the present invention relates to polyglycidyl compounds based on spirobisindanes, to a process for the preparation of these compounds as well as to their use for the production of moulded articles, coatings, matrix materials, casting compounds or adhesives.
  • polyglycidyl compounds are frequently used as reactive component in curable compositions, for example as hardeners or crosslinkers in powder coating compositions based on polyesters and polyacrylates.
  • polyglycidyl compounds containing more than two epoxy groups have as such the disadvantage of being liquid either at room temperature or at a little above room temperature.
  • Typical representatives of these viscous resins are, for example, the triglycidyl ester of tri- mellitic acid and the diglycidyl ester of 1 ,2-cyclohexanedicarboxylic acid.
  • the homogeneous incorporation of these liquid compounds into solid compositions requires substantially more elaborate processing than is the case when using glycidyl compounds which are already solid.
  • the main component of the solid polyglycidyl compounds are diglycidyl compounds based on bisphenol A. These in turn have disadvantages if they are used as sole crosslinker for curable compositions. They are not suitable for the production of coatings which are resistant to outdoor weathering.
  • JP Kokai Hei 8-217852 and JP Kokai Hei 9-124769 describe purely bifunctional 6,6'-diglycidyloxy-3,3 ⁇ 3,3'-tetraalkyl-1 ,1 '-spirobisindanes which are used in cured mixtures with phenol- or naphthol-based resins, preferably for sealing semi-conductor modules.
  • Z is a direct single bond or -O-; more than two of R ⁇ R 2 , R 3 and R 4 are -OH, -O-CO-R-CO-OH, -O-R-OH,
  • R is C r C 8 alkylene, C 5 -C 8 cycloalkylene, C 6 -C 14 arylene or partially hydrated C 6 -C 14 arylene, and the remaining R,, R 2 , R 3 and R 4 are a hydrogen atom or -O-C Cgalkyl, -O-C 5 -C 8 cycloalkyl, -O-C 6 -C 14 aryl, partially hydrated -O-C 6 -C 14 aryl or (meth)acrylate; and
  • R 5 , R 6 , R 7 and R 8 are each independently of one another C 1 -C 8 alkyl, C 5 -C 8 cycloalkyl, C 6 -C 14 aryl, partially hydrated C 6 -C 14 aryl or a hydrogen atom.
  • R 5l R 6 , R 7 and R 8 defined as C ⁇ C-oalkyl are straight-chain or branched radicals, for example methyl, ethyl, n-propyl, isobutyl, sec-butyl and tert-butyl as well as the different isomers of pentane, hexane, heptane and octane.
  • R 5 , R 6 , R 7 and R 8 defined as C 5 -C 8 cycloalkyl are, for example, radicals containing 5 to 8 ring- carbon atoms, e.g. of cyclopentane, cyclohexane, cycloheptane and cyclooctane as well as their substitution products, in particular their alkyl substitution products, such as the C,-C 4 - alkyl substitution products.
  • R 5 , R 6 , R 7 and R 8 defined as C 6 -C 14 aryl can be, for example, phenyl, tolyl, pentalinyi, indenyl, napthyl, azulinyl and anthryl.
  • R 5 , R 6 , R 7 and R 8 defined as partially hydrated C 6 -C 14 aryl are understood as being aryls which are partially hydrated by addition of hydrogen to one or several double bonds of the aromatic aryl, for example compounds of formula:
  • R 1f R 2 , R 3 and R 4 defined as -O-C C 8 alkyl, -O-C 3 -C 8 cycloalkyl, -O-C 6 -C 14 aryl or partially hydrated -O-C 6 -C 14 aryl have the same meaning as that given above for the corresponding radicals which are not bound to oxygen.
  • R defined as C 5 -C 8 cycloalkylene containing 5 to 8 ring-carbon atoms may be, for example, 1 ,2- and 1 ,3-cyclopentenyl, 1 ,2-, 1 ,3- and 1 ,4-hexenyl, 1 ,2-, 1 ,3-, and 1 ,4-heptenyl and 1 ,2-, 1 ,3-, 1 ,4- and 1 ,5-octenyl, 1 ,2-norbomyl as well as their substitution products, in particular their alkyl substitution products, such as the C r C 4 alkyl substitution products.
  • R defined as C 6 -C 14 arylene may be, for example, phenylene, tolyiene, pentalinylene, inde- nylene, napthylene, azuiinylene and anthrylene.
  • R defined as partially hydrated C 6 -C 14 arylene is understood as meaning arylenes which are partially hydrated by addition of hydrogen to one or several double bonds of the aromatic arylene.
  • polyglycidyl compounds will be understood as meaning compounds containing unsubstituted glycidyl groups as well as compounds containing glycidyl groups which are substituted by alkyl groups, preferably methyl groups.
  • the polyglycidyl compounds obtained after the glycidylisation of the polyfunctionai 1 ,1 '-spirobisindanes are always polyglycidyl ethers or polyglycidyl esters.
  • R 1 ( R 2 , R 3 and R 4 are accordingly determined by the choice of the radicals of the phenolic basic body used (in the case of SBI using pyrocatechol, i.e. 1 ,2-dihydoxybenzene), or by reacting the hydoxyl groups of the basic body by known subsequent reactions (reaction with anhydrides, etherification etc.), whereas R 5 , R 6 , R 7 and R 8 are determined by varying the ketone used (using e.g. acetone, i.e. dimethyl ketone, for the preparation of SBI).
  • a polyfunctionai 1 ,1 '-spirobisindane of formula I or a mixture of different polyfunctionai 1 ,1 '-spirobisindanes of formula I is reacted by one of the known processes with a stoichiometric excess of glycidyl chloride or ⁇ -methylglycidyl chloride in the presence of a suitable catalyst and, after adding a base, excess glycidyl chloride or ⁇ -methylglycidyl chloride is removed by distillation.
  • a general overview may be found, inter alia, in Lee Neville "Handbook of Epoxy Resins", McGraw Hill Book Company, 1982, chapter 3.
  • the compounds of formula I are preferably compounds, in which Z is a direct single bond.
  • the polyglycidyl compounds based on basic bodies according to formula I are particularly preferably those, wherein all R 1 ( R 2 , R 3 and R 4 are -OH, -O-CO-R-CO-OH, -O-R-OH,
  • R 1 f R 2 , R 3 and R 4 are -OH or
  • R is C 5 -C 8 cycloalkan-1 ,2-ylene.
  • R 5 , R 6 , R 7 and R 8 are determined, as mentioned above, by varying the ketone used.
  • R 5 R 6 , R 7 and R 8 are each independently of one another C ⁇ C-aalkyl or a hydrogen atom.
  • polyglycidyl compounds are most preferred, which are based on compounds of formula I, wherein all R 1t R 2 , R 3 and R 4 are hydroxyl and all R 5 R 6 , R 7 and R 8 are methyl, and -Z- is a direct bond.
  • this invention relates to reaction products of one of the polyglycidyl compounds described above with a less than stoichiometric amount of a compound containing two substituents reacting with epoxy groups.
  • the compounds described so far can be reacted in analogy to known glycidyl compounds with compounds reacting with epoxy groups.
  • reaction products are particularly preferred if the polyglycidyl compound and the compound containing two substituents reacting with epoxy groups are used in such amounts that there are 0.01 - 0.75 of those groups which react with an epoxy resin per one epoxy group of the polyglycidyl compound.
  • Such reactions are particularly suitable for adjusting the glass transition temperature (T g ) to the respective requirements, i.e. usually to increase the T g .
  • reaction products are also preferred if the compound containing two substituents reacting with epoxy groups is a compound of formula HO-CO-R 9 -CO-OH, HO-R 9 -OH, H-[O-R 9 -O-CO-NH-R 9 -NH-CO] v -O-R 9 -OH or H-[O-C u H 2u ] v -OH, wherein u is an integer from 2 to 4, v is an integer from 1 to 20, and
  • R 9 is CrC f jalkylene, C 5 -C 8 cycloalkylene, C 6 -C 14 arylene or partially hydrated C 6 -C 14 arylene, wherein
  • R 9 is preferably C 5 -C 8 cycloalkan-1 ,2-ylene or C 5 -C 8 cycIoalkan-1 ,4-ylene.
  • R 9 can, for example, correspond to those radicals which were cited above for R.
  • reaction products if the compound containing two substituents reacting with epoxy groups is 1 ,4-cyclohexanedicarboxylic acid or a cyclic anhydride. Typical examples thereof are the anhydrides of phthalic acid or of hexahydrophthaiic-acid.
  • novel compounds are valuable formulation components for curable compositions which comprise one of the novel polyglycidyl compounds or its reaction products and a compound reacting therewith with crosslinking.
  • the novel compounds can be combined with all customary crosslinkers or hardeners for epoxy resins.
  • the novel polyglycidyl compounds or their reaction products, where required also in combination with other epoxy resins, can be used for all applications in which epoxy resins are used, for example for the preparation of adhe- sives, moulding articles and coatings.
  • novel compounds are powder coating applications which are described in more detail below as Use Example.
  • the novel compounds can in this case replace, for example, the triglycidyl isocyanurate [TGIC] which is particularly widely used in this technology, without requiring any substantial changes in the other components of the powder coatings or in the preparation of coating formulations and without having to consider drawbacks with regard to the technical aspects of applying coating compositions.
  • TGIC triglycidyl isocyanurate
  • This invention therefore also relates to powder coatings comprising a carboxyl-terminated polyester and/or a free carboxyl group-containing acrylic resin as compound which reacts with crosslinking, which powder coatings comprise one of the above compounds, employing it as crosslinker.
  • the (meth)acrylate polymer is in this case preferably a copolymer of one or several acrylates and/or methacrylates, preferably of the corresponding alkyl esters containing 1 to 18, more preferably 1 to 8, carbon atoms in the alkyl group, with acrylic acid and/or methacrylic acid and, optionally, with additional ethylenically unsaturated comonomers.
  • the (meth)acrylate polymer has, for example, a molecular weight (number average Mn from GPC measurement with polystyrene standardisation) of 500 to 30000, preferably of 1000 to 10000. It furthermore preferably comprises 0.2 to 6 equivalents of free carboxyl groups.
  • the glass transition temperature of the (meth)acrylate polymers is conveniently above 20°C, preferably in the range from 30 to 100°C.
  • suitable (meth)acrylate monomers are ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and also, preferably, C r C 4 alkylmethacrylates, such as methyl methacrylate, ethyl methacrylate or butyl methacrylate.
  • (Meth)acrylate derivatives containing silane groups may also be used.
  • Suitable ethylenically unsaturated comononers are, for example, acrylo- or methacrylonitriles and also vinyl compounds.
  • Preferred comonomers are vinyl aromatic compounds, in particular styrene.
  • the above polymers can be prepared in known manner, for example by polymerising the monomers dissolved in suitable organic solvents, in particular in toluene or in mixtures of 1-methoxy-2-propanol, 1 -methoxy- 2-propylacetate and methyl isobutyl ketone (typically at a weight ratio of 70/20/10) in the presence of a suitable initiator, such as dicumyl peroxide, and of a chain-transfer agent such as thioglycolic acid. They can also be polymerised in the mass.
  • the carboxyl group-containing polyesters preferably have an acid number (given in mg KOH/g polyester) from 10 to 100 and a molecular weight (number average Mn) from 2000 to 10000. In the case of these polyesters, the ratio of Mw (weight average of the molecular weight) to Mn is usually from 2 to 10.
  • These polyesters are preferably solid at room temperature and preferably have a glass transition temperature from 35 to 120°C, preferably from 40 to 80°C. They are condensates of polyols with dicarboxylic acids and, optionally, polyfunctionai carboxylic acids (e.g. di-, tri- or tetracarboxylic acids) or the corresponding carbo- xyiic acid anhydrides.
  • Suitable polyols are, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1 ,3-butanediol, 1 ,4-butanediol, neopentanediol, isopentyl glycol, 1 ,6-hexanediol, glycerol, hexanetriol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, cyclohexanediol or 1 ,4-dimethylolcyclohexane.
  • Suitable dicarboxylic acids are, for example, isophthalic acid, terephthalic acid, phthalic acid, methylphthalic acids, tetra- hydrophthalic acid, methyltetrahydrophthalic acids, e.g. 4-methyltetrahydrophthalic acid, cyclohexanedicarboxylic acids, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid or 4,4'- diphenyldicarboxylic acid, etc.
  • Suitable tricarboxylic acids are typically aliphatic tricarboxylic acids, such as 1 ,2,3-propanetricarboxylic acid, aromatic tricarboxylic acids, such as trimesic acid, trimellitic acid and hemimellitic acid, or cycloaliphatic tricarboxylic acids, such as 6-me- thylcyclohex-4-ene-1 ,2,3-tricarboxylic acid.
  • Suitable tetracarboxylic acids are, for example, pyromellitic acid or benzophenone-S.S'A ⁇ -tetracarboxylic acid.
  • polyesters are often based on neopentyl glycol and/or trimethylolpropane as main alcoholic components as well as on adipic acid and/or terephthalic acid and/or isophthalic acid and/or trimellitic acid as main acid components.
  • the cited curable compositions preferably comprise the epoxy resin and the additional polymer in such amounts that the ratio of free carboxyl groups to epoxy groups in the composition is from 0.5 to 1 to 2 to 1 , preferably from 0.8 to 1 to 1.2 to 1 , more preferably about 1 to 1.
  • epoxy hardeners customarily used for powder coatings in combination with the novel polyglycidyl compounds, for example diglycidyl terephtha- late or glycidyl methacrylate homo- or copolymers (described, inter alia, in EP 0 653 466 A2).
  • epoxy resin mixtures can provide coatings having a particularly advantageous property profile with respect to the technical aspects of application because they permit adjusting or optimising the properties to the polyesters used.
  • Epoxy resin mixtures having an epoxy value of 1 - 10 equivalents/kg are preferred.
  • the curable compositions of this invention can aiso comprise other customary components, such as catalysts and/or accelerators, for example Actiron® NXJ-60 (2-propylimidazole), Actiron® NXJ-60 P (60 % by weight of 2-propylimidazole per 40 % by weight of solid carrier material), Bevanter® DT 3126 ([C 16 H 33 N(CH 3 ) 3 ] + Br) or triphenylphosphine, to enable a sufficiently fast curing reaction even at relatively low temperatures, for example in the range from 60 to 160°C.
  • catalysts and/or accelerators for example Actiron® NXJ-60 (2-propylimidazole), Actiron® NXJ-60 P (60 % by weight of 2-propylimidazole per 40 % by weight of solid carrier material), Beschreiber® DT 3126 ([C 16 H 33 N(CH 3 ) 3 ] + Br) or triphenylphosphine, to enable a sufficiently fast curing reaction even at
  • catalysts are often an organic amine or a derivative of an amine, preferably a tertiary amine or a nitrogen-containing heterocyclic compound.
  • Catalysts preferred for the reaction of epoxy groups with carboxyl groups are phenylimidazole, N-benzyldimethylamine and 1 ,8-di- azabicyclo[5,4,0]-7-undecene, where required on a silicate carrier material.
  • the catalyst or a catalyst mixture is usefully added in an amount from about 0.1 to 10, preferably from 0.5 to 5 % by weight.
  • the novel curable compositions may additionally contain further customary additives, for example light stabilisers, colourants, pigments, e.g.
  • novel curable compositions may also contain a suitable inert solvent or solvent mixture, for example xylene, butyl acetate, isobutanol, 1-methoxy-2-propanol, 1 -methoxy-2-propyl acetate or methyl isobutyl ketone (MIBK).
  • MIBK methyl isobutyl ketone
  • curable compositions of this invention can be used in the standard areas of curable epoxy resin composition technology, i.e. for example as coating composition, casting resin, impregnating resin, laminating resin, adhesive or sealing material.
  • Powder coatings of this invention can be prepared by simply mixing the components, for example in a ball mill. Another possibility, which is more preferred, is that which comprises fusing all the components, mixing and homogenising them, preferably in an extruder, such as in a Buss ko-kneader, cooling the mixture and comminuting it.
  • the powder coating mixtures preferably have an average particle size in the range from 0.015 to 500 ⁇ m, more preferably from 10 to 100 ⁇ m.
  • the powder coatings are cured on the object to be coated at a temperature of at least 100 °C, preferably from 150 to 250 °C. Curing usually requires about 5 to 60 minutes.
  • Objects and materials suitable for coating are all those which are stable at the temperatures required for curing, in particular metals and ceramics.
  • polyesters which consist to 50 % by weight, preferably to 90 % by weight and more (relative to the diol component), of neopentanediol and of aromatic or cyclo- aliphatic dicarboxylic acids, in particular terephthalic acid, as modules and which are commercially available e.g.
  • Crylcoat ® types [UCB] or under names such as Uralac® [DSM] or Grilesta® [EMS], provides powder coatings which result in weather-resistant coatings suitable for outdoor coatings and which are particularly flexible with respect to sudden or aiso prolonged mechanical stress.
  • UMB Crylcoat ® types
  • DSM Uralac®
  • EMS Grilesta®
  • T g value 26.4°C (DSC at 20°C/min heating rate) softening point: 65.3°C (ace. to DIN 51920, 2.0°C/min heating rate) epoxy value: 5.63 equivalents/kg (79.5 % of theory)
  • the idealised monomeric product corresponds to the glycidylisation product of formula I, wherein Z is a direct bond, R, R 2 R 3 and R 4 are glycidyl, and R 5 R 6 R 7 and R 8 are methyl.
  • T g value 68.8°C (DSC at 20°C/min heating rate) softening point: 112.8°C (ace. to DIN 51920, Mettler, 2°C/min heating rate)
  • R 5 R 6 R 7 and R 8 are methyl.
  • T g value 70.52°C (DSC, midpoint, 20°C/min heating rate) acid number: ⁇ 3mg KOH/g
  • T g value 39.89°C (DSC at 20°C/min heating rate)
  • R 10 , R ⁇ , R 12 and R 13 is the group of the following formula:
  • Example 4 Use of SBI-G as crosslinker for powder coatings based on polyesters.
  • the gel time of the powder coating formulation B (ace. to ISO standard 8130) is 160 s at
  • the powder coating is sprayed electrostatically onto test panels (Q-panel, of Q-Panel).
  • powder coating test panels which are coated with the novel hardener are distinguished by very beautiful surfaces and substantially improved flow.
  • the aspects of the panels of Example A as well as those of Example B readily bear comparison with panels coated with the so-called "high flow" hybrid powders or also with wet coating compositions.
  • the reverse side impact strength is determined by dropping a 2 kg die, at the underside of which there is a ball 20 mm in diametre, underside first from a specific height from the back onto the coated surface. The value indicated is the product of the weight of the die in kg and of the test height in cm at which the coating is still undamaged.
  • Example 5 Use of SBI-G as crosslinker for weather-resistant powder coatings based on polyesters.
  • the powder coatings listed in Table III are prepared in analogy to Example 4.
  • the white pigmented unstabilised powder coating test panels obtained are subjected to outdoor weathering.
  • the results obtained prove that the novel powder coatings have weather-resistant properties which match the quality of the reference formulations. Even after 10 months of outdoor weathering, the gloss and yellowness index values are on virtually the same scale as the starting values. This is surprising insofar as the claimed SBI-G is an aromatic compound, giving rise to expecatations of the typical bad behaviour of paint systems based on bisphenol A solid resins.

Abstract

L'invention concerne des composés du type polyglycidyle ayant en moyenne plus de deux groupes glycidyle par molécule (de préférence plus de deux et demi, et de préférence en particulier plus de trois) et une valeur Tg (déterminée par analyse calorimétrique différentielle, avec une vitesse d'échauffement de 20° C/min) supérieure à 20° C, dont la structure de base est du type 1,1'-spirobisindane polyfonctionnel de formule I ou une combinaison de différents 1,1'-spirobisindanes polyfonctionnels de formule I également. Dans ladite formule, Z est une liaison directe unique ou bien O-; plus deux éléments parmi R1, R2, R3 et R4 sont -OH, O-CO-R-CO-OH, -O-R-OH, -O-CO-NH-R-NH-CO-O-R-OH ou -[O-CmH2m]n-OH, sachant que m est un entier compris entre 2 et 4, n est un entier compris entre 1 et 20, et R est alkylène C1-C8, cycloalkylène C5-C8, arylène C6-C14 ou arylène C6-C14 partiellement hydraté, et les éléments restants parmi R1, R2, R3 et R4 sont un atome d'hydrogène ou -O- alkyle C1-C8, -O-cycloalkyle C5-C8, -O-aryle C6-C14, -O-aryle C6-C14 partiellement hydraté ou (méth)acrylate; et R5, R6, R7 et R8 sont chacun indépendamment alkyle C1-C8, cycloalkyle C5-C8, aryle C6-C14, aryle C6-C14 partiellement hydraté ou un atome d'hydrogène. Les composés considérés sont utilisés pour la fabrication d'articles moulés, de revêtements, de matériaux à matrice ou d'adhésifs.
EP98941293A 1997-07-16 1998-07-06 Spiro composes du type polyglycidyle et leur utilisation dans des resines epoxy Withdrawn EP1015440A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH174497 1997-07-16
CH174497 1997-07-16
PCT/EP1998/004168 WO1999003851A1 (fr) 1997-07-16 1998-07-06 Spiro composes du type polyglycidyle et leur utilisation dans des resines epoxy

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EP1015440A1 true EP1015440A1 (fr) 2000-07-05

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EP (1) EP1015440A1 (fr)
JP (1) JP2002511874A (fr)
KR (1) KR20010021700A (fr)
CN (1) CN1264373A (fr)
BR (1) BR9810600A (fr)
TW (1) TW515815B (fr)
WO (1) WO1999003851A1 (fr)

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WO2002022600A2 (fr) 2000-09-15 2002-03-21 Anormed Inc. Composes heterocycliques se liant avec les recepteurs de chimiokines
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KR20010021700A (ko) 2001-03-15
WO1999003851A1 (fr) 1999-01-28
TW515815B (en) 2003-01-01
JP2002511874A (ja) 2002-04-16
CN1264373A (zh) 2000-08-23
BR9810600A (pt) 2000-07-11

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