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WO2004083275A1 - Matieres a mouler thermodurcissables presentant une aptitude au façonnage amelioree - Google Patents

Matieres a mouler thermodurcissables presentant une aptitude au façonnage amelioree Download PDF

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Publication number
WO2004083275A1
WO2004083275A1 PCT/EP2004/002861 EP2004002861W WO2004083275A1 WO 2004083275 A1 WO2004083275 A1 WO 2004083275A1 EP 2004002861 W EP2004002861 W EP 2004002861W WO 2004083275 A1 WO2004083275 A1 WO 2004083275A1
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Prior art keywords
alkyl
alkylene
arylene
chr
molding compositions
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German (de)
English (en)
Inventor
Manfred Rätzsch
Martin Burger
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AMI Agrolinz Melamine International GmbH
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AMI Agrolinz Melamine International GmbH
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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/771—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur oxygen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/544—Polycondensates of aldehydes with nitrogen compounds

Definitions

  • the invention relates to thermosetting molding compositions with improved processability based on aminotriazines and to a process for their preparation.
  • Thermosetting molding compositions based on aminotriazine resins such as melamine-formaldehyde resins or melamine-urea-formaldehyde resins [Ulimanns Encyclopedia of Industrial Chemistry (1987), Vol. A2, 130-131] are known.
  • a disadvantage in the production of products from melamine resins is the difficult processability by conventional thermoplastic processing methods such as extrusion, injection molding or blow molding.
  • Low molecular weight melamine resin precondensates are too low in melt viscosity for these processing methods and can only be processed as highly filled molding compounds with long cycle times while the products are hardening (Woebcken, W., Kunststoff-Handbuch Vol. 10 "Duroplasts", Carl Hanser Verl. Kunststoff 1988, pp. 266-274). Because of the low melt viscosity of the melamine resin precondensates, fibers, foams or coatings made of melamine resins can only be produced from solutions of the melamine resin precondensates with curing during the shaping.
  • the aim of the invention is thermosetting molding compositions based on aminotriazines, which can be processed like thermoplastics from the melt.
  • thermosetting molding compositions the molding compositions according to the invention containing thermoplastically processable polyaminotriazine molding compositions containing carbamic acid ester groups A) 90 to 99% by mass of meltable polyaminotriazine ethers with molar masses of 500 to 5000 by thermal self-condensation of aminoriazine ethers of the structure
  • Ri -NH 2 ,, -NH-CHR 2 -OH, -NH-CHR 2 -0-R 3 , -NH-CHR 2 -0-R 4 -OH, -CH 3 , -C 3 H 7 , - C 6 H 5, -OH, phthalimido, succinimido, -NH-CO-C 5 -C 8 alkyl, -NH-C 5 -C 18 alkylene-OH, -NH-CHR 2 -0-C 5 -C 18 alkylene-NH 2 , -NH-C 5 -C 18 alkylene-NH 2 ,
  • R 2 -H, -C r C 7 alkyl
  • R 3 -C r C 18 - alkyl, -R 4 -OH,
  • R 4 -CH (CH 3 ) -CH 2 -0-C 2 -C 12 -alkylene-0-CH 2 -CH (CH 3 ) -, -CH (CH 3 ) -CH 2 -0-C 2 - C 12 -Aryle ⁇ -0-CH 2 -CH (CH 3 ) -,
  • X - ⁇ (CH 2 ) 2 . 8 -0-C0-C 6 -C 14 -arylene-C0-0- (CH 2 ) 2 . 8 ⁇ - or - ⁇ (CH 2 ) 2 . 8 -0-C0-C 2 -C 12 -alkylene-C0-0- (CH 2 ) 2 . 8 ⁇ -;
  • thermosetting molding compositions up to 75% by mass of fillers and / or reinforcing fibers, up to 50% by mass of further reactive polymers of the ethylene copolymer type, maleic anhydride copolymers, modified maleic anhydride copolymers, poly (meth) acrylates, polyamides, polyesters and / or polyurethanes, and up to 2 mass%, each based on the sum of polyaminotriazine ether and isocyanate, latent hardeners, stabilizers, UV absorbers and / or auxiliaries.
  • thermosetting molding compositions can be in the form of cylindrical, lenticular, pastille-shaped or spherical particles with an average diameter of 0.5 to 8 mm.
  • the ratio of aldehyde component / aminotriazine component is preferably 1: 1 to 3: 1.
  • suitable aminotriazine components in the meltable polyaminotriazine ethers which are defined by the substituent Ri in the structural formula, are melamine, acetoguanamine, benzoguanamine, butyroguanarnine, N- (4,6-diamino-1, 3,5-triazine-2-) yl) phthalimide and 2,4-diamino-6-succinimido-1, 3,5-triazine.
  • Suitable CrC 8 aldehyde components in the meltable polyaminotriazine ethers which are defined by the substituent R 2 in the structural formula, are formaldehyde, acetaldehyde and trimethylol acetaldehyde.
  • the meltable polytriazine ethers can be converted by reaction of aminotriazines with CC 8 aldehydes to aminotriazine precondensates, etherification of the aminotriazine precondensates with CC 4 alcohols, optionally with transetherification with C 5 -C 18 alcohols and / or diols of the HO type -R 4 -OH, and produce thermal self-condensation ion at 120 to 190 ° C.
  • R 3 in the structural formula defines the etherification component which is a C 18 -C 18 alcohol and / or a diol of the HO-R 4 -OH type.
  • CC 4 alcohols which can be present as etherification component R 3 in the meltable polyaminotriazine ethers are methanol, isopropanol and butanol.
  • C 5 -C 18 alcohols which may be present as etherification component R 3 in the meltable polyaminotriazine ethers are ethylhexyl alcohol, dodecyl alcohol and stearyl alcohol.
  • diols of the type HO-R 4 -OH, R 4 - [(CH 2 ) 2-8 -O-CO-C 6 -C 14 -arylene-CO-O- (CH 2 ) 2- 8 ] n -
  • esters and polyesters based on saturated dicarboxylic acids such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid and diols such as ethylene glycol, butanediol, neopentyl glycol and / or hexanediol.
  • diols such as ethylene glycol, butanediol, neopentyl glycol and / or hexanediol.
  • Bis (hydroxyethyl) terephthalate preferred.
  • diols of the type HO-R 4 -OH, R 4 - [(CH 2 ) 2- 8-O-CO-C 2 -C 12 alkylene-CO-O- (CH 2 ) 2- 8] ⁇ -
  • etherification component R 3 in the meltable polyaminotriazine ethers are polyesters based on saturated dicarboxylic acids such as adipic acid and / or succinic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid and / or itaconic acid and diols such as ethylene glycol, butanediol, neopentyl glycol and / or hexanediol.
  • diols of the type HO-R 4 -OH, R 4 sequences of the type containing siloxane groups
  • C 1 -C 4 -alkyl dC -alkyl which may be present as etherification component R 3 in the meltable polyaminotriazine ethers are 1,3-bis (hydroxybutyl) tetramethyldisiloxane and 1,3-bis (hydroxyoctyl) tetraethyldisiloxane.
  • polyester sequences with diols containing siloxane groups of the type HO-R 4 -OH, R 4 - [(X) r -O-CO- (Y) s -CO-O- (X) r ] - which are used as etherification component R 3 can be contained in the meltable polyaminotriazine ethers, at them
  • X - ⁇ (CH 2 ) 2 . 8 -0-CO-C 6 -C 14 arylene-CO-0- (CH 2 ) 2 . 8 ⁇ - or - ⁇ (CH 2 ) 2 . 8 -0-CO-C 2 -C 12 -alkylene-CO-0- (CH 2 ) 2 . 8 ⁇ -;
  • polyether diols containing siloxane groups HO-R 4 -OH, R 4 polyether sequences of the type
  • diols based on alkylene oxide adducts of melamine of the 2-amino-4,6-bis (hydroxy-C 2 -C 4 -alkyleneamino) -1,3,5-triazine type which are used as etherification component R 3 in
  • the meltable polyaminotriazine ethers can be contained are diols based on melamine and ethylene oxide or propylene oxide.
  • phenol ether diols based on dihydric phenols and C 2 -C 8 diols of the bis (hydroxy-C 2 -C 8 alkylene-O-) C 6 -C 18 arylene type which contain R 3 as etherification component in the meltable polyaminotriazine ethers can be, are ethylene oxide adducts or propylene oxide adducts with diphenylolpropane.
  • ethereal component R 3 may also contain trihydric alcohols such as glycerol or tetravalent alcohols such as erythritol or mixtures thereof with dihydric alcohols in the meltable polyaminotriazine ethers.
  • the meltable polyaminotriazine ethers are preferably etherified melamine resins based on melamine, formaldehyde and methanol.
  • thermoset molding compositions examples include Al 2 O 3, Al (OH) 3, barium sulfate, calcium carbonate, glass spheres, silica, mica, quartz powder, slate powder, hollow microspheres, carbon black, talc, rock powder, wood powder, cellulose powder and / or shell and core flours such as peanut shell flour or olive flour.
  • the reinforcing fibers possibly contained in the thermosetting molding compositions are inorganic fibers, in particular glass fibers and / or carbon fibers, natural fibers, in particular cellulose fibers such as flax, jute, kenaf and wood fibers, and / or plastic fibers, in particular fibers made of polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate, polypropylene, polyesters and / or polyamides.
  • ethylene copolymers optionally contained in the thermosetting molding compositions as further reactive polymers are partially saponified ethylene-vinyl acetate copolymers, ethylene-butyl acrylate-acrylic acid copolymers, ethylene-hydroxyethyl acrylate copolymers or ethylene-butyl acrylate-glycidyl methacrylate copolymers ,
  • maleic anhydride copolymers optionally contained in the thermoset molding compositions are C 2 -C 20 olefin - maleic anhydride copolymers or C H. polymers of maleic anhydride and C 8 -C 2 o-vinyl aromatics.
  • modified maleic anhydride copolymers optionally contained in the thermosetting molding compositions are preferably partially or completely esterified, amidated or imidized maleic anhydride copolymers.
  • poly (meth) acrylates optionally contained in the thermosetting molding compositions are copolymers based on functional unsaturated (meth) acrylate monomers such as acrylic acid, hydroxyethyl acrylate, glycidyl acrylate, methacrylic acid, hydroxybutyl methacrylate, or glycidyl methacrylate and non-functional unsaturated (meth) - Acrylate monomers such as ethyl acrylate, butyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl acrylate and / or butyl methacrylate and / or C 8 -C 2 o-vinyl aromatics.
  • functional unsaturated (meth) acrylate monomers such as acrylic acid, hydroxyethyl acrylate, glycidyl acrylate, methacrylic acid, hydroxybutyl methacrylate, or glycidyl methacrylate and non
  • Copolymers based on methacrylic acid, hydroxyethyl acrylate, methyl methacrylate and styrene are preferred.
  • the polyamides optionally contained in the thermoset molding compositions are polyamide-6, polyamide-6,6, polyamide-11, polyamide-12, polyaminoamides from polycarboxylic acids and polyalkylene amines, and the corresponding methoxylated polyamides.
  • polyesters optionally contained in the thermosetting molding compositions are polyesters with molar masses from 2000 to 15,000 composed of saturated dicarboxylic acids such as phthalic acid, isophthalic acid, adipic acid and / or succinic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid and / or itaconic acid and diols such as ethylene glycol, Butanediol, neopentyl glycol and / or hexanediol. Branched polyesters based on neopentyl glycol, trimethylolpropane, isophthalic acid and azelaic acid are preferred. - ••
  • thermoset molding compositions examples include uncrosslinked polyurethanes based on tolylene diisocyanate, diphenylmethane diisocyanate, butane diisocyanate and / or hexane diisocyanate as diisocyanate components and butane diol, hexane diol and / or polyalkylene glycols as diol components with molecular weights from 2,000 to 30,000.
  • the latent hardeners contained in the thermoset molding compositions are preferably weak acids, in particular
  • thermosetting molding compositions are piperidine derivatives, benzophenone derivatives, benzotriazole derivatives, triazine derivatives and / or benzofuranone derivatives.
  • auxiliaries which may be present in the thermoset molding compositions are processing aids such as calcium stearate, magnesium stearate and / or waxes.
  • thermosetting molding compositions with improved processability are produced by a process in which mixtures of
  • meltable polyaminotriazine ethers with molecular weights of .500 to 5000, which are obtained by thermal self-condensation of aminotriazine ethers of the structure
  • Ri -NH 2 ,, -NH-CHR 2 -OH, -NH-CHR 2 -0-R 3 , NH-CHR 2 -0-R 4 -OH, -CH 3 , -C 3 H 7 , -C 6 H 5, -OH, phthalimido, succinimido, -NH-CO-C 5 -C 18 alkyl, -NH-C 5 -C 18 alkylene-OH, -NH-CHR 2 -0-C 5 - C 18 alkylene-NH 2 , -NH-C 5 -C 18 alkylene-NH 2>
  • R 2 -H, -CC 7 - alkyl
  • R 3 -C ⁇ -C 18 - alkyl, -R 4 -OH,
  • R 4 -CH (CH 3 ) -CH 2 -0-C 2 -C 12 -alkylene-0-CH 2 -CH (CH 3 ) -, -CH (CH 3 ) -CH 2 -0-C 2 - C 12 arylene-0-CH 2 -CH (CH 3 ) -,
  • the melt in kneaders at temperatures of 120 to 190 ° C. and residence times of 1 to 20 minutes, and the polyaminotriazine ethers containing carbamic acid ester groups are discharged after cooling the melt to 85 to 130 ° and granulated, the melt of the polyamino triazine ethers containing carbamic acid ester groups before discharge up to 75% by mass of fillers and / or reinforcing fibers, up to 50% by mass of further reactive polymers of the ethylene copolymer type, maleic anhydride copolymers, modified maleic anhydride copolymers, poly (meth) acrylates, Polyamides, polyesters and / or polyurethanes, and up to 2% by mass, based in each case on the polytriazine ethers containing carbamic acid ester groups, latent hardeners, stabilizers, UV absorbers and / or auxiliaries, can be added.
  • Double screw extruders L / D are preferred as kneaders. , 3.2-48. Suitable with counter-rotating screw arrangement and several degassing zones.
  • the melt can be fed into a melt filter using a gear pump.
  • the melt can be converted into granulate particles in pastilation plants by metering the melt via a feed device onto a continuous steel belt and cooling and solidifying the pastilles deposited.
  • meltable polyaminotriazine ethers with molar masses from 500 to 5000 are precondensates that contain 4,6-bis (ethoxymethylamino) -2-butoxymethylamino-1, 3,5-triazine, 2,4,6- Tris (dimethoxymethyl-imino) -1, 3,5-triazine or 2,4,6-trimethoxymethylamino-1,3,5-triazine as the main component in a mixture with their higher molecular weight oligomers.
  • thermosetting molding compositions A preferred process variant in the production of the thermosetting molding compositions is that the self-condensation of aminotriazine ethers of the structure
  • meltable polyaminotriazine ethers with molecular weights of. 500 to 5000 and the implementation of the meltable polyaminotriazine ether with the diisocyanates in the melt in a continuous kneader is carried out in successive reaction stages.
  • 2,4,6-Tris (methoxymethylamino) -1,3,5-triazine is preferably used as the aminotriazine ether in the process for the production of thermoset molding compositions.
  • thermosetting molding compositions according to the invention are that, owing to the higher melt viscosity compared to conventional triazine derivative precondensates such as melamine-formaldehyde precondensates or guanamine-formaldehyde precondensates, they are processed like thermoplastics by melt processing methods such as extrusion or injection molding at temperatures of 130 to 220 ° C. can be.
  • melt processing methods such as extrusion or injection molding at temperatures of 130 to 220 ° C. can be.
  • Preferred areas of application are hot melt adhesive and the production of plates, tubes, profiles, injection molded parts, fibers, coatings, hollow bodies and foams.
  • thermosetting molding compositions according to the invention insofar as they contain no fillers, reinforcing fibers and / or further reactive polymers, are soluble in polar solvents of the CC 10 type, alcohols, dimethylformamide or dimethyl sulfoxide in concentrations of up to 60% by mass.
  • the solutions or dispersions are suitable as adhesives, impregnating agents, paint resin or laminating resin formulations or for the production of foams, microcapsules or fibers.
  • the advantages of the solutions or dispersions of the thermosetting molding compositions according to the invention compared to the corresponding triazine resin precondensates are the higher viscosity and the resultant better flow properties or higher strengths of non-cured intermediates in fiber or foam production.
  • the invention is illustrated by the following examples:
  • thermoset molding compound 2,4,6-tris (methoxymethylamino) -1, 3,5-triazine is used as the etherified aminotriazine precondensate, bis (hydroxyethyl) terephthalate as the diol component for the transetherification and diphenyloxide diisocyanate as the diisocyanate.
  • the transetherification and thermal self-condensation to the polyaminotriazine ether is carried out in the measuring kneader (from Haake Polylabsystem 540p). After preheating to 170 ° C., 32.5 g of bis (hydroxyethyl) terephthalate and 39.5 g of 2,4,6-tris (methoxymethylamino) -l, 3,5-triazine are metered into the kneading chamber and at at a speed of 50 min "1 until a torque of 3 Nm is reached after a reaction time of 6 min. The methanol released during the compounding is removed from the kneading chamber by vacuum.
  • thermoset molding composition After cooling to 120 ° C., 4.5 g of diphenyloxide diisocyanate added, kneaded for a further 6 min, the polyamino triazine ether containing carbamic acid ester groups was discharged and, after cooling, ground in a universal mill 100 UPZ / II (Alpine Hosokawa) with a beating disc and 2 mm sieve.
  • the viscosity of the thermoset molding composition at 140 ° C. is 390 Pa.s.
  • cellulose nonwovens 120 g / m 2 , Lenzing AG, Austria
  • the finely ground thermosetting molding compound average particle diameter 0.1 mm
  • the prepregs produced in this way have a resin application of approx. 50%.
  • the prepregs are cut to a size of 30x20 cm.
  • 3 prepregs plus an untreated cellulose fleece are placed on top of one another in a press mold (30x20cm) preheated to 160 ° C and the press is slowly moved in, the prepregs not yet moving due to the Let the hardened thermoset molding compound slightly deform. Under a pressure of 160 bar, the temperature is raised to 185 ° C and pressed for 15 minutes. The finished workpiece is removed, slowly cooled, and the through Resin emerging on the plunge edge of the press tool grinded burr.
  • Test specimens milled out of the workpiece have an elastic modulus of 5.9 GPa, an elongation at maximum force of 2.9% and an impact resistance of 11.5 kJ / m 2 in the bending test.
  • a melamine dispersion is prepared in a 30 l stirred autoclave by introducing 1.0 kg of melamine in 13.7 kg of methanol at 95 ° C., and after. Setting one. pH of 6 in the stirred autoclave as an aldehyde component, a mixture of 3 kg of formaldehyde, 1, 29 kg of methanol and 4.31 kg of water, which is preheated to 90 ° C, metered under pressure, and the reaction mixture at a reaction temperature of 95 ° C and a reaction time of 5 min.
  • a pH of 9 is set by adding n / 10 sodium hydroxide solution, and the etherified aminotriazine resin condensate dissolved in the water-methanol mixture is transferred to a first vacuum evaporator after adding 2.23 kg of butanol. in which the solution of the etherified aminotriazine resin condensate is concentrated at 80 ° C. to a highly concentrated aminotriazine resin solution which has a solids content of 75% by mass and a butanol content of 10% by mass.
  • the highly concentrated solution of the etherified aminotriazine resin is subsequently transferred to a second vacuum evaporator and concentrated at 90 ° C. to a syrupy melt which has a solids content of 95% by mass and a butanol content of 5% by mass.
  • the syrupy melt is fed at 3.5 kg / h into the feed hopper of a laboratory extruder GL 27 D44 (Leistritz) with vacuum degassing zones after the feed zone and before the product discharge and a side flow metering for liquid media, temperature profile 220 ° C / 240 o C / 240 o C / 240 o C / 240 o C / 240 o C / 200 ° C / 170 ° C / 150X / 150 ° C / 150 ° C, extruder speed 100 min "1 , dosed, the aminotriazine ether thermally condensed and the volatile components at 100 mbar A 0.12 kg / h bisphenol A diisocyanate is metered into the melt of the polyaminotriazine ether via a side stream metering and with the Implemented polyaminotriazine ether. After a second vacuum degassing at 150 mbar, the emerging strand of the polya
  • the polyaminotriazine ether has a weight average molecular weight (GPC) of 2200 and a molar ratio of carbamic acid ester groups / triazine segment of 1:20
  • An aminotriazine dispersion is prepared in a 30 l stirred autoclave by introducing 0.9 kg melamine and 0.1 kg benzoguanamine in 15 kg methanol at 95 ° C, and after adjusting the pH to 6 ⁇ 2 in the stirred autoclave, a mixture as an aldehyde component 2.7 kg of formaldehyde, 0.3 kg of glyoxal and 3 kg of water, which has been preheated to 90 ° C., are metered in under pressure, and the reaction mixture is reacted at a reaction temperature of 90 ° C. and a reaction time of 10 min.
  • a pH of 9.2 is set by adding n / 10 sodium hydroxide solution, and the etherified aminotriazine resin condensate dissolved in the water / methanol mixture is added to a first vacuum evaporator after adding 0.6 kg of butanol transferred in which the solution of the etherified aminotriazine resin condensate is concentrated at 80 ° C. to a highly concentrated aminotriazine resin solution which has a solids content of 76% by mass and a butanol content of 3.1% by mass.
  • the highly concentrated solution of the etherified aminotriazine resin is then mixed in a mixing section with 0.8 kg of Simulsol BPLE (oligoethylene glycol ether of bisphenol A), transferred to a second vacuum evaporator and concentrated at 90 ° C. to a syrupy melt which has a solids content of 98% by mass and has a butanol content of 2.2% by mass.
  • Simulsol BPLE oligoethylene glycol ether of bisphenol A
  • the syrupy melt of the etherified aminotriazine resin condensate is fed at 3.3 kg / h into the feed hopper of a laboratory extruder GL 27 D44 (Leistritz) with two vacuum degassing zones after the feed zone as well as before the product discharge and side stream dosing devices for solid and liquid media, temperature profile 220 ° C / 240 ° C / 240 ° C / 240 o C / 240 o C / 240 ° C / 200 ° C / 170 o C / 150 ° C / 150 ° C / 150 ° C ° C, extruder speed 100 min "1 , dosed, the aminotriazine ether is condensed and the reaction mixture is degassed at 150 mbar, and the polyaminotriazine ether is melted at 0.31 by means of a side stream metering kg / h of tolylene diisocyanate metered, homogenized and converted to polyamin
  • a masterbatch of 37.4 mass% polyamide-12, 60 mass% glass fibers, 2 mass% zinc stearate and 0.6 mass is introduced into the melt of the polyaminotriazine ether containing carbamic acid ester groups % Phthalic anhydride metered, and the emerging strand cut in a granulator.
  • thermoset molding compound is injected at a melt temperature of 210 ° C into standard test specimens which have a flexural strength of 22.6 kp / mm 2 , a tensile elongation of 2.2% and a Charpy impact strength of 9.5 kp cm / cm 2 .

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  • Polymers & Plastics (AREA)
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Abstract

Selon l'invention, des matières à mouler thermoplastiques à base de polyaminotriazine, ces matières contenant des groupes ester d'acide carbamique, peuvent être produites par réaction de polyaminotriazine-éthers fusibles avec des diisocyanates à des températures comprises entre 120 et 190 DEG C. Ces matières peuvent être utilisées pour produire des plaques, des tubes, des profilés, des pièces moulées par injection, des fibres et des produits alvéolaires.
PCT/EP2004/002861 2003-03-19 2004-03-18 Matieres a mouler thermodurcissables presentant une aptitude au façonnage amelioree Ceased WO2004083275A1 (fr)

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DE10313198.1 2003-03-19
DE2003113198 DE10313198A1 (de) 2003-03-19 2003-03-19 Duroplastformmassen verbesserter Verarbeitbarkeit

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CN115141341A (zh) * 2022-06-26 2022-10-04 瀚寅(苏州)新材料科技有限公司 一种全水发泡聚氨酯用组合聚醚及其制备方法

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Publication number Priority date Publication date Assignee Title
DE102006034608A1 (de) * 2006-07-21 2008-02-14 Ami-Agrolinz Melamine International Gmbh Thermoplastisch verarbeitbare Duroplastformmassen mit verbessertem Eigenschaftsspektrum
DE102008026266A1 (de) * 2008-06-02 2009-12-03 Henkel Ag & Co. Kgaa Formkörper aus verklebten Granulaten
IES20090970A2 (en) * 2009-12-23 2011-05-11 C & F Tooling Ltd An alternator

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EP1279686A2 (fr) * 2001-07-26 2003-01-29 Agrolinz Melamin GmbH Polymères à partir de dérivés de triazine

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Publication number Priority date Publication date Assignee Title
DE2414427A1 (de) * 1974-03-26 1975-10-23 Cassella Farbwerke Mainkur Ag Hitzehaertendes ueberzugsmittel in form einer dispersion
DE4120323A1 (de) * 1991-06-20 1992-12-24 Bayer Ag Verfahren zur herstellung von harnstoffgruppen aufweisenden melaminharzen, die so erhaltenen harze und ihre verwendung
EP1279686A2 (fr) * 2001-07-26 2003-01-29 Agrolinz Melamin GmbH Polymères à partir de dérivés de triazine

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CN115141341A (zh) * 2022-06-26 2022-10-04 瀚寅(苏州)新材料科技有限公司 一种全水发泡聚氨酯用组合聚醚及其制备方法

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