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EP1904546A1 - Résine de mélamine - Google Patents

Résine de mélamine

Info

Publication number
EP1904546A1
EP1904546A1 EP06791524A EP06791524A EP1904546A1 EP 1904546 A1 EP1904546 A1 EP 1904546A1 EP 06791524 A EP06791524 A EP 06791524A EP 06791524 A EP06791524 A EP 06791524A EP 1904546 A1 EP1904546 A1 EP 1904546A1
Authority
EP
European Patent Office
Prior art keywords
melamine resin
melamine
resin according
etherified
transetherification
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Withdrawn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
EP06791524A
Other languages
German (de)
English (en)
Inventor
Steffen Pfeiffer
Werner Deutschbauer
Roland Raninger
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.)
AMI Agrolinz Melamine International GmbH
Original Assignee
AMI Agrolinz Melamine International 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 AMI Agrolinz Melamine International GmbH filed Critical AMI Agrolinz Melamine International GmbH
Publication of EP1904546A1 publication Critical patent/EP1904546A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
    • C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
    • C08G12/427—Melamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/32—Modified amine-aldehyde condensates

Definitions

  • the invention relates to a melamine resin according to the preamble of claim 1, a process for its preparation according to claim 20 and its use according to claim 23.
  • Partially crosslinked melamine resins which are processable in the melt phase are known. These are melamine resins in which the primary condensation products of melamine and formaldehyde are etherified with alcohols.
  • the properties of these partially crosslinked melamine resins are influenced by the corresponding preparation processes, the alcohols used for the etherification, the associated degrees of polymerization and crosslinking and the fillers and additives customarily added to the resins.
  • WO 03/046053 describes molding compositions of melamine resins etherified with alcohols, which are in principle suitable for thermoplastic processing methods but have a very narrow thermoplastic processing window. This means that the final curing of the resins often begins as soon as the molding tool melts.
  • WO 03/106558 likewise relates to molding compositions of melamine resins reposted with alcohols. They are formed by etherification of melamine-aldehyde precondensates with low molecular weight alcohols, followed by transetherification with higher molecular weight alcohols.
  • the crosslinked resins produced in this way have a good melting behavior, that is, there is a sufficiently large processing window between their melting temperature and the beginning of the curing temperature.
  • a disadvantage of the known etherified melamine resins is that they are highly crosslinked and therefore also have a relatively high viscosity in the melt.
  • the viscosity increases further, so that a homogeneous distribution of the fillers in the resin is hardly possible.
  • the high viscosity causes a poor flow behavior of the resin melt in the processing tool.
  • a crosslinked melamine resin ether is mixed here with a crosslinked thermoplastic.
  • Crosslinked thermoplastics such as an ethylene-vinyl acetate copolymer or an ethylene-acrylic acid ester copolymer, act as lubricants and thus improve the flow behavior of the molding compositions.
  • the disadvantage here is that deteriorate by the addition of thermoplastics, the mechanical properties of the molding compositions.
  • the invention is therefore based on the problem to provide a partially crosslinked melamine resin, which has a good flow behavior, but at the same time shows good mechanical properties.
  • the melamine resin according to the invention is characterized in that it has a substantially linear structure and shows a dependence of the viscosity on the shear rate.
  • the essentially linear melamine resins are present as linear or weakly crosslinked chain molecules. These chain molecules can slide on one another at a sufficiently high temperature, whereby the melamine resin becomes meltable and thermoplastically processable. Surprisingly, the melamine resins show a dependence of the viscosity of the resin melt on the shear rate, which is called non-Newtonian behavior. As the shear rate increases, the viscosity of the resin melt decreases. This means that the melamine resins have a very good flow behavior in the melt phase, distribute themselves excellently in the shaping tool and, even with high proportions of fillers, the viscosity remains sufficiently low so that the fillers can be homogeneously distributed in the resin matrix.
  • the melamine resins according to the invention thus have a unique combination of thermoplastic and thermosetting properties.
  • the melamine resins may also be referred to as melamine resins.
  • the substantially linear structure and a dependence of the viscosity of the shear rate exhibiting melamine resin is composed of triazine rings having monosubstituted amino groups and bis-substituted amino groups, wherein the triazine rings are linked via the monosubstituted amino groups by means of condensation and / or etherification. Linkage via the monosubstituted amino groups achieves a loose, substantially linear network.
  • the melamine resins advantageously have molar masses of between 1500 and 200,000. This is a broad molecular weight distribution.
  • N 1 is the number of molecules of molecular weight M 1 and M 1 is the molecular weight of molecule type i.
  • the preferred molar ratio of melamine / formaldehyde in the melamine resins is in the range of 1: 3 to 1: 5.
  • the melamine resins according to the invention differ from the known etherified melamine resins in their higher formaldehyde content.
  • the degree of precrosslinking of the melamine resins is determined decisively by the ratio of melamine / formaldehyde during the synthesis of the precondensate.
  • a molar melamine / formaldehyde ratio of 1: ⁇ 3 the formation of monosubstituted amino groups on the melamine ring is preferred and there are even unsubstituted NH 2 groups on the melamine ring.
  • Many mono-substituted and unsubstituted amino groups as in the known etherified melamine resins lead to a stronger cross-linking and linking of the melamine rings by self-condensation and / or etherification, resulting in the formation of undesirable rigid, solid and branched networks.
  • Umetherung the primary etherified groups are formed with diols and / or polyols.
  • the choice of alkanols, diols and polyols can be used to influence the chain lengths and thus the degree of crosslinking of the melamine resins.
  • C 1 - to C 4 -alkanols in particular methanol
  • polyester diols, butanediols or polyetherdiols is advantageous.
  • the ratio of alkanol to diol and / or polyol is in a range of 8: 1 to 1: 1, preferably 4: 1 to 2: 1. With these alcohols good conversions are achieved with good resin properties.
  • the transetherification is carried out at pH greater than or equal to 7.0.
  • a basic pH ensures that almost all of the monosubstituted methoxy groups react with the diols and polyols, thus favoring the formation of linear structures.
  • the transetherification of etherified primary groups is advantageously carried out in a temperature range between 150 0 C to 250 ° C. Preference is given to a residence time in the transetherification which is between 0.5 and 15 minutes. The reaction is slower at low temperatures and faster at high temperatures.
  • additives in particular flame retardants, pigments, stabilizers, catalysts, UV absorbers and / or free-radical scavengers are added to the melamine resin.
  • fillers are in particular those of the type melamine, urea, cellulose, wood, urea-formaldehyde resins, melamine-formaldehyde resins, polyether polyols and / or polyester polyols use.
  • the urea-formaldehyde resins and melamine-formaldehyde resins used as fillers can be completely etherified, partially etherified and unetherified.
  • Additives and fillers are added to the melamine resins to special
  • Resin properties such as toughness, elasticity, color, electrical properties to achieve.
  • additive and filler amounts of up to 80% are possible.
  • the melamine resin has a glass point greater than 35 ° C.
  • the molar mass average M w is usually greater than 5000.
  • Such a melamine resin has particularly good properties with regard to storability, miscibility, and processability.
  • the object of the invention is also achieved by a method for producing a
  • the pH of the melamine resin solution is adjusted to ⁇ 7 and the melamine resin is concentrated to the resin melt. This is done, for example, in one or more thin film evaporators.
  • the melamine resin melt is transesterified at 150 to 250 0 C with diols and / or polyols, whereupon the melamine resin is cooled and made up.
  • the melamine resin is obtained as granules.
  • the transetherification takes place continuously in the extruder or residence time reactor or discontinuously in the kneader.
  • higher temperatures and lower residence times prevail in the extruder and lower temperatures and longer residence times in the residence time reactor.
  • the diols and / or polyols used for the transetherification are added before, during or after the concentration.
  • the additives and fillers are preferably added after the transetherification. There they can be mixed particularly homogeneously with the resin due to the good flow behavior and the good wettability of Melaminhharzschmelze.
  • the melamine resins are used for the production of molding compositions for melt processing and for the production of composite materials, in particular wood composites.
  • composite materials in particular wood composites.
  • a very good wetting of the wood particles and an excellent sliding behavior in the shaping tool are achieved with the melamine resins according to the invention.
  • the melamine resins can be used for the production of plates, pipes, profiles, injection molded parts, fibers and foams, as well as for processing from solution or dispersion as adhesive, impregnating resin, paint resin or laminating resin or for the production of foams, microcapsules or fibers.
  • the use of the melamine resins according to the invention is advantageous where a corresponding theological behavior is desired. This is for example Injection molding applications the case or when large amounts of fillers must be incorporated into the melamine resins.
  • Figure 1 a diagram showing the viscosity of the melamine resin as
  • Trimethylolpropane added. Subsequently, the solution is continuously concentrated over two thin-film evaporator to a residual solvent content of ⁇ 5% by mass.
  • the etherified melamine-formaldehyde precondensates from Examples 1 and 2 are metered at 10-12 kg / h.
  • the extruded from the extruder strand of Polytriazinethers is assembled in a roll granulator.
  • the resulting melamine resin has a viscosity at 130 ° C of 2 to 200 Pa * s and a determined by HPLC or GC conversion of diol from 50 to 80%.
  • the viscosity of the sliding resin produced under these conditions is 2 Pa * s at 130 0 C at a diol conversion of 65% (HPLC).
  • the viscosity of the sliding resin produced under these conditions is 120 Pa * s at 13O 0 C with a diol conversion of 75% (GC).
  • the glass transition temperature T 9 of the melamine resin is 41 ° C.
  • the viscosity of the sliding resin produced under these conditions is 30 Pa * s at 130 ° C with a diol conversion of 63% (GC).
  • the glass transition temperature T g of the melamine resin is 36 ° C.
  • the melamine resin has a weight average molecular weight of 9000 g / mol.
  • the viscosity of the Gleitharzes produced under these conditions is 200 Pa * s at 130 0 C at a diol conversion of 67% (GC).
  • the glass transition temperature T 9 of the melamine resin is 47 ° C.
  • the melamine resin has a weight average molecular weight of 15,000 g / mol.
  • the viscosity of the Gleitharzes produced under these conditions is 1500 Pa * s at 100 0 C at a triol conversion of 70% (GC).
  • the glass transition temperature T 9 of the melamine resin is 37 ° C.
  • the melamine resin has a weight average molecular weight of 35,000 g / mol.
  • the transetherification and further condensation of the precondensates to the sliding resin takes place in a residence time reactor with an average residence time of 5 to 10 minutes and temperatures of 150 to 200 ° C at a pressure of 200-500 mbar. This melt is then metered into the feed zone of the extruder. The extruded from the extruder strand of Polytriazinethers is assembled in a roll granulator.
  • the transetherification with 1,4-butanediol according to Example 3 takes place in a residence time reactor for a period of 5 minutes and at a temperature of 160 ° C.
  • the subsequent metering takes place in an extruder with the following temperature profile:
  • the viscosity of the sliding resin produced under these conditions is 70 Pa * s at 130 ° C with a diol conversion of 72% (GC).
  • the glass transition temperature T 9 of the melamine resin is 45 ° C.
  • the melamine resin has a weight average molecular weight of 25,000 g / mol.
  • the transetherification with 1,4-butanediol according to Example 3 takes place in a residence time reactor for a period of 7 minutes and at a temperature of 16O 0 C.
  • the subsequent metering takes place in an extruder with the following temperature profile:
  • the viscosity of the sliding resin produced under these conditions is 100 Pa * s at 130 ° C with a diol conversion of 76% (GC).
  • the glass transition temperature T 9 of the melamine resin is 48 ° C.
  • viscosity and the glass transition point of the melarmin resins according to the invention can be influenced by the various parameters such as the amount of diol or polyol, temperature setting and residence time in the residence time reactor and extruder.
  • the glass point is a measure of the linearity and uniformity of the sliding resin. The higher the glass point for a given weight average molecular weight, the more linear the melamine resin is built up.
  • FIG. 1 shows a functional relationship between viscosity and shear rate typical for one embodiment of the melamine resins according to the invention, measured at 130 ° C. It can be seen that in the measured shear region there is an almost linear dependence of the viscosity on the shear rate, which is referred to as non-Newtonian behavior referred to as.

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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)
  • General Chemical & Material Sciences (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une résine de mélamine qui se caractérise par une constitution sensiblement linéaire et par une viscosité dépendant du taux de cisaillement. La présente invention porte également sur un procédé pour produire cette résine de mélamine et sur son utilisation.
EP06791524A 2005-06-20 2006-06-19 Résine de mélamine Withdrawn EP1904546A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005029683A DE102005029683A1 (de) 2005-06-20 2005-06-20 Melaminharz
PCT/EP2006/006185 WO2006136457A1 (fr) 2005-06-20 2006-06-19 Résine de mélamine

Publications (1)

Publication Number Publication Date
EP1904546A1 true EP1904546A1 (fr) 2008-04-02

Family

ID=36928337

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06791524A Withdrawn EP1904546A1 (fr) 2005-06-20 2006-06-19 Résine de mélamine

Country Status (6)

Country Link
US (1) US20090239978A1 (fr)
EP (1) EP1904546A1 (fr)
CA (1) CA2611194A1 (fr)
DE (1) DE102005029683A1 (fr)
RU (1) RU2007146819A (fr)
WO (1) WO2006136457A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SI2197927T1 (en) * 2007-10-12 2018-01-31 Borealis Agrolinz Melamine Gmbh Aromatic resin, which can be thermoplastic, durable finely-fibrous nonwovens, as well as the process and device for their production
JP4888330B2 (ja) * 2007-10-22 2012-02-29 トヨタ自動車株式会社 直接噴射式の内燃機関
CN104774427B (zh) * 2015-05-07 2016-03-02 成都玉龙化工有限公司 一种高密度软质三聚氰胺泡沫及制备方法
CN110305275B (zh) * 2019-07-08 2021-11-16 金陵科技学院 氨甲基膦基脲醛低聚物钢筋阻锈剂的制备方法
CN113185745A (zh) * 2021-04-08 2021-07-30 峰特(浙江)新材料有限公司 一种无机填料的三聚氰胺甲醛泡沫

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DE2430899C3 (de) * 1974-06-27 1981-06-19 Cassella Ag, 6000 Frankfurt Verfahren zur Herstellung von niedrigviskosen körperreichen Melaminharz-Lösungen mit geringem Gehalt an freiem Formaldehyd
US4528344A (en) * 1984-05-21 1985-07-09 Ppg Industries, Inc. Low molecular weight resins from nonaromatic polyols and aminoplasts
AT398768B (de) * 1991-08-05 1995-01-25 Chemie Linz Gmbh Modifizierte melaminharze sowie prepregs und laminate auf basis dieser melaminharze
DE4420013A1 (de) * 1994-06-08 1995-12-14 Basf Ag Melaminharz-Mischungen
DE10056398B4 (de) * 2000-11-14 2006-12-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Aus der Schmelze verarbeitbares Aminoharz auf Basis von 1,3,5-Triazinen und Aldehyden
DE10136321C1 (de) * 2001-07-26 2002-12-12 Agrolinz Melamin Gmbh Linz Polymere aus Triazinderivaten
AT411761B (de) * 2002-06-14 2004-05-25 Agrolinz Melamin Gmbh Aminoplast-formmassen für erzeugnisse verbesserter flexibilität
AR040209A1 (es) * 2002-06-14 2005-03-16 Agrolinz Melamin Gmbh Material de moldeo de amino resina para productos con flexibilidad mejorada y productos de amino resina con flexibilidad mejorada
AT411685B (de) * 2002-06-14 2004-04-26 Agrolinz Melamin Gmbh Zusammensetzungen zur herstellung von aminoplasterzeugnissen
DE10246472A1 (de) * 2002-09-27 2004-04-08 Agrolinz Melamin Gmbh Endlosfäden mit hoher Dimensionsstabilität, Hydrolysebeständigkeit und Flammfestigkeit
DE10261804B4 (de) * 2002-12-19 2008-05-21 Ami-Agrolinz Melamine International Gmbh Direktsyntheseverfahren zur Herstellung von veretherten Melaminharzkondensaten, Melaminharzkondensate und deren Verwendung
DE10313200A1 (de) * 2003-03-19 2004-10-07 Ami-Agrolinz Melamine International Gmbh Prepregs für Faserverbunde hoher Festigkeit und Elastizität
DE10318481B4 (de) * 2003-04-16 2006-09-07 Ami-Agrolinz Melamine International Gmbh Verfahren zur kontinuierlichen Synthese eines Melaminflüssigharzes
DE10333892A1 (de) * 2003-07-22 2005-02-10 Ami-Agrolinz Melamine International Gmbh Kunststofferzeugnis hoher Festigkeit und Flexibilität
DE10333893A1 (de) * 2003-07-22 2005-02-10 Kompetenzzentrum Holz Gmbh Kunststoffe und Holz enthaltende Verbundwerkstoffe

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Also Published As

Publication number Publication date
CA2611194A1 (fr) 2006-12-28
RU2007146819A (ru) 2009-07-27
US20090239978A1 (en) 2009-09-24
WO2006136457A1 (fr) 2006-12-28
DE102005029683A1 (de) 2007-01-04

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