EP2970711A1 - Utilisation de polyesters ignifuges de manière inhérente dans des adhésifs et des agents d'étanchéité - Google Patents

Utilisation de polyesters ignifuges de manière inhérente dans des adhésifs et des agents d'étanchéité

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Publication number
EP2970711A1
EP2970711A1 EP14708855.3A EP14708855A EP2970711A1 EP 2970711 A1 EP2970711 A1 EP 2970711A1 EP 14708855 A EP14708855 A EP 14708855A EP 2970711 A1 EP2970711 A1 EP 2970711A1
Authority
EP
European Patent Office
Prior art keywords
adhesives
formula
diol
polyester
groups
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Withdrawn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
EP14708855.3A
Other languages
German (de)
English (en)
Inventor
Christina DIEHL
Gabriele Brenner
Bernhard Schleimer
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa 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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2970711A1 publication Critical patent/EP2970711A1/fr
Withdrawn legal-status Critical Current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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6926—Dicarboxylic acids and dihydroxy 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
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • 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
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • 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
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to the use of inherent flame retardant polyesters as or in adhesives, sealants and coatings, inherent flame retardant polyesters and methods for their preparation.
  • Hotmelt adhesives represent an important class of adhesives for many applications, for example in the automotive industry, furniture manufacturing or textile bonding. They are solid at room temperature and are melted by heating and applied to the substrate at elevated temperature. Upon cooling, they solidify again, thus ensuring a firm bond.
  • Hotmelt adhesives are reactive hotmelt adhesives that additionally crosslink after application and thereby cure irreversibly. These include, for example, moisture-curing hot melt adhesives, which crosslink by reaction with atmospheric moisture.
  • flame retardants are usually used as the formulation component.
  • mineral substances for example aluminum hydroxide or antimony oxide
  • organic flame retardants such as halogen-containing, and due to the lower toxicity increasingly phosphorus-containing substances are used.
  • the application EP 1975217 describes flame-retardant adhesive and sealants which contain a mono- or diphosphinic acid salt as flame retardant.
  • a flame retardant generally has a detrimental effect on the adhesion properties of an adhesive formulation. Overall, the bonding is thus significantly weakened by the use of an additive flame retardant.
  • Object of the present invention is to provide an alternative solution for introducing a flame retardant in adhesives or sealants, not to a Deterioration of the adhesive or sealing properties leads.
  • This object is achieved by the use of flame-retardant polyester as or in adhesives, sealants and coatings.
  • a first object of the present invention is the use of polyesters based on di- or polycarboxylic acids and di- or polyols as adhesives or sealants or as an ingredient in adhesives, sealants and
  • R (l) wherein R is a saturated linear or branched alkyl radical having 1 to 10 carbon atoms and A and B may be identical or different and are selected from saturated linear or branched alkylene groups having 1 to 10 carbon atoms or from mono - or polyalkylene glycol groups.
  • R is a saturated linear or branched alkyl radical having 1 to 10 C atoms, in particular having 1 to 3 C atoms.
  • Examples of preferred alkyl radicals are methyl and ethyl groups.
  • a and B can be identical or different and can be selected from saturated linear or branched alkylene groups having 1 to 10 carbon atoms or from mono- or polyalkylene glycol groups.
  • alkylene groups are alkylene groups having 1 to 10 carbon atoms, preferably having 1 to 3 carbon atoms. Examples more preferred
  • Alkylene groups are ethylene and propylene groups.
  • mono- or polyalkylene glycol groups these are preferably selected from ethylene glycol groups of the general formula -CH 2 -CH 2 (-O-CH 2 -CH 2 ) n- or Propylene glycol groups of the formula -CH 2 -CH (CH 3 ) (- O-CH 2 -CH (CH 3 )) n- with n an integer between 1 and 10.
  • polyesters may be amorphous, liquid or (partially) crystalline at room temperature.
  • Suitable di- or polycarboxylic acids and their derivatives are both aromatic compounds such as dimethyl terephthalate, terephthalic acid,
  • Examples are cyclic and linear aliphatic dicarboxylic acids such as
  • Cyclohexanedicarboxylic acid hexahydrophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, 1, 12-dodecanedicarboxylic acid and
  • the polyester contains adipic acid and sebacic acid.
  • the diols or polyols contained in the polyesters used according to the invention may contain, in addition to the diol of the formula (I), further diols or polyols.
  • the diols or polyols may be aliphatic or cycloaliphatic diols, such as 1, 2-ethanediol, 1, 3-propanediol, 1, 2-propanediol,
  • it may be oligomeric diols such as oligoethylene glycol,
  • Oligopropylene glycol and other oligoether act.
  • polyols with more than two functional groups such as
  • Trimethylolpropane pentaerythrol or glycerol can be used.
  • lactones and hydroxycarboxylic acids can be used as mono-, di- or polyols.
  • diol of the formula (I) preference is given to containing no further diols or polyols with ether groups, for example oligoethylene glycol, oligopropylene glycol and other oligoethers in the polyester used according to the invention.
  • a particularly preferred polyester consists of adipic acid, hexanediol-1, 6,
  • the proportion of the diol of the formula (I) in the polyester is arbitrary. However, there usually exists an optimum level at which the phosphorus content is sufficiently high for a flame retardant effect in the adhesive or sealant, but at the same time, the physical properties of the polyester are not excessively affected.
  • the phosphorus content of the polyester is therefore preferably 100 to 20,000 ppm, most preferably 5,000 to 15,000 ppm. This corresponds to a proportion of the diol of the formula (I) of from 0.1 to 15 mol%, particularly preferably from 4 to 12 mol%, based on the sum of the diols or polyols of the polyester used according to the invention.
  • the synthesis of the polyester is preferably carried out via a melt condensation.
  • the polycondensation takes place in the melt at temperatures between 150 and 280 ° C within 3 to 30 h.
  • a large part of the released amount of water is at
  • Distilled off normal pressure In the course of the remaining reaction water and volatile diols is split off until the desired molecular weight is reached. Optionally, this can be facilitated by reduced pressure, enlargement of the surface or by passing an inert gas stream.
  • the reaction may additionally be accelerated by adding an entraining agent and / or a catalyst before or during the reaction.
  • Suitable entrainers are, for example, toluene and xylenes.
  • Typical catalysts are organotitanium or tin compounds such as tetrabutyl titanate or dibutyltin oxide. Also conceivable are catalysts which are based on other metals such. As zinc or antimony based and metal-free esterification catalysts.
  • Other additives and driving aids such as antioxidants or color stabilizers possible.
  • polyesters used according to the invention have hydroxyl and / or
  • Carboxyl end groups preferably the functionality is between 1, 0 and 3.0.
  • the concentration of hydroxyl end groups is between 0 and 200, preferably between 5 and 50 mg KOH / g.
  • concentration of acid end groups determined according to DIN EN ISO 21 14, is between 0 and 50 mg KOH / g, but preferably below 2 mg KOH / g.
  • the number-average molecular weight of the polyester used according to the invention is 500-30,000 g / mol, preferably 1,000-20,000 g / mol. It is determined according to DIN 55672-1 by means of gel permeation chromatography in tetrahydrofuran as eluent and polystyrene for calibration.
  • the glass transition temperature of the polyesters of the invention is in the range of -80 ° C to 100 ° C, preferably between -50 ° C and + 50 ° C. In addition, one or more melting and recrystallization points may occur.
  • the determination of the thermal properties is carried out according to the DSC method according to DIN 53765.
  • polyesters containing diols of the formula (I) a flame retardant is introduced into the adhesives and sealants, without the properties of the adhesive bonds or the sealing properties are impaired.
  • the polyester used according to the invention contains a phosphorus-containing comonomer, which acts as an inherent flame retardant, so that the subsequent addition of the adhesives or sealants with
  • Flame retardants can be omitted. As a reactive instead of an additive
  • resulting adhesive formulation is not adversely affected compared to a non-flame retardant formulation.
  • the covalent linkage of the flame retardant within the polyester also ensures that they are homogeneously distributed in the adhesives or sealants and can not migrate, that is can not be washed out. Thus, a long-lasting Flame protection ensured.
  • the use according to the invention may be any kind of adhesives known to the person skilled in the art with regard to the adhesives.
  • the adhesives are hot-melt adhesives.
  • the hot melt adhesives are thermoplastic hot melt adhesives that cure purely physically.
  • thermoplastic hot melt adhesives When used in thermoplastic hot melt adhesives that is
  • number average molecular weight in particular 10,000 - 30,000 g / mol, preferably 10,000 - 20,000 g / mol.
  • the proportion of the diol of the formula (I) in these cases is preferably 4 to 12 mol%, based on the sum of the diols or polyols of the polyester used according to the invention and mixtures thereof. These amounts of the diol of formula (I) are already sufficient to provide effective flame retardancy
  • the hot melt adhesives are reactive hotmelts (RHM), which additionally crosslink chemically, with moisture-curing hotmelt adhesives being particularly preferred.
  • RHM reactive hotmelts
  • the numbers are medium
  • Molecular weight of the polyester used according to the invention preferably 500 -
  • the proportion of the diol of the formula (I) is arbitrary and is preferably 4 to
  • Formulating ingredients the amount of the diol of formula (I) is sufficient to ensure effective flame retardancy.
  • a preferred example of reactive hot melt adhesives are moisture-curing Melt adhesives. As a rule, these are reaction products of the polyesters used according to the invention with an excess of polyisocyanates which after application with moisture, for. As humidity, react and lead to additional networking.
  • the adhesives can be produced in a simple manner. If, according to one of the preferred embodiments, further components are used with the polyester used according to the invention, the adhesive is produced in the simplest case by mixing the mixture and the additional components.
  • the mixing can be carried out with or without solvent, preferably without solvent and most preferably in the melt.
  • the mixing can be carried out, for example, in a stirred tank, a kneader or an extruder.
  • the melting temperature depends on the viscosity of the constituents. It is usually in a range of 80 to 180 ° C.
  • the moisture-curing hot melt adhesives described above can be prepared at temperatures between 50 and 130 ° C depending on the viscosity of the respective formulation. In a several hours tempering of the
  • Adhesive for further processing is recommended a storage temperature of ⁇ 100 ° C, since at higher temperatures as side reaction, the formation of carbodiimides occurs. This leads to a significant increase in viscosity and a strong foaming of the formulation.
  • the moisture-crosslinking hot melt adhesives additionally contain isocyanates and / or polyisocyanates.
  • the OH: NCO ratio of polyester to isocyanate and / or polyisocyanate is generally 1: 1, 2 to 1: 3, preferably 1: 1, 5 to 1: 2.5.
  • the polyisocyanates may be difunctional and / or multifunctional, aromatic, aliphatic or / and cycloaliphatic isocyanates and carbodiimide-modified isocyanates or isocyanate-terminated prepolymers.
  • Aromatic polyisocyanates are particularly preferred.
  • Examples of polyisocyanates are 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, toluene diisocyanate isomers, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and mixtures thereof.
  • it is 4,4'-diphenylmethane diisocyanate and Mixtures of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate.
  • the moisture-crosslinking hotmelt adhesives additionally comprise organosilanes in addition to or instead of the polyisocyanates.
  • the functionalization of the polyesters used according to the invention can be carried out by a stepwise reaction with polyisocyanates to isocyanate-terminated prepolymers and subsequent reaction with organosilanes or by reaction with an adduct of polyisocyanates and organosilanes.
  • the reaction of the polyesters with an isocyanatoalkylsilane takes place in an OH / NCO ratio of 1: 1 to 1: 1, 5.
  • organosilanes are aminopropyltrimethoxysilane,
  • Aminopropyltriethoxysilane N-methyl-aminopropyltrimethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, N-phenyl-aminopropyltrimethoxysilane
  • the proportion of the polyesters used according to the invention is 1-99% by weight, and preferably 5-85% by weight.
  • polyesters used according to the invention in addition to the polyesters used according to the invention, other polyols are present in the reactive hotmelt adhesives, such as polyesterpolyols, polyetherpolyols and any desired hydroxyl-functional components.
  • the admixed polyester polyols may be liquid or solid, amorphous or (partly) crystalline polyesters of any structure having number average molecular weights (M n ) between 1000 g / mol and 30 000 g / mol, preferably between 2000 g / mol and 10000 g / mol (calculated from the hydroxyl number), with linear polyester polyols being preferably used.
  • the admixed polyether polyols are polyether di- and triols. Examples include homopolymers and copolymers of ethylene glycol, propylene glycol and 1,4-butanediol.
  • the number-average molecular weight (M n ) of the mixed polyether polyols should be in a range of 200 g / mol to 10,000 g / mol, preferably, between 400 g / mol and 6000 g / mol.
  • Examples of any hydroxy-functional components are functionalized (H acide), thermoplastic polyurethanes (TPU) and / or polyacrylates and / or ethylene-vinyl acetate copolymers (EVA).
  • hot melt adhesives may contain other additives.
  • additives may be: non-functionalized polymers, e.g. B. thermoplastic
  • TPU Polyurethanes
  • EVA ethylene-vinyl acetate copolymers
  • Pigments or fillers eg. Talc, silica, titania,
  • Tackifier like.
  • rosin resins for example, rosin resins, hydrocarbon resins, phenolic resins, hydrolysis stabilizers and anti-aging and auxiliary agents
  • Adhesives, sealants and coatings comprising polyesters based on di- or polycarboxylic acids and diols or polyols, where the polyesters comprise at least one diol of the formula (I)
  • R is a saturated linear or branched alkyl radical having 1 to 10 carbon atoms and A and B may be identical or different and are selected from saturated linear or branched alkylene groups having 1 10 C atoms or from mono- or polyalkylene glycol groups also
  • the adhesives of the invention are particularly suitable for the production of bonds.
  • the hot melt adhesives of the invention are suitable for bonding a variety of substrates, in particular for bonding metallic substrates, wood, textiles and very particularly for bonding various plastics.
  • the type and extent of the bond are not limited.
  • the bonds are preferably adhesions in the wood and furniture industry (for example Montageverklebung as well as the lamination and lamination of decorative films of fiberboard, production of sandwich composites for the production of lightweight panels), in the automotive sector (for example
  • Retainerverklebitch as well as the lamination and lamination of films and textiles on door side parts and headliner, the seat manufacturing), in the
  • a further subject of the present invention are polyesters based on dicarboxylic polycarboxylic acids and diols or polyols which do not contain an ether group, characterized in that the polyesters contain at least one diol of the formula (I)
  • R (l) wherein R is a saturated linear or branched alkyl radical having 1 to 10 carbon atoms and A and B may be identical or different and are selected from saturated linear or branched alkylene groups having 1 to 10 carbon atoms or from mono - or polyalkylene glycol groups. It is essential that, in addition to the diol of the formula (I), no further diols or polyols having ether groups are contained in the polyester according to the invention.
  • R is a saturated linear or branched alkyl radical having 1 to 10 C atoms, in particular having 1 to 3 C atoms.
  • Examples of preferred alkyl radicals are methyl and ethyl groups.
  • a and B can be identical or different and can be selected from saturated linear or branched alkylene groups having 1 to 10 carbon atoms or from mono- or polyalkylene glycol groups.
  • alkylene groups are alkylene groups having 1 to 10
  • Alkylene groups ethylene and propylene groups.
  • these are preferably selected from ethylene glycol groups of the general formula -CH 2 -CH 2 (-O-CH 2 -CH 2 ) n or propylene glycol groups of the formula -CH 2 -CH (CH 3) (- O-CH 2 -CH ( CH 3 )) n- with n an integer between 1 and 4.
  • ethylene glycol groups of the general formula -CH 2 -CH 2 (-O-CH 2 -CH 2 ) n or propylene glycol groups of the formula -CH 2 -CH (CH 3) (- O-CH 2 -CH ( CH 3 )) n- with n an integer between 1 and 4.
  • polyesters according to the invention in addition to the diol of the formula (I), further mono-, di- or polyols may be present. Suitable are all aliphatic or cycloaliphatic diols which contain no ether group. However, unsuitable are ether-group-containing aliphatic or cycloaliphatic diols. These include, for example, diethylene glycol, dipropylene glycol, triethylene glycol and oligomeric diols, especially oligoethylene glycol, oligopropylene glycol and other oligoethers. These diols show in the presence of a diol of the formula (I) over the non-ether-containing diols a prolonged reaction time during the
  • Diethylene glycol especially in the presence of phosphorus-containing compounds for cyclization to the highly volatile dioxane.
  • non-ether group-containing aliphatic diols are suitable. These include, for example, 1, 2-ethanediol, 1, 3-propanediol, 1, 2-propanediol,
  • polyols with more than two functional groups such as
  • Trimethylolpropane, pentaerythrol or glycerol can be used.
  • lactones and hydroxycarboxylic acids can be used as mono-, di- or polyols.
  • Suitable di- or polycarboxylic acids and derivatives thereof are aromatic compounds such as dimethyl terephthalate, terephthalic acid,
  • Examples are cyclic and linear aliphatic dicarboxylic acids such as
  • Cyclohexanedicarboxylic acid hexahydrophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, 1, 12-dodecanedicarboxylic acid and
  • aliphatic dicarboxylic acids such as adipic acid and / or sebacic acid are used as di- or polycarboxylic acids.
  • a particularly preferred polyester consists of adipic acid, hexanediol-1, 6, neopentyl glycol and the diol of the formula (I).
  • the application DE 2646218 also describes phosphorus-containing polyesters.
  • the phosphorus-containing diol is based on 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOP), which reacts with aromatic dicarboxylic acids and other diols
  • DOP 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide
  • the good compatibility of the reactive flame retardant with the polyester is based on the chemically similar structure of the biphenyl derivative DOP with aromatic dicarboxylic acids.
  • the present invention relates to polyesters which are preferred in
  • Hot melt adhesives are used.
  • the physical properties of the polyesters are of great importance.
  • the desired polyester properties such as low viscosities, high crystallinities or high UV stability, often can not be adjusted.
  • DOP-based reactive flame retardants relates to use in reactive hot melt adhesives. These are melted by the reaction of hydroxyl-terminated polyesters with polyisocyanates
  • Phosphonates such as the diol of formula (I).
  • Another advantage of the phosphorus-containing diol according to formula (I) is that, compared with the already known DOP-based diol, a significantly reduced phosphorus content is sufficient to achieve adequate flame retardancy in the adhesive or sealant.
  • Ether-group-containing diols They are therefore soluble in water and thus for the
  • Water-soluble means that 20 percent and neutralized with NaOH aqueous solutions of the described polyester have no turbidity.
  • polyesters according to the invention are not soluble in water, since apart from the diol of the formula (I), no further ether-containing diols are used. This makes them more suitable for use in hot melt adhesives.
  • polyesters according to the invention overcome the above-mentioned disadvantages of the prior art and are therefore particularly suitable as or in adhesives, in particular in hotmelt adhesives, with reactive hotmelt adhesives being particularly preferred. Even without further statements, it is assumed that a person skilled in the art can use the above description to the greatest extent.
  • the preferred ones are therefore particularly suitable as or in adhesives, in particular in hotmelt adhesives, with reactive hotmelt adhesives being particularly preferred.
  • Titanium catalyst added and the pressure in the apparatus gradually reduced to 10 mbar. After reaching the desired hydroxyl and acid number range, the reaction is complete.
  • the polyester P1 has a hydroxyl value of 40 mg KOH / g, measured according to DIN 53240-2 and an acid number of 1 mg KOH / g, measured according to DIN EN ISO 21 14, on.
  • the incorporation of the reactive flame retardant in the polyester chain can be detected by 31 P phosphor NMR.
  • the signal at 33 ppm breaks down due to the covalent bond to the polyester and is slightly upfield shifted.
  • the polyester P2 has a hydroxyl number of 40 mg KOH / g, measured according to DIN 53240-2 and an acid number of 1 mg KOH / g, measured according to DIN EN ISO 21 14, on.
  • polyester P1 250 g of the polyester P1 are melted in a 500 ml flat-bottomed flask and dried at 130 ° C. under reduced pressure. Thereafter, 49 g of 4,4'-diphenylmethane diisocyanate (MDI), which corresponds to an OH / NCO ratio of 1 / 2.2, was added and rapidly homogenized. For complete reaction of the reactants is stirred for 45 minutes at 130 ° C under a protective gas atmosphere. Subsequently, the moisture-curing hot melt adhesive is filled.
  • MDI 4,4'-diphenylmethane diisocyanate
  • polyester P1 250 g are melted in a 500 ml flat-bottomed flask.
  • the flame retardant properties are determined according to the test standard UL 94 on test bars from a cured 0.5-1 mm thick RHM film. The curing took place within seven days at 20 ° C and 65% relative humidity in a climatic chamber. Results:
  • RHM 1 has no flame retardancy.
  • RHM 2 and RHM 3 are the least flammable and have the highest
  • the determination of the adhesive properties on various substrates was carried out according to the method DIN EN 1465 after a curing time of seven days at 20 ° C and 65% relative humidity.
  • the percentage mass loss after extraction of the cured reactive hot melt adhesive in boiling acetone was determined after eleven hours.
  • RHM1 has a mass loss of 1 1%, RHM 2 of 22% and RHM 3 of 13%.
  • polyesters with inherent flame retardancy in hot melt adhesives ensures adequate flame retardance as well as adhesive properties comparable with conventional, flameproof formulations.
  • Flame retardant is covalently bound to the polyester chains and can not migrate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Sealing Material Composition (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation de polyesters ignifuges de manière inhérente comme ou dans des adhésifs, des agents d'étanchéité et des revêtements, ainsi que des polyesters ignifuges de manière inhérente et des procédés de préparation correspondants.
EP14708855.3A 2013-03-15 2014-03-06 Utilisation de polyesters ignifuges de manière inhérente dans des adhésifs et des agents d'étanchéité Withdrawn EP2970711A1 (fr)

Applications Claiming Priority (2)

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DE102013204550.6A DE102013204550A1 (de) 2013-03-15 2013-03-15 Verwendung von Polyestern mit inhärentem Flammschutz in Kleb- und Dichtstoffen
PCT/EP2014/054361 WO2014139858A1 (fr) 2013-03-15 2014-03-06 Utilisation de polyesters ignifuges de manière inhérente dans des adhésifs et des agents d'étanchéité

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EP2970711A1 true EP2970711A1 (fr) 2016-01-20

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EP (1) EP2970711A1 (fr)
JP (1) JP2016518466A (fr)
KR (1) KR20150132290A (fr)
CN (1) CN105102557B (fr)
BR (1) BR112015022139A2 (fr)
DE (1) DE102013204550A1 (fr)
MY (1) MY172773A (fr)
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MY181850A (en) 2015-02-05 2021-01-11 Evonik Operations Gmbh Isocyanate-free synthesis of carbonate-modified polymers
US10435602B2 (en) 2015-03-02 2019-10-08 Evonik Degussa Gmbh Adhesives with low VOC and fogging values
US10246617B2 (en) 2015-03-02 2019-04-02 Evonik Degussa Gmbh Adhesives with low VOC and fogging values
EP3078723B1 (fr) * 2015-04-09 2018-10-31 Evonik Degussa GmbH Additifs à base d'isocyanatoalkyl-trimethoxysilanes et moyens ignifuges aptes à réagir à ceux-ci
US10336925B2 (en) * 2015-09-08 2019-07-02 Resinate Materials Group, Inc. Polyester polyols for reactive hot-melt adhesives
EP3243863A1 (fr) 2016-05-09 2017-11-15 Evonik Degussa GmbH Utilisation de copolymeres sequences dans des colles
CN111615529A (zh) 2018-01-16 2020-09-01 赢创运营有限公司 含纳米颗粒的组合物
WO2019241473A1 (fr) * 2018-06-14 2019-12-19 H.B. Fuller Company Adhésif thermofusible ininflammable
EP3636687A1 (fr) 2018-10-12 2020-04-15 Evonik Operations GmbH Adhésifs réactifs thermiquement solubles
CN111518266B (zh) * 2020-06-16 2022-04-12 万华化学集团股份有限公司 一种聚酯多元醇及其制备方法和应用
KR102383278B1 (ko) * 2020-12-04 2022-04-06 주식회사 빅스 우수한 접착 특성과 내열성 및 세탁 후 내구성을 갖는 난연성 습기경화형 접착제의 제조방법 및 이를 이용한 섬유코팅 원단
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DE102013204550A1 (de) 2014-09-18
KR20150132290A (ko) 2015-11-25
MY172773A (en) 2019-12-12
WO2014139858A1 (fr) 2014-09-18
BR112015022139A2 (pt) 2017-07-18
CN105102557A (zh) 2015-11-25
US9840581B2 (en) 2017-12-12
CN105102557B (zh) 2017-08-25
JP2016518466A (ja) 2016-06-23

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