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
  • 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
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
  • C08G18/6423—Polyalkylene polyamines; polyethylenimines; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C279/00—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
  • C07C279/04—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton
  • C07C279/12—Derivatives of guanidine, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of guanidine groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso 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
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular 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
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
  • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0206—Polyalkylene(poly)amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • 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
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible

Definitions

• Guanidinruppen containing compounds and their use as additives in the production of polyurethane systems are provided.
• the invention relates to aminofunctional polymer compounds having guanidine groups, their preparation and their use for the preparation of polyurethane systems and polyurethane systems prepared accordingly.
• Polyurethane systems are z. Polyurethane coatings, polyurethane adhesives, polyurethane sealants, polyurethane elastomers or polyurethane foams / foams.
• Polyurethane foams are used in a wide variety of applications due to their excellent mechanical and physical properties.
• a particularly important market for various types of polyurethane foams such as conventional ether and ester polyol based flexible foams, cold foams (often referred to as HR foams), rigid foams, integral foams and microcellular foams, as well as foams whose properties lie between these classifications, such as , B. semi-rigid systems, represents the automotive and furniture industry.
• the formaldehyde should originate from the raw materials and should be present in particular in the amine catalysts (tertiary amines) used.
• this document proposes to add a primary amine to the tertiary Armin catalyst.
• This primary amine may, for. B. also be a guanidine.
• US Pat. No. 6,040,315A describes the preparation of guanidine group-containing copolymers by copolymerization of amino-functional polymers and guanidine carbonate, the reaction being carried out with a guanidine carbonate to give amino-functional polymers of greater than 5: 4.
• the copolymers are described as gastric acid deacidifying agents.
• EP 0915083 A2 describes the preparation of substituted guanidine derivatives which, for. B. as sterically hindered bases, biocides and complex ligands are known in which an alkylated isourea is reacted with a primary or secondary amine.
• biocides and complex ligands are known in which an alkylated isourea is reacted with a primary or secondary amine.
• the object of the present invention was therefore to provide an additive which prevents the emission of formaldehyde over a relatively long period of time or to which it reduces the abovementioned limits to a limited extent.
• amino-functional polymer compounds of the below-mentioned formula (Ia), in particular guanidine-containing amino-functional polymer compounds of the formula (I) below achieve this object.
• the present invention therefore relates to compounds of the formula (I) as defined below and in claim 1.
• the compounds of the formula (I) according to the invention have the advantage that, when used as an additive in polyurethane foam production, the emission of formaldehyde is also determined after storage for 3 months to a value of 0.02 mg formaldehyde / kg PU foam according to VDA 275 limit.
• the indices given may be both absolute numbers and averages, and for polymeric compounds, the indices are preferably average values.
• the compound according to the invention is characterized in that it has the formula (I)
• R 1 2 N-CH 2 - preferably H 2 N-CH 2 -
• R 1b R 1 or -C (NR 4 2 ) (NR 4 ), preferably R 1 ,
• R 2 identical or different alkyl or aryl radical having 1 to 24 carbon atoms, preferably methyl,
• c 0 or 1, preferably 0
• x 0 to 300, preferably 1 to 90, in particular> 2 to 30,
• x ' 2 to 150, preferably 2 to 50, in particular 2 to 25,
• y 0 to 300, preferably 1 to 90, in particular 2 to 30,
• y ' 0 to 300, preferably 0.5 to 90, in particular 1 to 30,
• x + x '+ y is greater than or equal to 3, preferably greater than or equal to 5,
• R 4 is identical or different alkyl or aryl radical, preferably having 3 to 10 carbon atoms, preferably alkyl radicals having 3 to 6 carbon atoms, particularly preferably cyclohexyl or isopropyl radicals, or H, preferably cyclohexyl or isopropyl radicals or H, particularly preferably cyclohexyl or isopropyl radicals,
• a 0 to 3, preferably 1 or 2
• b 0 to 3, preferably 0 or 1
• a + b is greater than or equal to 1.
• x + x '+ y + y' is greater than or equal to 3.
• y ' is greater than or equal to 5.
• the compounds of the formula (I) preferably have a molecular weight Mn of 400 to 25,000 g / mol.
• Particularly preferred compounds of the formula (I) are those in which all the radicals R are either cyclohexyl or isopropyl radicals or H.
• the compounds of formula (I) according to the invention are e.g. thereby obtainable or can be obtained by reacting a compound of the formula (III)
• Compounds of formula (IV) is at least 1 to 2, preferably 1 to 2 to 1 to 20, preferably 1 to 5 to 1 to 10. Accordingly, the process according to the invention for the preparation of compounds of the formula (I) is characterized in that a compound of the formula (III)
• RaXxY y (IN) with R, X, Y, Y, a, x, y and y 'as defined for formula (I) and the proviso that x + y is greater than or equal to 3, preferably greater than or equal to 5, with a compound of the formula (IV)
• Compounds of formula (IV) is at least 1 to 2, preferably 1 to 2 to 1 to 20, preferably 1 to 5 to 1 to 10.
• XR 1 2 N-CH 2 - preferably H 2N-CH 2 -,
• Y is -CH 2 -NR-CH 2 -, preferably -CH NH-CH
• R 1b R 1 or C (NR 4 2 ) (NR 4 ), preferably R 1 ,
• R 2 identical or different alkyl or aryl radical having 1 to 24 carbon atoms, preferably methyl,
• c 0 or 1, preferably 0
• x 0 to 300, preferably 1 to 90, in particular> 2 to 30
• x ' 0 to 150, preferably 0 to 50, in particular 2 to 25,
• y 0 to 300, preferably 1 to 90, in particular 2 to 30,
• y ' 0 to 300, preferably 0.5 to 90, in particular 1 to 30,
• x + x '+ y is greater than or equal to 3, preferably greater than or equal to 5,
• R 4 is identical or different alkyl or aryl radical, preferably having 3 to 10 carbon atoms, preferably alkyl radicals having 3 to 6 carbon atoms, particularly preferably cyclohexyl or isopropyl radicals, or H, preferably cyclohexyl or isopropyl radicals or H, particularly preferably cyclohexyl or isopropyl radicals,
• a 0 to 3, preferably 1 or 2
• b 0 to 3, preferably 0 or 1
• a + b is greater than or equal to 1
• the compound of the formula (Ia) used is preferably a compound of the formula (I) as described above.
• the compounds of formula (Ia) are preferably a reaction mixture containing one or more organic isocyanates having two or more Isocyanate functions, one or more polyols having two or more isocyanate-reactive groups, catalysts for the reactions isocyanate-polyol and / or isocyanate-water and / or the isocyanate trimerization, water, optionally physical blowing agents, optionally flame retardants and optionally further Additive added.
• the amount of compounds of the formula (Ia) added to the reaction mixture is from 0.1 to 10 parts by mass of compounds of the formula (Ia) per 100 parts by mass of polyols.
• the preparation of the polyurethane system, in particular of the polyurethane foam, in which one or more compounds of the formula (Ia) is used according to the invention can be carried out in a manner known to the person skilled in the art. A basic overview can be found z. In G. Oertel, Polyurethane Handbook, 2nd edition, Hanser / Gardner Publications Inc., Cincinnati, Ohio, 1994, p. 177-247.
• isocyanate component all isocyanates, in particular the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se, may be present in the reaction mixture.
• Suitable isocyanates in the sense of this invention are preferably all polyfunctional organic isocyanates, such as 4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI).
• MDI 4,4'-diphenylmethane diisocyanate
• TDI toluene diisocyanate
• HMDI hexamethylene diisocyanate
• IPDI isophorone diisocyanate
• Particularly suitable is the mixture known as "polymeric MDI"("crudeMDI") of MDI and higher condensed analogues having an average functionality of 2 to 4, and the various isomers of TDI in pure form or as a mixture of isomers.
• Particularly preferred isocyanates are mixtures of TDI and MDI.
• Suitable polyols for the purposes of this invention are preferably all organic substances having a plurality of isocyanate-reactive groups, as well as their preparations.
• Preferred polyols are all polyether polyols and polyester polyols customarily used for the preparation of polyurethane systems, in particular polyurethane foams.
• the polyols are preferably not compounds having at least one 5- or 6-membered ring composed of one or two oxygen atoms and carbon atoms.
• Polyether polyols are obtained by reacting polyhydric alcohols or amines with alkylene oxides.
• Polyester polyols are based on esters of polybasic carboxylic acids (which may be either aliphatic, for example adipic acid, or aromatic, for example phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols).
• natural oils based on natural oils natural oil based polyols, NOPs
• These polyols are derived from natural oils such as soy or palm oil and can be used unmodified or modified.
• a suitable ratio of isocyanate to polyol is in the range of 10 to 1000, preferably 40 to 350. This index describes the ratio of actually used isocyanate to isocyanate (calculated for a stoichiometric reaction with polyol). An index of 100 indicates a molar ratio of the reactive groups of 1 to 1.
• Suitable further catalysts which may additionally be present in the additive composition according to the invention are substances which catalyze the gel reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) or the di- or trimerization of the isocyanate.
• Typical examples are amines, e.g.
• Triethylamine dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1, 2-dimethylimidazole, N-ethylmorpholine, tris (dimethylaminopropyl) hexahydro-1,3,5-triazine, dimethylaminoethanol, dimethylaminoethoxyethanol and bis (dimethylaminoethyl) ether, Tin compounds such as dibutyltin dilaurate and potassium salts such as potassium acetate.
• Suitable water contents in the additive compositions according to the invention depend on whether or not physical blowing agents are used in addition to the water. In the case of pure water-driven foams, the values are typically from 1 to 20 pphp, if other blowing agents are additionally used, the amount of use is reduced to usually 0 or 0.1 to 5 pphp. To obtain high foam chamber weights, neither water nor other blowing agents are used.
• Suitable physical blowing agents for the purposes of this invention are gases, for example liquefied C0 2 , and volatile liquids, for example hydrocarbons having 4 or 5 carbon atoms, preferably cyclo, iso and n-pentane, hydrofluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141b, oxygen-containing compounds such as methyl formate and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1, 2-dichloroethane.
• ketones eg acetone
• aldehydes eg methylal
• Suitable flame retardants in the context of this invention are preferably liquid organic phosphorus compounds, such as halogen-free organic phosphates, e.g. Triethyl phosphate (TEP), halogenated phosphates, e.g. Tris (1-chloro-2-propyl) phosphate (TCPP) and tris (2-chloroethyl) phosphate (TCEP) and organic phosphonates, e.g. Dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus.
• halogenated compounds for example halogenated polyols, and solids such as expanded graphite and melamine are suitable as flame retardants.
• polyurethane systems are used.
• polyurethane is used here as a generic term for a diisocyanate or polyisocyanates and polyols or other isocyanate-reactive species, such as. Amines to understand produced polymer, wherein the urethane bond does not have to be exclusive or predominant type of bond. Also, polyisocyanurates and polyureas are expressly included.
• the use of the compounds of the formula (Ia), preferably of the compounds of the formula (I) according to the invention for the preparation of polyurethane systems, in particular polyurethane foams or the preparation of the polyurethane systems / polyurethane foams can be carried out by all methods familiar to the skilled worker, for example by hand mixing or preferably with the aid of from High pressure or low pressure foaming machines.
• the process according to the invention can be carried out continuously or batchwise. A discontinuous implementation of the method is preferred in the production of molded foams, refrigerators or panels. Continuous process control is preferred in the manufacture of insulation boards, metal composite elements, blocks or spraying processes.
• the compounds according to the invention are preferably mixed together directly before or else only during the reaction (to form the urethane bonds).
• the combination / addition of the compound takes place in a mixing head.
• the polyurethane systems according to the invention are characterized in that they contain from 0.05 to 10% by mass, preferably from 0.1 to 5% by mass, based on the total composition of the polyurethane system, of compounds of the formula (Ia), preferably compounds of the formula (I ) exhibit.
• the polyurethane systems of the invention may preferably z.
• a rigid polyurethane foam a flexible polyurethane foam, a viscoelastic foam, an HR foam, a semi-rigid polyurethane foam, a thermoformable ble polyurethane foam or an integral foam, preferably a polyurethane HR foam.
• the polyurethane systems of the invention preferably polyurethane foams, z.
• refrigerator insulation insulation board, sandwich element, pipe insulation, spray foam, 1- & 1, 5-component foam foam, imitation wood, model foam, packaging foam, mattress, furniture upholstery, automotive seat cushion, headrest, instrument panel, automotive
• N, N-dicyclohexylcarbodiimides (order number D80002) and two aqueous solutions of amino-functional polymers of general formula 1 (amino-functional polymer A (order number: 482595) and amino-functional polymer B (order number 408700) Both amino-functional polymers were dried by distillation so far that the water content was ⁇ 1% by mass.
• Guanidine carbonate (CAS: 593-85-1) was purchased from Sigma-Aldrich (order number G1 1659) and used as received.
• Table 1 Raw materials for the production of foam moldings Polyetherol trifunctional, MW 6000, Bayer MaterialScience
• Tegoamine DEOA 85 (diethanolamine 85% in water)
• the amounts of additive used were chosen so that the sum of the amounts of primary amine, secondary amine and guanidine functions in the test formulation was constant.
• the amine number based on the sum of primary amine, secondary amine and guanidine functionalities of the additive was estimated on the basis of the available structural information (Table 2).
• the foaming was carried out by hand mixing.
• polyol, crosslinker, catalyst, additive, water and silicone stabilizer were weighed into a beaker and premixed with a paddle stirrer for 60 s at 1000 rpm. Subsequently, the isocyanate was added and stirred at a stirrer speed of 2500 rpm 7s.
• the reaction mixture was sealed in a box mold heated to 57 ° C. (dimensions 40 ⁇ 40 ⁇ 10 cm). The finished foam was removed from the mold after 3.5 minutes.
• the amounts used and reactants can be found in Table 3.
• VDA 275 "Moldings for the vehicle interior - determination of formaldehyde release.” Measuring method according to the modified bottle method; Source: VDA 275, 07/1994, www.vda .de) analyzed for their formaldehyde content, which is explained below. measuring principle
• specimens of a given mass and dimension were fixed over distilled water in a closed 11-glass bottle and stored at a constant temperature for a defined time. Thereafter, the bottles were cooled and determined in distilled water, the absorbed formaldehyde. The determined amount of formaldehyde was based on dry molding weight (mg / kg).
• the foams After demolding the foams, they were stored for 24 hours at 21 ° C and about 50% relative humidity. Test specimens were then uniformly distributed across the width of the (cooled) molding at appropriate and representative locations. Thereafter, the foams were wrapped in an aluminum foil and sealed in a polyethylene bag.
• the size of the specimens was 100x40x40mm thickness (about 9g). Per specimen 3 specimens were removed for the determination of formaldehyde.
• the samples were weighed to the nearest 0,001g before analysis on the analytical balance.
• 50 ml of distilled water were pipetted into each of the glass bottles used. After attaching the specimens in the glass bottle, the vessel was closed and kept for 3 hours in a warming cabinet at a constant temperature of 60 ° C. After the test period, the vessels were removed from the oven. After 60 minutes of service life at room temperature, the test specimens were removed from the test bottle. Subsequently, the derivatization was carried out according to the DNPH method (dinitrophenylhydrazine). To 900 ⁇ of the water phase with 100 ⁇ of a DNPH solution are added. The DNPH solution is prepared as follows: 50mg DNPH in 40mL MeCN (acetonitrile) is acidified with 250 ⁇ HCl (1:10 dil) and made up to 50mL with MeCN. Device parameters HPLC
• the foaming results show that PU foams having reduced formaldehyde emissions can be produced by adding the additives according to the invention.

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• 2012
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• 2013
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