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
  • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
  • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate 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
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1841—Catalysts containing secondary or tertiary amines or salts thereof having carbonyl groups which may be linked to one or more nitrogen or oxygen atoms
• • 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
  • C08G18/708—Isocyanates or isothiocyanates containing non-reactive high-molecular-weight 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
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C09D127/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/205—Compounds containing groups, e.g. carbamates
• • 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

Definitions

• the present invention relates to novel, low-monomer, low-viscosity solutions of diisocyanate-toluene-based isocyanato-isocyanurates in branched dialkyl phthalates as an ecologically acceptable plasticizer for polyvinyl chloride, a process for the preparation of these solutions and their use as additives for coating agents based on plasticizer-containing polyvinyl chloride.
• the homogeneity of the plastisol-polyisocyanate mixture is decisive for optimal coating results. Since polyisocyanates are generally very highly viscous or even solid, solvents are usually used to improve processability, which preferably also act as plasticizers in the PVC-based coating and can therefore also remain there (H. Kittel, “Textbook of paints and coatings "2nd ed. 1998, S. Hirzel Verlag Stuttgart, p. 342 ff.” Polyvinyl compounds ").
• plasticizers for PVC coatings are, for example, phthalic acid esters, adipic acid esters, phosphoric acid esters, sebacic acid esters, azelates or modified oils. Polyesters are also described as plasticizers ("Plasticizers", Kulkarni, K.B. in Popular Plastics (1966), 11 (6), 71-2).
• good adhesion i.e. good processability, i.e. low viscosity ( ⁇ 20,000 mPas at 23 ° C), low content of free diisocyanatotoluene (TDI) ( ⁇ 0.2% free TDI), as well as solvents that are not to be labeled as "toxic”.
• good adhesion properties are usually obtained when the adhesion promoters contain> 25% by weight solids .. A combination of all these product properties has not been described in the existing prior art.
• DE-A 24 19 016 describes polyisocyanates dissolved in plasticizers for PVC, such as high-boiling esters, including phthalic acid with 7-9 carbon atoms in the alcohol residue.
• Non-specific lists include, among others, tertiary amines as catalysts for isocyanurate formation. The However, the required combination of the product properties of viscosity, residual monomer content and solid content described above is not achieved by these systems.
• US-A 4 115 373 describes the trimerization of isocyanates such as i.a. Toluene diisocyanate in inert solvents with a wide boiling point range using Mannich bases as catalysts.
• the polyisocyanates thus produced have a free monomer content of ⁇ 0.7% by weight.
• Non-specific lists include as solvents: also called low molecular weight phthalic esters such as dibutyl phthalate and butyl benzyl phthalate.
• solvents also called low molecular weight phthalic esters such as dibutyl phthalate and butyl benzyl phthalate.
• DE-A 30 41 732 describes polyisocyanates which are based on 4,4'-diisocyanatodiphenylmethane and TDI.
• polyisocyanates based on TDI mixtures with isomer contents of approximately 35% by weight of 2.6 diisocyanatotoluene are also used.
• the products obtained do not meet the required product properties with regard to the solids content, the viscosity and the residual monomer content of TDI.
• Patent application DE 10 229 780 describes a process for the preparation of TDI-based polyisocyanates with residual monomer contents of ⁇ 0.2% by weight. However, the production of plasticizer-containing solutions with the required low viscosities and mechanical properties is not disclosed.
• polyisocyanate should be based on the industrially available isomer mixtures of 2,4- and 2,6-diisocyanatotoluene, preferably the so-called Desmodur ® T80 from Bayer AG Leverkusen, DE.
• the invention relates to a process for the preparation of TDI-based isocyanurate polyisocyanate solutions, in which A) in a solvent which contains at least one dialkyl phthalate with branched alkyl radicals
• the invention further relates to the TDI-based isocyanurate polyisocyanate solutions obtainable by the process according to the invention with a viscosity at 23 ° C. of ⁇ 20,000 mPas, a content of free non-trimerized TDI residual monomers of ⁇ 0.2% by weight and a solids content based on the contained isocyanurate polyisocyanate of> 25 wt .-%.
• Component A) preferably uses isomeric diisononyl phthalates as branched dialkyl phthalates, particularly preferably those with a boiling point at 1013 mbar of at least 250 ° C. which are liquid at room temperature.
• Diisononyl phthalate is usually understood to mean diesters of the formula (I)
• Formula (I) the branched alkyl chains (iso-C 9 H 19 ) are not defined in more detail.
• DUMP diisononyl phthalates
• Palatinol ® N BASF, Ludwigshafen DE
• Diplast ® NS Lico-Bassham
• Jayflex ® DI P phthalic diester with branched C 8 -C ⁇ o alkyl groups wherein a high proportion of Co-group is present
• Exxon-Mobil Chemical Houston, USA or Vestinol 9 ® DINP (Oxeno Olefinchemie GmbH, Marl, DE).
• Preferred diisononyl phthalates are Jayflex DINP ® ® and Vestinol 9 DINP is particularly preferred ® Vestinol 9 DINP.
• Binary mixtures of diisocyanatotoluene isomers are typically used in component B). These isomer mixtures preferably contain 2,4-diisocyanatotoluene in a mixture with 5 to 25% by weight of 2,6-diisocyanatotoluene, based on the total mixture.
• the TDI isomer mixture particularly preferably contains 2,4-diisocyanatotoluene in a mixture with 15-25% by weight of 2,6-diisocyanatotoluene.
• An example of this are particularly preferably to TDI isomer is available commercially from Bayer AG, Leverkusen, DE available Desmodur ® T80.
• the trimerization catalyst C contains nitrogen bases of the Mannich type ( ⁇ -aminocarbonyl compounds).
• Suitable phenols for the production of the Mannich bases to be used according to the invention are mono- or polyhydric phenols with at least one CH bond capable of condensation to formaldehyde in the o- and / or p-position to the phenolic hydroxyl groups.
• examples are phenols such as cresols, xylenols, dihydroxylbenzenes, nonylphenols, nonylcresols, tert-butylphenols, isodecylphenols, ethylphenols, etc.
• the phenols used can also be substituted by substituents such as chlorine or bromine.
• multinuclear phenols such as 4,4'-dihydroxydiphenylmethane, tetrachloro- and tetrabromo-4,4'-dihydroxy-diphenylmethane, tetrachloro- and tetrabromo-4,4'-dihydroxy-diphenylmethane, 4, 4'-dihydroxydiphenyl or 2,4-dihydroxydiphenylmethane can be used.
• Formaldehyde in the form of an aqueous formalin solution or para-aldehyde or trioxane is preferably used as the aldehyde.
• Mannich bases which are produced with other aldehydes such as, for example, butyl aldehyde or benzaldehyde, are also suitable for the process according to the invention.
• the preferred secondary amine is dimethylamine.
• Mannich bases based on other C-H-acidic compounds are likewise suitable for the process according to the invention, but less preferred.
• trimerization catalysts of component C) are used in the process according to the invention in amounts of 0.001 to 5, preferably 0.01 to 3% by weight, based on the total diisocyanate mixture.
• trimerization of the compounds of component B) is carried out in the presence of solvent component A) essential to the invention, however, in the strict absence of aliphatic hydroxyl groups and urethane groups.
• the trimerization reaction takes place in the temperature range from 40 to 140 ° C., preferably 40 to 80 ° C., the trimerization being terminated by thermal decomposition of the catalyst or, preferably, by adding a catalyst poison.
• Suitable catalyst poisons for stopping the trimerization reaction are, for example, acids or acid derivatives, such as perfluorobutanesulfonic acid, propionic acid, the isomeric phthaloyl chloride, benzoic acid, benzoyl chloride or quaternizing agents such as e.g. Methyl toluenesulfonate. Mono- or di-phosphoric acid esters are also suitable for this.
• the TDI from B) is trimerized under the abovementioned conditions and using the Components A) and C) described above, where the amount of component B) already corresponds to the target TDI-based amount of polyisocyanate of> 25% by weight or more TDI is used at the beginning and the desired solids content later during or after Completion of the trimerization is adjusted by adding further solvent of component A).
• the procedure in practice is typically that a mixture of component B) in solvent A) is added to the catalyst at room temperature or even at the intended reaction temperature, continuously or, if appropriate, in portions, and the reaction temperature is controlled the speed of the addition of catalyst or by external heating or cooling within the temperature ranges mentioned until the NCO content of the mixture has dropped to the target value.
• the reaction is then preferably stopped by adding a catalyst poison.
• the trimerization must be carried out until the content of free TDI monomers in the reaction mixture is ⁇ 0.2% by weight.
• TDI-based isocyanurate polyisocyanate solutions which contain an isocyanurate polyisocyanate content of more than 25% by weight, preferably 25 to 50% by weight, particularly preferably 26 to 35% by weight, and at the same time a viscosity at 23 ° C. of ⁇ 20,000 mPas, preferably ⁇ 10,000 mPas and a residual monomer content of preferably 0.005-0.2% by weight.
• the solutions according to the invention are clear, almost colorless liquids which, even after storage for several weeks, tend neither to crystallize nor to form precipitates or phase separation. In addition, even after storage, they are distinguished by an extremely low content of free TDI, which is a particular advantage of the solutions according to the invention because of the relatively low boiling point of this toxicologically objectionable diisocyanate.
• DE-A 24 19 016 of the prior art contains neither information about the use of Mannich bases for the trimerization of TDI or TDI isomer mixtures, nor the use of branched dialkyl phthalates such as, in particular, the isomeric diisononyl phthalates.
• the products produced according to DE-A 24 1 016 already have viscosities of 35,000 mPas / 23 ° C. at solids contents of ⁇ 15% by weight. The extent to which the described procedure is suitable for producing low-monomer products with ⁇ 0.2% by weight of free TDI cannot be seen.
• Example 17 describes the trimerization of TDI with 35% by weight of the 2,6-isomer in the presence of Mannich bases in dioctyl phthalate.
• TDI residual TDI content
• solids contents solids contents of ⁇ 25% by weight
• these products already have viscosities of approximately 9000 mPas / 23 ° C.
• a further trimerization to lower the residual monomer content ⁇ 0.2% by weight would lead to a drastic increase in viscosity, so that products outside the specification essential to the invention would be obtained.
• This specification can only be achieved through the use of branched aliphatic dialkyl phthalates, especially diisonyl phthalate.
• the solutions according to the invention are suitable as adhesion promoters for soft PVC and in particular as adhesion promoters for PVC plastisols.
• the solutions according to the invention are particularly advantageous as adhesion promoters between substrates made of man-made fibers with groups which are reactive towards NCO groups, e.g. Polyamide or polyester fibers and PVC plastisols or soft PVC melts are used.
• NCO groups e.g. Polyamide or polyester fibers
• PVC plastisols or soft PVC melts are used.
• the adhesion of soft PVC or PVC plastisols to flat substrates, i.e. Films are improved.
• the procedure can be such that the solutions according to the invention are printed, knife-coated, screened or sprayed onto the substrates to be coated or applied by dipping.
• one or more adhesive-free PVC layers are applied to the substrate surfaces pretreated in this way, for example as plastisols or by extrusion or melting rollers. coating or applied by lamination.
• the solutions according to the invention can particularly preferably also be added to a PVC plastisol before its application.
• solutions according to the invention are normally used in amounts such that 0.5 to 2000% by weight, preferably 2 to 30% by weight, of isocyanurate polyisocyanate are present, based on plasticizer-free polyvinyl chloride.
• the solutions according to the invention can, however, also be used in any other quantities which are adapted to the respective field of application.
• the production of the finished layers that is to say the reaction of the NCO groups of the adhesion promoter with the substrate and the gelation of the PVC layer, takes place independently of the type of application, in the customary manner at higher temperatures, the PVC depending on the composition -Shifts temperatures between 130 and 210 ° C are common.
• the solutions according to the invention are suitable as additives to improve the adhesion for coatings based on plasticized PVC, in particular for the production of tarpaulins, air-inflated halls and other textile structures, flexible containers, tent roofs, awnings, protective clothing, conveyor belts, flock carpets or foam synthetic leather.
• the solutions according to the invention are particularly well suited as adhesion-promoting additives in the coating of substrates with groups reactive towards isocyanate groups, in particular when coating substrates based on chemical fibers with groups reactive toward isocyanate groups.
• the characteristics of the products were the solids content (thick film method: lid, lg sample, 125 ° C convection oven, based on DIN EN ISO 3251), the viscosity (rotary viscometer VT550 at 23 ° C from Haake GmbH, Düsseldorf, DE) and the residual monomer content determined on TDI (gas chromatography, Hewlett Packard 5890 according to DIN ISO 55956).
• Desmodur ® T80 TDI Iso erengemisch of 80 wt% of 2,4-TDI and 20 wt% of 2,6 TDI, Bayer AG, Leverkusen, Germany.
• Desmodur ® T65 TDI isomer mixture of 65% by weight 2.4 TDI and 35% by weight 2.6 TDI, Bayer AG, Leverkusen, DE
• Adimoll ® DO Di-ethyl-2-hexyladi ⁇ at, Bayer AG, Leverkusen, DE
• Desmodur ® T65 were at 50 ° C in 390 g dioctyl phthalate (DOP) with a total of 2.2 ml of a catalyst based on a Mannich base of i-nonylphenol, formaldehyde and dimethylamine according to Example 2 of US-B 4 115 373 trimerized. After a total of 370 minutes, the reaction was interrupted by adding 1 ml of a solution of 1 ml of perfluorobutanesulfonic acid in 2 ml of dimethylformamide. A clear solution with a solid of 24.7%, an NCO content of 3.8%, a viscosity of 12,000 mPas (23 ° C) and a residual monomer content of free TDI of 0.41%.
• DOP dioctyl phthalate
• the choice of the solvent has a decisive influence on the result of the trimerization.
• the desired combination of properties cannot be achieved by using the plasticizers or solvents described in the prior art, such as di-ethyl-2-hexyl adipate or ethylene glycol di-benzoate.
• Example 3 180 g Desmodur ® T80 were incubated at 45 ° C in 414.6 grams of Jayflex DINP ® with a total of 4.8 g of a catalyst I (30% solution in butyl acetate / xylene 50:50 vohvol) trimerized. After a total of 48 hours, the reaction was interrupted by adding 6.11 g of para-toluenesulfonic acid methyl ester and the mixture was stirred at 60-70 ° C. for one hour. A clear solution with a solids content of 30%, an NCO content of 5.61%, a viscosity of 7,900 mPas (23 ° C.) and a residual monomer content of free TDI of 0.14% was obtained.
• Desmodur ® T80 were trimerized at 75 ° C in 715 g Vestinol ® 9 DINP with a total of 7.96 g of a catalyst I (30% solution in butyl acetate / xylene 50:50 vohvol). After a total of 56 hours, the reaction was interrupted by adding 3.98 g of para-toluenesulfonic acid methyl ester and the mixture was stirred at 60-70 ° C. for one hour. A clear solution with a solids content of 28.5%, an NCO content of 4.8%, a viscosity of 10,000 mPas (23 ° C.) and a residual monomer content of free TDI of 0.15% was obtained.
• the application was made one-sided on the side of the fabric on which the adhesive line was later applied.
• the non-stick impregnation was dried in the hood before further processing.
• Blanket squeegee approx. 45 cm wide with pointed squeegee
• Blanket squeegee approx. 45 cm wide with blunt squeegee
• Polyester fabric 1100 dtex, weave L 1/1, setting 9/9 Fd / cm
• Polyamide 6.6 fabric 940 dtex, weave L 1/1, setting 8.5-9.5 Fd / cm
• Tissue samples measuring approximately 40 x 25 cm were used for the test.
• the plastisol was produced in a mixer from Drais, Mannheim, DE by stirring (2.5 h) at maximum speed and water cooling under vacuum.
• the adhesive line based on the above plastisol with varying adhesion promoter contents was applied to the respective polyester and polyamide fabric with a rubber squeegee (Lückenhaus, DE, polyester fabric, 1100 dtex, weave L 1/1, setting 9/9 Fd / cm or polyamide 6.6 fabric: 940 dtex, weave L 1/1, setting 8.5-9.5 Fd / cm).
• the coating weight was approx. 100 g / m 2 and the coating was carried out on an area of approx. 30 x 20 cm.
• the adhesive coats were then pre-gelled by storing them at 140 ° C. in a convection oven for 2 minutes before the top coats were applied.
• the first top coat based on the above plastisol was applied with a rubber blanket with a blunt squeegee (coating weight approx. 850 g / m 2 ) and pre-gelled for 1 minute by heating at 140 ° C. in the heating cabinet. Coating the back of the fabric The subsequent top coat on the back of the fabric prevented the fabric from tearing and fraying when the layers were separated by the tractor. The coating on the back of the fabric was applied with a rubber blanket with a blunt squeegee (coating weight approx. 150 g / m 2 ) and pre-gelled for 1 minute by heating at 140 ° C. in the heating cabinet.
• the second top coat also based on the above-described P VC plastisol, was applied to the first pre-gelled top coat with a rubber blanket with a blunt squeegee (coating weight approx. 1400 g / m 2 ) and tempered at 140 ° C in Heating cabinet pre-gelled for 2 minutes.
• Test specimens measuring 5 x 26 cm were punched out of the tissue samples produced in this way.
• the adhesive strengths were then determined using these samples using a Lloyd M 5 K tractor.
• the values obtained indicate the force in Newtons that is necessary to detach 5 cm of the coating from the carrier fabric (peeling test).
• the stated values were obtained by averaging at least 3 individual measurements.
• Adhesion promoter made of polyester fabric Polyamide fabric Example 1 (2% in the line) 170 N / 5cm 191 N / 5cm Example 1 (4% in the line) 181 N / 5cm 226 N / 5cm Example 1 (6% in the line) 212 / 5cm 225 N / 5cm example 2 (2% in the line) 176 N / 5cm 194N / 5cm example 2 (4% in the line) 230 N / 5cm 252 / 5cm example 2 (6% in the line) 215 N / 5cm 253 N / 5cm example 3 ( 4% in the adhesive line) 206 N / 5cm 230 N / 5cm

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Polyurethanes Or Polyureas (AREA)
• Paints Or Removers (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2004
  • 2004-01-23 DE DE102004003794A patent/DE102004003794B4/de not_active Expired - Fee Related
• 2005
  • 2005-01-21 US US10/586,596 patent/US20080287613A1/en not_active Abandoned
  • 2005-01-21 AT AT05701100T patent/ATE373029T1/de active
  • 2005-01-21 EP EP05701100A patent/EP1711546B1/de not_active Expired - Lifetime
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  • 2005-01-21 ES ES05701100T patent/ES2292098T3/es not_active Expired - Lifetime
  • 2005-01-21 DE DE502005001483T patent/DE502005001483D1/de not_active Expired - Lifetime
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