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
• • 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
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
  • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• • 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
  • C08G18/027—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing urethodione 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
• • 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
  • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • 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
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

• This invention relates to the preparation and use of low monomer 1: 1 adducts of hydroxyalkyl (meth) acrylates and diisocyanates.
• the monoadducts (1: 1 adducts) of hydroxy (meth) acrylates and diisocyanates are valuable, versatile synthetic building blocks due to their inherent hetero-functionality.
• Application fields are z.
• acrylic-functionalized derivatives by reaction of the isocyanate group with monofunctional reagents or the preparation of corresponding acrylic-functionalized, UV-curable resins by reacting the isocyanate group with polyfunctional reactants.
• polyisocyanates by z.
• Groups of such polymers provide easy and mild access to tailored polymers with a unique property profile.
• This process inevitably produces a mixture of hetero-functional monoadduct (1: 1 adduct), bisadduct (1: 2 adduct) and residual monomer (free diisocyanate) in the ratio of about 1: 2: 1 by using an excess of diisocyanate the content of bisadduct of the mixture can be suppressed.
• the proportion of residual monomer increases.
• the bis-adducts as diacrylates, no longer satisfy the desired criterion of hetero-functionality, in contrast to the corresponding monoadduct. They reduce the quality of the monoadduct and also do not remain without effect on the quality and the characteristics of the desired end products. The same considerations apply to the excess starting diisocyanate remaining in the adduct. In addition, diisocyanates are very reactive compounds. Representatives of this substance class are therefore classified as toxic for this reason. A high residual content of monomeric diisocyanate in the product should therefore be avoided in principle.
• EP 1 179 555 describes the preparation of such low-monomer adducts from hydroxyalkyl (meth) acrylates and diisocyanates by separating off the monomer by means of short-path distillation under very specific conditions: During short-path distillation, polymerization-inhibiting gases must be present in sufficient concentration. Although this is technically possible, but quite expensive and also carries the risk that in case of incorrect implementation, the product polymerized within the Kurzwegdestillationskolonne and thereby a considerable cleaning effort is necessary.
• the diisocyanates used have no uretdione groups.
• the object was therefore to find a method which overcomes the disadvantages of the previous methods, i. high monomer content, high content of bisadducts, tendency to polymerization in the distillative separation of monomeric diisocyanates, does not include and especially without any special technical effort monomer-poor 1: 1 adducts of hydroxyalkyl (meth) acrylates and diisocyanates makes accessible.
• the invention therefore provides a process for preparing low-monomer 1: 1 adducts of hydroxyalkyl (meth) acrylates and diisocyanates by the following steps:
• the invention also provides the use of the monomer-poor 1: 1 adducts of hydroxyalkyl (meth) acrylates and diisocyanates in binders and coating compositions, especially in formulations as paint sealant or adhesive compositions for painting, bonding or sealing of metal, plastic, glass -, wood, MDF (Middle Density Fiber) - or leather substrates or other substrates.
• monomer-poor 1: 1 adducts of hydroxyalkyl (meth) acrylates and diisocyanates in binders and coating compositions, especially in formulations as paint sealant or adhesive compositions for painting, bonding or sealing of metal, plastic, glass -, wood, MDF (Middle Density Fiber) - or leather substrates or other substrates.
• Uretdione group-containing polyisocyanates are well known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929,724 and EP 417,603.
• a comprehensive review of industrially relevant processes for the dimerization of isocyanates to uretdiones is provided by J. Prakt. Chem. 336 (1994) 185-200.
• the reaction of isocyanates to uretdiones in the presence of soluble Dimehs mecanicskatalysatoren such as.
• dialkylaminopyridines trialkylphosphines, phosphorous acid triamides or imidazoles.
• the reaction - optionally carried out in solvents, but preferably in the absence of solvents - is stopped when a desired conversion is achieved by addition of catalyst poisons.
• the conversion should not be higher than about 20%, preferably 15%, depending on the diisocyanate used, since it would otherwise be too large due to the oligomer formation after cleavage of the uretdione Concentration of free diisocyanate comes.
• Excess monomeric diisocyanate is subsequently separated by short path evaporation. Short path distillation is carried out at 80-220 ° C / 0.1-20 mbar. The temperature and the negative pressure depend on the viscosity behavior of the respective products.
• the short-path evaporator may be a glass or metal apparatus.
• the reaction mixture can be freed from the catalyst in the course of the monomer separation.
• catalyst poisons can be dispensed with in this case.
• a wide range of isocyanates is suitable for preparing the diisocyanates containing uretdione groups.
• IPDI isophorone diisocyanate
• HDI hexamethylene diisocyanate
• 2,2'-dicyclohexylmethane diisocyanate / 2,4'-dicyclohexylmethane diisocyanate 4,4'-dicyclohexylmethane diisocyanate (H 12 MDI)
• 2-methylpentadiisocyanate MPDI
• TMDI norbornane diisocyanate
• the uretdione-containing diisocyanates used in the first step according to the invention are dimers of a diisocyanate having a uretdione group of the following formula I.
• Suitable hydroxyalkyl (meth) acrylates are all compounds which carry at least one methacrylate or acrylate function, as well as exactly one Hydroxyl group. Further constituents may be aliphatic, cycloaliphatic, aromatic or heterocyclic alkyl groups. Oligomers or polymers are also conceivable.
• Diisocyanate (I) with a hydroxyalkyl (meth) acrylate wherein the molar ratio is 1: 2 to 1: 2.6.
• the NCO / OH group ratio is correspondingly 1: 1, 0 to 1: 1, 3, preferably 1: 1, 0 to 1: 1, 1, more preferably 1: 1.
• the reaction can be carried out in an inert solvent (free of alcohol, amino, thiol and acid groups) such as e.g. For example, acetone, methyl ethyl ketone, tetrahydrofuran, ethyl acetate, butyl acetate or toluene occur.
• Preferred solvent is ethyl acetate and acetone.
• the reaction can be carried out with and without urethanization catalysts, preferably with catalysts such as Dibutyltin dilaurate (DBTL), bismuth neodecanoate, zinc octoate, diazabicyclooctane (DABCO), tertiary amines.
• DBTL Dibutyltin dilaurate
• DABCO diazabicyclooctane
• the reaction takes place at temperatures from 40 0 C to 80 0 C so that only the free NCO groups of the uretdione group-containing diisocyanate (I) react with the OH groups and the presence of uretdione group is not cleaved back into free NCO groups.
• the reaction time is variable, since it is essential to the invention that the reaction takes place with complete reaction of the free NCO groups with the OH groups.
• Complete reaction means that the reaction product prepared in the 1st step has a content of free NCO groups of 0 to 0.5 wt .-%.
• a possibly present excess of hydroxyalkyl (meth) acrylate can be separated at this point by distillation, for example, by short path distillation at temperatures below 100 0 C without hesitation.
• Suitable reaction units are all customary equipment, boilers, static mixers, extruders, etc., preferably aggregates which have a mixing function or stirring function.
• the possibly used solvent is separated off at the end of the reaction, preferably by distillation, such as. Example by means of a rotary evaporator, short-path evaporator, thin-film evaporator or other gentle distillation process.
• the reaction product thus obtained is an adduct of the OH groups of two molecules of hydroxyalkyl (meth) acrylate with the two terminal, ie free NCO groups of uretdione-containing diisocyanate (I).
• antioxidants already in the first step are advantageous.
• Suitable antioxidants are, for example, catechol, 4-methoxyphenol, 4-tert-butyloxyphenol, 4-benzyloxyphenol, ⁇ -naphthol, ⁇ -naphthol, phenothiazine, 10-10-dimethyl-9,10-dihydroacridine, bis- [2-hydroxy -5-methyl-3-cyclohexylphenyl] -methane, bis [2-hydroxy-5-methyl-3-tert-butylphenyl] -methane, hydroquinone, pyrogallol, 3,4- Dihydroxy-1-tert-butylbenzene, 4-methoxy-2 (or 3) -tert.-butylphenol (BHA), BHA also in combination with bis [2-carboxyethyl] sulfide (TDPA), 4-methyl- 2,6-di-tert-but
• the phenolic antioxidants may also be combined with phosphorous acid esters according to formula II wherein X is oxygen or sulfur, and wherein R 1 , R 2 and R 3 are the same or different alkyl, alkylene (1) -yl, aryl or aralkyl radicals each represent 1 - 20 carbon atoms.
• the phenolic antioxidants may also be combined with thioethers or amines such as 2-anilinonaphthalene (PBN), 1-anilinonaphthalene (PAN) or 1, 4-dianilinobenzene.
• PBN 2-anilinonaphthalene
• PAN 1-anilinonaphthalene
• 4-dianilinobenzene a compound that has a high degree of polymerization-inhibiting principles due to their chemical structure, such as. B. 2,2'-thiobis- (4-tert-octylphenol).
• antioxidants preferably takes place already in the 1st step, but can in principle also take place only in the 2nd step.
• the cleavage of the uretdione group of the adduct from the first step to free NCO groups takes place to form two monomer-poor 1: 1 adducts of one molecule of diisocyanate and one molecule of hydroxyalkyl (meth) acrylate.
• reaction units are all conventional apparatuses such as boilers, static mixers, extruders, etc., preferably assemblies that include a mixture or stirring function.
• the time can be between a few minutes and several days.
• the progress of the cleavage is followed titrimetrically via the determination of the free NCO groups. The cleavage is continued as long as the free NCO content increases, and then terminated by cooling.
• the monomeric 1: 1 adducts obtained in accordance with the invention have a content of monomeric diisocyanates of less than 1% by weight, preferably less than 0.5% by weight.
• Monomeric hydroxyalkyl (meth) acrylate is not left over, since any excess after the first step reacts completely with the now vacant NCO groups.
• the present invention is further illustrated by examples but not limited.
• the product from 2. was heated in a round bottomed flask with stirring (3a: 140 ° C., 3b: 170 ° C.) while dry air was passed over.
• the NCO content was measured after some time:

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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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Polyurethanes Or Polyureas (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Paints Or Removers (AREA)
• Adhesives Or Adhesive Processes (AREA)

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• 2009
  • 2009-04-09 DE DE102009002301A patent/DE102009002301A1/de not_active Withdrawn
• 2010
  • 2010-02-08 CN CN201080015852.8A patent/CN102388076B/zh not_active Expired - Fee Related
  • 2010-02-08 KR KR1020117023581A patent/KR20120027139A/ko not_active Application Discontinuation
  • 2010-02-08 WO PCT/EP2010/051466 patent/WO2010115644A1/de active Application Filing
  • 2010-02-08 JP JP2012503930A patent/JP5619139B2/ja not_active Expired - Fee Related
  • 2010-02-08 US US13/201,469 patent/US8729259B2/en not_active Expired - Fee Related
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