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US20180186917A1 - Reaction products containing urethane groups and urea groups - Google Patents

Reaction products containing urethane groups and urea groups Download PDF

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Publication number
US20180186917A1
US20180186917A1 US15/740,624 US201615740624A US2018186917A1 US 20180186917 A1 US20180186917 A1 US 20180186917A1 US 201615740624 A US201615740624 A US 201615740624A US 2018186917 A1 US2018186917 A1 US 2018186917A1
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Prior art keywords
radical
general formula
integer
urea groups
containing urethane
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US15/740,624
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Inventor
Andreas OKKEL
Wolfgang Pritschins
Michael BESSEL
Irina GIEBELHAUS
Marcus Meichsner
Monika Roch
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BYK Chemie GmbH
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BYK Chemie GmbH
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Assigned to BYK-CHEMIE GMBH reassignment BYK-CHEMIE GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OKKEL, Andreas, ROCH, Monika, MEICHSNER, MARCUS, GIEBELHAUS, Irina, BESSEL, MICHAEL, PRITSCHINS, WOLFGANG
Publication of US20180186917A1 publication Critical patent/US20180186917A1/en
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    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
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Definitions

  • the present invention relates to reaction products containing urethane and urea groups, to a process for preparation thereof, to the use thereof as wetting agents, dispersants, dispersion stabilizers and/or adhesion promoters, and to compositions comprising them.
  • wetting agents in dissolved or dispersed form in a liquid lower the surface tension or interfacial tension and hence increase the wetting capacity of the liquid. In this way, wetting agents in many cases actually enable any surface wetting at all.
  • Dispersants are generally suitable for stabilization of solid particles in binders, varnishes, pigment pastes, plastics and plastics mixtures, adhesives and sealants, for reduction of the viscosity of corresponding systems and for improving the flow properties.
  • Dispersion stabilizers are used for stabilization of dispersions that have already been produced.
  • Dispersants of this kind are surface-active substances of anionic, cationic and/or uncharged structure. These substances are either applied directly to the solid in a small amount or added to the dispersion medium.
  • a further major factor is that reagglomeration can occur after the dispersion process even after complete deflocculation of the solid agglomerates into primary particles, which partly or completely negates the expenditure on dispersion. Inadequate dispersion or reagglomeration typically results in unwanted effects, such as a rise in viscosity in liquid systems, a drift in the hue and a loss of gloss in varnishes and coatings, and also a reduction in the mechanical strength and material homogeneity in plastics.
  • Useful wetting agents and dispersants in practice include various types of compound. The particular reason for this is that there exist a high number of different systems based, in particular, on various kinds of binders combined with different particles to be dispersed, such as pigments, fillers and fibers.
  • WO-A-2012/175159 describes the preparation of specific additive compositions which can be regarded as high-quality wetting agents and dispersants.
  • Adhesion promoters are all components that lead to bond strength between materials to be combined with one another, for example coatings on various substrates such as metal, plastic, wood and glass.
  • adhesion promoters there is a structural relationship between adhesion promoters and wetting agents and dispersants, in such a way that adhesion promoters can correspond structurally to a wetting agent and dispersant having no sterically stabilizing side chains.
  • R is the organic radical of a corresponding polyisocyanate R(NCO) x , R is a branched or unbranched, saturated or unsaturated organic radical having 1 to 150 carbon atoms and does not contain any free isocyanate groups,
  • the Y radical(s) is/are independently the organic radical(s) of a corresponding alcohol Y(OH) q where q is an integer from 1 to 5 and Y is a branched or unbranched, saturated or unsaturated organic radical having 1 to 1000 carbon atoms,
  • the X group(s) is/are independently O, NH and/or NZ 2 and the XH group(s) is/are independently a hydroxyl group OH, a primary amino group NH 2 and/or a secondary amino group NHZ 2 where
  • k is an integer from 0 to 9
  • j is an integer from 0 to 9
  • i is an integer from 0 to 9
  • the G radical is a branched or unbranched, saturated or unsaturated organic radical
  • the A radical(s) is/are independently a radical of the general formula (II)
  • the R 1 radical is H or NH 2 or a branched or unbranched, saturated or unsaturated organic radical having 1 to 25 carbon atoms or, if Z b is C and R 2 is —CH ⁇ N—, where the nitrogen atom of the R 2 radical is bonded directly to Z b to form a 5-membered ring, R 1 is OH,
  • the Z a group is CH or N or CR 3 where the R 3 radical is a branched or unbranched, saturated or unsaturated organic radical having 1 to 18 carbon atoms,
  • the Z b group is CH or N or, if R 1 is OH, Z b is C,
  • R 2 radical is H or, if R 1 is OH, R 2 is —CH ⁇ N—,
  • the Z 1 radical(s) is/are independently the organic radical of a corresponding species of the general formula (III)
  • Z 1 is a branched or unbranched, saturated or unsaturated organic radical containing 1 to 150 carbon atoms
  • the P radical(s) is/are independently a radical of the general formula (IVa)
  • the Q radical(s) is/are independently a radical
  • V radical(s) is/are independently a radical
  • the “reaction product containing urethane and urea groups” comprises one or more species of the general formula (I) as main reaction product(s), meaning that the amount of the species of the general formula (I), the reaction product containing urea and urethane groups, is at least 40% by weight, more preferably at least 60% by weight and especially preferably at least 90% by weight, based on the total weight of the reaction product containing urethane and urea groups.
  • the reaction product containing urethane and urea groups consists essentially of one or more species of the general formula (I).
  • “essentially consisting of” is understood herein to mean a content of species of the formula (I) in the total weight of the reaction product containing urethane and urea groups of at least 95% by weight.
  • compositions here encompasses both compounds having a specific molecular weight and species that contain polymeric radicals and hence have a weight-average and a number-average molecular weight.
  • reaction products containing urethane and urea groups may in the simplest case be molecularly homogeneous products when exclusively molecularly homogeneous, essentially chemically pure compounds Y—(OH) q , R(NCO) x , Z 1 —(HX) w and a species for introducing the A radical are used for preparation thereof, in which, consequently, Y is non-polymeric, all Y are identical, all R are identical, all X are identical, all A are identical and all Z 1 are identical.
  • the simplest molecularly homogeneous products of the invention containing at least one species of general formula (I) arise in the case when x assumes the value of 2 and, consequently, a and b each assume the value of 1.
  • reaction products containing urethane and urea groups may also be molecularly inhomogeneous products. This is the case, for example, when the Y radical is polymeric in nature and hence per se introduces molecular inhomogeneity into the products.
  • reaction products containing urethane and urea groups may, finally, also be mixtures when the “reaction products containing urethane and urea groups” contain different species of general formula (I). This is the case, for example, when the species differ in the variables a and/or b and/or c.
  • the reactants for preparation of the reaction products containing urethane and urea groups contain different Y and/or R and/or A and/or Z 1 radicals.
  • the mixtures may be mixtures of chemically homogeneous reaction products containing urethane and urea groups that contain polymeric radicals, or mixtures of one or more chemically homogeneous reaction products containing urethane and urea groups with one or more reaction products containing urethane and urea groups and polymeric radicals.
  • hydroxyl group and “primary amino group” and “secondary amino group” should be understood in the sense of their general meaning. This means more particularly that they are present as an independent functional group and not part of an overall further functional group. Thus, in the context of this invention, the OH functionality of a carboxyl group is not a hydroxyl functionality.
  • the inventive reaction products containing urethane and urea groups comprise at least one species of the general formula (I)
  • the species of the general formula (I) contain at least one —NH—(CO)-A radical, which means that the species of the general formula (I) has at least one urea group, and at least one NH—(CO)—O—Y—(OH) r (PO) s radical, by virtue of which the species of the general formula (I) has at least one urethane group.
  • the species of general formula (I) may have one or more —NH—(CO)—X—Z. This (XP) p (XH) y radicals, by means of which further urethane and/or urea groups are introduced into the species of the general formula (I) depending on the X group(s).
  • the sum total a+b+c of all radicals bonded to R in the species of the general formula (I) is limited to the value of x, where x is an integer from 2 to 10.
  • the R radical is the organic radical of a corresponding polyisocyanate R(NCO) x . This means that the number of radicals bonded to R results from the number of isocyanate groups in the corresponding polyisocyanate R(NCO) x .
  • R radical does not contain any free isocyanate groups
  • all x free isocyanate groups of the polyisocyanate R(NCO) x have been converted to urethane and urea groups, such that the reaction product containing urethane and urea groups or the species of the general formula (I) present therein does not have any free isocyanate groups.
  • free isocyanate group should be understood in the sense of its general definition and describes isocyanate groups that are in free form and can be used for direct reaction with alcohols and/or primary and/or secondary amino groups. This means more particularly that uretdione groups and isocyanurate groups or what are called blocked isocyanate groups do not constitute free isocyanate groups.
  • x in the general formula (I) is an integer from 2 to 7, more preferably from 2 to 5, especially preferably of 2 or 3. Most preferably, x is the value of 2.
  • a is an integer from 1 to 6, more preferably an integer from 1 to 4, especially preferably of 1 or 2.
  • b is an integer from 1 to 6, more preferably an integer from 1 to 4, especially preferably of 1 or 2.
  • x is an integer from 2 to 7
  • a is an integer from 1 to 6
  • b is an integer from 1 to 6.
  • x assumes the value of 2
  • a is 1
  • b is 1.
  • the species of the general formula (I) has a —NH—(CO)-A radical and a —NH—(CO)—O—Y—(OH) r (PO) s radical.
  • the species of the general formula (I) does not contain any —NH—(CO)—X—Z 1 —(XP) p (XH) y radicals.
  • the species in addition to the —NH—(CO)-A and —NH—(CO)—O—Y—(OH) r (PO) s radicals that are essential to the invention, may contain one or more —NH—(CO)—X—Z 1 —(XP) p (XH) y radicals.
  • reactive OH or XH groups bonded to Y and Z 1 can be used as attachment points in order to construct larger structures through reactions with further polyisocyanates R(NCO) x .
  • the variables p and s indicate the number of OH or XH groups that have reacted with a free isocyanate group of a polyisocyanate R(NCO) x .
  • the simplest structures of the species of the general formula (I) arise in the cases where the variables s and p assume the value of 0. This case is also referred to hereinafter as a species of the general formula (I) with a 0th generation structure.
  • the variable p is an integer from 0 to 3, preferably of 0 or 1.
  • s is an integer from 0 to 3, preferably of 0 or 1.
  • the OH groups bonded to Y and the XH groups bonded to Z 1 are capable of reacting reactions with a free isocyanate group of a further polyisocyanate R(NCO) x to form urethane and urea groups.
  • the remaining free isocyanate groups of the polyisocyanate R(NCO) x can in turn react with the further reactants in the reaction mixture.
  • the reactive groups bonded to Y and/or Z 1 serve as attachment points for construction of larger structures. This case is referred to as a 1 st generation structure.
  • Species of the general formula (I) having a 1st generation structure can in turn enter into the reactions described above, so as then to result in formation of 2nd generation structures. It is essential to the invention that the at least one species of the general formula (I) has no more than a 2nd generation structure in the reaction product containing urethane and urea groups.
  • the species of the general formula (I) have a number-average molecular weight in the range from 253 to 250 000 g/mol, more preferably from 500 to 200 000 g/mol, especially preferably from 800 to 150 000 g/mol, most preferably from 1000 to 100 000 g/mol.
  • the R radical corresponding to the polyisocyanate R(NCO) x is a branched or unbranched, saturated or unsaturated organic radical having 1 to 150 carbon atoms.
  • the organic R radical may additionally contain uretdione and/or urethane groups, but ones that do not react under the given conditions.
  • the organic R radical is in the form of a hydrocarbyl radical, more preferably of an arylene group, of an alkylarylene group and/or of an acyclic, cyclic, branched or unbranched alkylene group.
  • the R radical does not contain any free isocyanate groups.
  • Preferred polyisocyanates R(NCO) x are those in which x is an integer from 2 to 7. Preference is further given to polyisocyanates in which x is an integer from 2 to 5, more preferably of 2 or 3. Very particular preference is given to diisocyanates R(NCO) 2 .
  • the diisocyanates it is further preferable that the diisocyanate R(NCO) 2 has two isocyanate groups of different reactivity.
  • Preferred diisocyanates having groups of different reactivity are toluene 2,4-diisocyanate and isophorone diisocyanate.
  • Polyisocyanates R(NCO) x in which x is an integer from 2 to 10 are known in principle from the prior art.
  • EP 0154678 A1 describes corresponding polyisocyanates in which x assumes a value of greater than 2.
  • polyisocyanates examples include those that can be obtained by addition of diisocyanates onto polyols. These are available, for example, under the Desmodur L trade name. Further polyisocyanates are obtainable by biuret reactions from diisocyanates. These are available, for example, under the Desmodur N trade name. Additionally useful are polyisocyanates having an isocyanurate base structure that are obtained by cyclization of diisocyanates. Corresponding products are available under the Desmodur HL, Desmodur IL, Polurene KC or Polurene HR trade names. In addition, it is possible to use tolylene diisocyanate-isophorone diisocyanate isocyanurate or trimeric isophorone diisocyanate.
  • polyisocyanates are commercial products that frequently do not have their underlying chemical formula in pure form, but are mixtures of polyisocyanates having similar structure.
  • Polyisocyanates R(NCO) x in which x assumes the value of 2 are covered by the umbrella term of “polyisocyanates” in the context of this invention, but are also referred to more specifically as diisocyanates.
  • Diisocyanates of this kind are, for example, 1,4-diisocyanatobutane, hexamethylene diisocyanate (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4′-diisocyanatodicyclohexylmethane (H12MDI), tolylene diisocyanate (TDI), 1-isocyanato-1-methyl-4
  • diisocyanates available as commercial products are Desmodur T100 (100% 2,4-TDI, Bayer AG), Desmodur T80 (80% 2,4-TDI, 20% 2,6-TDI, Bayer AG), Desmodur T65 (65% 2,4-TDI, 35% 2,6-TDI, Bayer AG), Desmodur N3400 (aliphatic HDI uretdione, Bayer AG), Thanecure T9 (aromatic TDI uretdione, TSE Industries), Crelan VP LS 2147 and Crelan VP LS 2347 (aliphatic IDPI uretdiones, Bayer AG).
  • Preparation of the inventive reaction products containing urethane and urea groups can be accomplished using one or more monomeric, oligomeric or polymeric diisocyanates.
  • the Y radical(s) of the general formula (I) is/are independently the organic radical(s) of a corresponding alcohol
  • Y—(OH) q where q is an integer from 1 to 5 and Y is a branched or unbranched, saturated or unsaturated organic radical having 1 to 1000 carbon atoms.
  • the organic Y radical may have additional heteroatoms such as O, S, Si and/or N, or contain ether, urethane, carbonate, amide, urea and/or ester groups.
  • additional heteroatoms such as O, S, Si and/or N, or contain ether, urethane, carbonate, amide, urea and/or ester groups.
  • the hydroxyl groups, primary amino groups and secondary amino groups that are extremely reactive toward isocyanate groups must not be present in Y.
  • hydrogen may be replaced by halogen (for example fluorine and/or chlorine).
  • the Y radical may bear further groups, such as C ⁇ C double bonds, which are inert in the formation of the addition product.
  • ester, ether, urethane, carbonate and/or siloxane groups present may be present in block structure (for example poly(ethylene oxide block-propylene oxide block-epsilon-caprolactone), form a gradient or else be in a random arrangement.
  • block structure for example poly(ethylene oxide block-propylene oxide block-epsilon-caprolactone), form a gradient or else be in a random arrangement.
  • Y contains at least one polyether radical, polyester radical, hydrocarbyl radical and/or polysiloxane radical.
  • the parameter q of the alcohol Y—(OH) q can affect the structure of the general formula (I) present in the reaction product of the invention containing urethane and urea groups.
  • reaction products containing urethane and urea groups comprising at least one species of the species of the general formula (I)
  • mixtures of different alcohols Y—(OH) q which differ by their q value. If corresponding mixtures of different alcohols Y—(OH) q with different q values are used, it is preferable that at least 40%, further preferably 50% and more preferably 60% of the alcohols Y—(OH) q have a value of q of 1.
  • alkanols, cycloalkanols or phenols can be reacted with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, aliphatic or aromatic glycidyl ethers such as isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresyl glycidyl ether and phenyl glycidyl ether. It is also possible to use mixtures of these raw materials. In the case of mixed polyethers, these may be arranged randomly, in gradient form or in blocks.
  • These polyethers preferably have a number-average molecular weight (M n ) in the range from about 100 to 25 000, more preferably from 150 to 15 000 and particularly typically from 200 to 10 000 g/mol.
  • polyethers based on ethylene oxide, propylene oxide and mixtures thereof Preference is given to polyethers based on ethylene oxide, propylene oxide and mixtures thereof.
  • hydroxy-functional vinyl compounds such as hydroxybutyl vinyl ether
  • monohydroxy-functional polyoxyalkylene monoalcohols such as allyl polyethers (e.g.
  • polyoxyalkylene monoalcohols such as Polyglycol B 11/50, Polyglycol B 11/70, Polyglycol B 11/100, Polyglycol B 11/150, Polyglycol B 11/300 or Polyglycol B 11/700 from Clariant AG, Pluriol® A 1000 PE, Pluriol® A 1320 PE, or Pluriol® A 2000 PE from BASF AG or Terralox WA 110 from DOW Chemicals
  • polyoxyalkylene monoalcohols such as Polyglycol B 11/50, Polyglycol B 11/70, Polyglycol B 11/100, Polyglycol B 11/150, Polyglycol B 11/300 or Polyglycol B 11/700 from Clariant AG, Pluriol® A 1000 PE, Pluriol® A 1320 PE, or Pluriol® A 2000 PE from BASF AG or Terralox WA 110 from DOW Chemicals
  • Y contains 1 to 450 ether oxygen atoms which are preferably present in groups having ether oxygen atoms that are derived from polytetrahydrofuran, polyoxetanes and/or polyoxiranes.
  • Y contains 3 to 400 ether oxygen atoms, where at least 50 mol %, preferably at least 80 mol %, of the ether oxygen atoms are present in ethylene oxide and/or polypropylene oxide structural units.
  • the hydrocarbyl radicals are preferably in the form of an aryl radical, of a branched or unbranched aralkyl radical and/or of an acyclic, cyclic branched or unbranched alkyl radical. It is also possible to use mixtures of such compounds, i.e. at least two different compounds Y—(OH) q .
  • the aliphatic or araliphatic compounds Y—(OH) q may be in straight-chain or branched, saturated or unsaturated form. Saturated species are preferred.
  • Examples of Y—(OH) q with hydrocarbyl radicals, in the case that q is 1, are methanol, ethanol, butanol, ethylhexanol, decanol, isotridecyl alcohol, lauryl alcohol, stearyl alcohol, isobornyl alcohol, benzyl alcohol, propargyl alcohol, oleyl alcohol, linoleyl alcohol, oxo alcohols, neopentyl alcohol, cyclohexanol, fatty alcohols, alkylphenols, alkylnaphthols, phenylethanol.
  • Examples of Y(—OH) q with hydrocarbyl radicals, if q is greater than 1, are butanediol, hexanediol, cyclohexanedimethanol, neopentyl glycol, ethylene glycol, glycerol and trimethylolpropane.
  • Y—(OH) q may be polyolefin polyols or monools, such as nonhydrogenated, partly hydrogenated and/or fully hydrogenated polybutadienes, non-hydrogenated, partly hydrogenated and/or fully hydrogenated polyisoprenes, polyisobutylenes, polypropylenes or ethylene/butylene copolymers. These compounds are known. For example, the route to hydroxy-functional polyisobutylenes is described in U.S. Pat. No. 6,875,897.
  • Hydroxy-functional acrylates or methacrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl (meth)acrylate, are examples of suitable monohydroxy monoesters.
  • Polyesters can be prepared, for example, by reaction of dicarboxylic acids and the esterifiable derivatives thereof, such as anhydrides, acid chlorides or dialkyl esters (such as dimethyl esters or diethyl esters) by reaction with diols and mono-, di- or trifunctional starter components.
  • dihydroxy polyesters can be suppressed if required through use of appropriately stoichiometric amounts of monohydroxy compounds.
  • the esterification can be conducted in neat form or else by azeotropic esterification in the presence of an entraining agent.
  • dicarboxylic acids are succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic acid or dimerized fatty acids, and the isomers and hydrogenation products thereof.
  • corresponding diols are: ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, neopentyl glycol, cis-1,2-cyclohexanedimethanol, trans-1,2-cyclohexanedimethanol, and polyglycols based on ethylene glycol and/or propylene glycol.
  • Preferred polyesters for use as Y—(OH) q are those which can be obtained by polycondensation of one or more optionally alkyl-substituted hydroxycarboxylic acids and/or ring-opening polymerization of the corresponding lactones such as propiolactone, valerolactone, butyrolactone, caprolactone and/or substituted lactones by means of a mono-, di- or trihydroxy starter component (as described in U.S. Pat. No. 4,647,647). Preferably, these have a number-average molecular weight M n of 150 to 5000 g/mol.
  • Usable starter components T-(OH) q are in principle also all other compounds listed as Y—(OH) q .
  • Lactone polymerization is conducted by known processes, initiated, for example, by titanates, p-toluenesulfonic acid or dibutyltin dilaurate, at temperatures of, for instance, 70° C. to 180° C.
  • titanates p-toluenesulfonic acid or dibutyltin dilaurate
  • polyesters based on epsilon-caprolactone optionally in combination with delta-valerolactone.
  • Y—(OH) q it is also possible to use polyurethanes, polyether-polyurethanes, polyester-polyurethanes and/or polyether-polyester-polyurethanes, which can be obtained by addition reaction of diisocyanates with dihydroxyl compounds in the presence of mono-, di- or trifunctional starter components.
  • Hydroxyl compounds used to form the compounds Y—(OH) q containing urethane groups are preferably diols having 2 to 12 carbon atoms, polyoxyalkylene glycols and dihydroxy-functional polyesters.
  • the Y radical may also contain carbonate groups as obtained by known reactions with open-chain and/or cyclic carbonates.
  • Suitable examples are linear polyesters or polycarbonatediols that have been modified with carbonates, as used in polyurethane production. Examples are described in U.S. Pat. No. 4,101,529.
  • Suitable carbonates are, for example, aliphatic, cycloaliphatic, araliphatic and/or aromatic carbonic esters, such as dialkyl carbonates, e.g. dimethyl carbonate, diethyl carbonate or diphenyl carbonate, catechol carbonate or cyclic alkylene carbonates.
  • Particularly suitable are cyclic alkylene carbonates having 5- or 6-membered rings, which may optionally be substituted.
  • Preferred substituents are aliphatic, cycloaliphatic and/or aromatic groups having up to 30 carbon atoms.
  • suitable cyclic alkylene carbonates are ethylene carbonate, propylene carbonate, glycerol carbonate, trimethylene carbonate, 4-methyltrimethylene carbonate, 5-methyltrimethylene carbonate, 5,5-dimethyltrimethylene carbonate, 5,5-diethyltrimethylene carbonate or 5-methyl-5-propyltrimethylene carbonate.
  • hydroxy-functional poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines it is also possible for hydroxy-functional poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines to function as Y—(OH) q . Preference is given to using monohydroxy-functional compounds.
  • Poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines are obtained by cationic, ring-opening polymerization of 2-alkyl-2-oxazolines or 2-alkyl-2-oxazines with initiators such as para-toluenesulfonic acid, methyl tosylate or methyl triflate.
  • the oxazolinium or oxazinium end groups that result from the living cationic polymerization mechanism can be converted to the more stable hydroxyamides by alkaline hydrolysis via amino ester end groups.
  • An alternative route for preparation of monohydroxy-functional poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines is polymerization with 2-(4-hydroxyphenyl)-N-methyl-2-oxazolinium trifluoromethanesulfonate as the initiating species (A. Gross, G. Maier, O. Nuyken, Macromol. Chem. Phys. 197, 2811-2826 (1996)).
  • poly-2-ethyl-2-oxazoline is suitable for highly polar systems by virtue of its water solubility, while poly-2-lauryl-2-oxazoline, for example, is compatible in nonpolar systems.
  • block copolymers are formed from 2-ethyl-2-oxazoline and 2-lauryl-2-oxazoline, the polymers feature particularly broad compatibility.
  • Poly-2-alkyl-2-oxazolines or poly-2-alkyl-2-oxazines of this kind usually have a number-average molecular weight M n of 300 to 20 000 g/mol, preferably of 500 to 10 000 g/mol.
  • M n number-average molecular weight
  • 2-oxazolines which may possibly have additional functional groups.
  • Species of this kind are, for example, corresponding fatty acid-based 2-oxazolines.
  • OH-functional polymers of ethnically unsaturated monomers can be introduced in a known manner via hydroxy-functional ethylenically unsaturated monomers, via hydroxy-functional initiators or via hydroxy-functional chain transfer agents, for example in free-radical polymerization.
  • Particularly high selectivities in relation to the hydroxy functionality can be achieved by controlled or living polymerization methods, for example ATRP, NMP, RAFT or anionic polymerization.
  • Preference is given to monohydroxy-functional polyacrylic esters or polymethacrylic esters. Compounds of this kind have already been used in this field of industry for preparation of other dispersants, as described in U.S. Pat. No.
  • polyacrylate macromers such as Actflow UMM 1001 from Soken Chemical & Engineering Co. are available. These polyacrylates usually have a number-average molecular weight M n of 300 to 20 000 g/mol, preferably usually from 500 to 10 000 g/mol. These may be arranged in a block structure or else randomly or form a gradient.
  • OH-functional ethylenically unsaturated monomers are hydroxyalkyl (meth)acrylates of straight-chain, branched or cycloaliphatic diols having 2 to 36 carbon atoms, such as 3-hydroxypropyl methacrylate, 3,4-dihydroxybutyl monomethacrylate, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl methacrylate, 2,5-dimethylhexane-1,6-diol monomethacrylate;
  • caprolactone- and/or valerolactone-modified hydroxyalkyl (meth)acrylates (where the hydroxy (meth)acrylates are preferably derived from straight-chain, branched or cycloaliphatic diols having 2 to 8 carbon atoms);
  • alkyl (meth)acrylates of straight-chain, branched or cycloaliphatic alcohols having 1 to 22 carbon atoms such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate and t-butyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl methacrylate and aryl (meth)acrylates such as phenyl acrylate (where the aryl radicals may each be unsubstituted or up to tetrasubstituted), such as 4-nitrophenyl methacrylate;
  • ethylenically unsaturated heterocycles for example 4-vinylpyridine and 1-[2-(methacryloyloxy)ethyl]-2-imidazolidinone;
  • vinyl esters of carboxylic acids having 1 to 20 carbon atoms such as vinyl acetate; maleimide, N-phenylmaleimide and N-substituted maleimides with straight-chain, branched or cycloaliphatic alkyl groups having 1 to 22 carbon atoms, such as N-ethylmaleimide and N-octylmaleimide; (meth)acrylamide; N-alkyl- and N,N-dialkyl-substituted acrylamides having straight-chain, branched or cycloaliphatic alkyl groups having 1 to 22 carbon atoms, such as N-(t-butyl)acrylamide and N,N-dimethylacrylamide.
  • Preferred non-OH-functional monomers are alkyl (meth)acrylates, aryl (meth)acrylates, aralkyl (meth)acrylates and styrene.
  • polysiloxanes As Y—(OH) q it is also possible to use mono- or polyhydroxy-functional polysiloxanes.
  • the polysiloxanes can preferably be described by the following general formula:
  • R 13 and R 14 are different than R 16 .
  • the polysiloxane radicals may also take the form of organomodified polysiloxane radicals.
  • reaction product containing urethane and urea groups comprising at least one species of general formula (I), contains at least one A radical therein.
  • a radical(s) in the general formula (I) is/are independently a radical of the general formula (II)
  • the R 1 radical is H or NH 2 or a branched or unbranched, saturated or unsaturated organic radical having 1 to 25 carbon atoms or, if Z b is C and R 2 is —CH ⁇ N—, where the nitrogen atom of the R 2 radical is bonded directly to Z b to form a 5-membered ring, R 1 is OH.
  • R 1 is H or a branched or unbranched, saturated or unsaturated organic radical having 1 to 25, more preferably 1 to 18, especially preferably 1 to 10 and most preferably 1 to 6 carbon atoms. More preferably, the R 1 radical is H or a C 1 - to C 6 -alkyl radical or a phenyl radical. If R 1 is OH, this means that the correspondingly tautomeric resonance structural formula is also covered thereby.
  • the Z a group is CH or N or CR 3 where the R 3 radical is a branched or unbranched, saturated or unsaturated organic radical having 1 to 18, more preferably 1 to 10 and especially preferably 1 to 6 carbon atoms.
  • the Z a group is preferably CH or N, more preferably N.
  • the Z b group is CH or N or, if R 1 is OH, Z b is C.
  • the Z b group is preferably CH or N, more preferably N.
  • both Z a and Z b are N, and so component A comprises a 1,3,5-triazine as base structure.
  • R 2 radical is H or, if R 1 is OH, R 2 is —CH ⁇ N—.
  • R 2 is H.
  • the A radical of the general formula (II) is the corresponding radical of an appropriate primary amine of the general formula (IIa)
  • R 1 , Z a , Z b and R 2 are as defined for the general formula (II).
  • Primary amines of the general formula (IIa) are characterized in that they have two amino groups in the formula representation, where at least one of these amino groups is a primary amino group.
  • the second amino group may be a primary or secondary amino group.
  • the two primary amino groups differ in terms of their reactivity toward free isocyanate groups.
  • the reactivity is automatically different since primary amino groups react at a significantly faster rate than secondary amino groups.
  • the effect of the preferred different reactivity of the two amino groups is that only one of the amino groups reacts with a free isocyanate group of a polyisocyanate. It is preferable that the primary amine of the general formula (IIa) has two primary amino groups having different reactivities toward free isocyanate groups.
  • components of the general formula (IIa) are 2,4-diamino-1,3,5-triazines, 2,6-diaminopyridines, 2,4,6-triamino-1,3,5-triazine (melamine) and 2-amino-1,9-dihydropurin-6-one (guanine).
  • Preferred components of the general formula (IIa) used are 2,4-diamino-1,3,5-triazines, preference being given particularly to 2,4-diamino-6-phenyl-1,3,5-triazine (benzoguanamine (BGA)) and 2,4-diamino-6-methyl-1,3,5-triazine (acetoguanamine (AGA)).
  • the at least one species of the general formula (I) present in the inventive reaction product containing urethane and urea groups may contain one or more Z 1 radicals.
  • the (HX) y -Z 1 —(XH) p+1 component of the general formula (III) is preferably used for reacting any free isocyanate groups still present, such that the species of general formula (I) no longer contains any free isocyanate groups.
  • the (HX) y -Z 1 —(XH) p+1 component of the general formula (III) can also be introduced into the species of general formula (I) in a controlled manner. This can serve, for example, to introduce an additional group with pigment affinity into the species of the general formula (I).
  • the (HX) y -Z 1 — (XH) p+1 component of the general formula (III) can assume the role of a branching unit or a chain terminator, depending on the number of reactive XH groups bonded to Z 1 . It is thus possible to use this component to control the structure of the species of the general formula (I) and to adjust the density of bonding groups desired according to the application, for example properties that affect flocculation and/or adhesion.
  • the Z 1 radical(s) of the general formula (I) is/are independently the organic radical(s) of a corresponding species of the general formula (III)
  • the X group(s) is/are independently O, NH and/or NZ 2 and the XH group(s) is/are independently a hydroxyl group OH, a primary amino group NH 2 and/or a secondary amino group NHZ 2 .
  • k is an integer from 0 to 9
  • j is an integer from 0 to 9
  • i is an integer from 0 to 9
  • G is a branched or unbranched, saturated or unsaturated organic radical containing preferably 1 to 100 carbon atoms, more preferably 1 to 60 carbon atoms, especially preferably 1 to 30 and most preferably 1 to 18 carbon atoms, and P is as defined for the general formula (IVa).
  • the organic G radical does not have any HX groups reactive toward isocyanate groups.
  • the organic G radical may optionally also contain heteroatoms, especially oxygen and/or nitrogen atoms. These are preferably in the form of ether oxygen atoms and/or tertiary amino groups.
  • Z 1 is a branched or unbranched, saturated or unsaturated organic radical which contains 1 to 150 carbon atoms and is free of XH groups.
  • the organic Z 1 radical contains from 1 to 80 carbon atoms, more preferably from 1 to 40 carbon atoms and especially preferably 1 to 20 carbon atoms.
  • the organic Z 1 radical does not have any HX groups reactive toward isocyanate groups.
  • the organic G radical may optionally also contain heteroatoms, especially oxygen and/or nitrogen atoms. These are preferably in the form of ether oxygen atoms and/or tertiary amino groups and/or amide groups.
  • the organic Z 1 radical contains at least one tertiary amino group. Most preferably, the organic Z 1 radical contains at least one tertiary amino group and at least one amide group.
  • Examples of commercially available (HX) y —Z 1 —(XH) p+1 components are amino alcohols having tertiary amino groups and a sum total of 2 to 10 OH, NH 2 and/or NHZ 2 groups, for example trialkanolamines such as triethanolamine, triisopropanolamine, N-alkyldialkanolamines such as N-methyldiethanolamine, N-butyldiethanolamine, N-methyldiisopropanolamine, bis(2-hydroxyethyl)dodecylamine, bis(2-hydroxyethyl)octadecylamine, N-alkyl(aminoalkyl)hydroxyalkylamines such as aminopropylmethylethanolamine, N,N-dialkyl(dihydroxyalkyl)amines such as 3-(diethylamino)propane-1,2-diol, tetrakis(hydroxyalkyl)alkylenediamines such as
  • polyamines having at least one tertiary amino group and 2 to 10 primary and/or secondary amino groups for example trisaminoalkylamines such as tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, tris(3-aminopropyl)amine, N-alkyldiaminoalkylamines such as N,N-bis(3-aminopropyl)methylamine, N,N-dimethyldialkylenetriamines such as N,N-dimethyldipropylenetriamine, heterocyclic amines such as 1,4-bis(3-aminopropyl)piperazine and polyethyleneimines having 2 to 10 primary and/or secondary amino groups.
  • trisaminoalkylamines such as tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, tris(3-aminopropyl)amine
  • a further group of (HX) y —Z 1 —(XH) p+1 compounds can be obtained by modification of amino alcohols, amines and polyamines containing primary or secondary amino groups with a modifying component MZ bearing epoxy and/or acrylic ester groups.
  • hydroxy-functional acrylates for example hydroxyethyl acrylate, or epoxides, for example 2-ethylhexyl glycidyl ether
  • amino alcohols having secondary amino groups for example N-(2-hydroxyethyl)aniline
  • the aforementioned reactions with epoxides or hydroxy acrylates are appropriately effected within a temperature range from 20 to 140° C., preferably at not more than 120° C. and more preferably at not more than 100° C.
  • reaction with the epoxides gives rise to a secondary hydroxyl group and to a secondary or tertiary amino group on the nitrogen atom involved in the reaction.
  • amines suitable for reaction with the component MZ are, for example, aliphatic and araliphatic amines having at least one primary or secondary amino group, such as butylamine, ethylhexylamine, benzylamine, oleylamine, dibutylamine, xylylenediamine, 1,4-bis(4-aminophenoxy)benzene; aliphatic and araliphatic amino alcohols having at least one primary or secondary amino group, such as ethanolamine, butanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 2-amino-2-methylpropane-1,3-diol, 2-amino-2-ethylpropane-1,3-diol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris(hydroxymethyl)aminomethane; and alipha
  • polyfunctional acrylates suitable as component MZ are: di-, tri-, tetrafunctional polyester acrylates, polyether acrylates, polyether/ester acrylates, urethane or epoxy acrylates, mono-, di-, tri- or polyalkylene glycol diacrylates, for example mono-, di-, tri- or polyethylene glycol diacrylate, mono-, di-, tri- or polypropylene glycol diacrylate, butanediol diacrylate, hexane-1,6-diol diacrylate, trimethylolpropane triacrylate, neopentyl glycol propyleneoxy diacrylate, tricyclodecanediol diacrylate, glycerol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, di(trimethylolpropane) tetraacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate,
  • polyfunctional epoxides are: mono-, di-, tri- or polyalkylene glycol glycol diglycidyl ethers, for example: mono-, di-, tri- or polyethylene glycol diglycidyl ether, propanediol diglycidyl ether, di-, tri- or polypropylene glycol diglycidyl ether, butane-1,4-diol diglycidyl ether, hexane-1,6-diol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, di-, tri- or polyglycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol pentagly
  • monofunctional acrylates are alkyl acrylates, for example methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and lauryl acrylate; monoacrylates of short-chain ethers, such as tetrahydrofurfuryl acrylate, methoxyethoxyethyl acrylate, 1-butoxypropyl acrylate, cyclohexyloxymethyl acrylate, methoxymethoxyethyl acrylate, benzyloxymethyl acrylate, furfuryl acrylate, 2-butoxyethyl acrylate, 2-ethoxyethyl acrylate, allyloxymethyl acrylate, 1-ethoxybutyl acrylate, 1-ethoxy
  • Suitable hydroxy-functional acrylates are, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-(2-hydroxyethoxy)ethyl acrylate, 2-hydroxy-3-[3-(trimethoxysilyl)propoxy]propyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, polyethylene glycol acrylates, for example the AE-90, AE-200 and AE-400 products sold by NOF under the BLEMMER® trade name, polypropylene glycol acrylates for example the AP-150, AP-400 and AP-550 products sold by NOF under the BLEMMER® trade name and lactone-modified hydroxyethyl acrylates, for example the FA products sold by the DAICEL Corporation under the Placcel trade name.
  • Suitable monofunctional epoxides are, for example, aliphatic, cycloaliphatic and/or aromatic glycidyl ethers, for example C 1 -C 20 -alkyl glycidyl ethers, phenyl glycidyl ether, cresyl glycidyl ether, naphthyl glycidyl ether, butyl glycidyl ether, p-tert-butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, C 12 -C 14 glycidyl ethers, allyl glycidyl ether, 2,3-epoxypropyl neodecanoate (Cardura® E 10, Resolution Performance Products).
  • aromatic glycidyl ethers for example C 1 -C 20 -alkyl glycidyl ethers, phenyl glycidy
  • HX y —Z 1 —(XH) p+1 species of the general formula (III) in which Z 1 has at least one tertiary amino group and one amide group are listed hereinafter by way of example:
  • Corresponding species in which Z 1 has both a tertiary amino group and an amide group are generally not commercially available. They are preferably obtained by reacting one or more components D with one or more components B and/or C.
  • Component D is independently selected from the group of ethylenically unsaturated carboxylic acids, esters thereof and acid halides thereof, where at least one C ⁇ C double bond and at least one C ⁇ O double bond are in conjugated form and the C ⁇ O double bond is selected from the group of the carboxylic acids, the carboxylic esters and the carbonyl halides.
  • alkyl acrylates for example methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and lauryl acrylate; monoacrylates of short-chain ethers, such as tetrahydrofurfuryl acrylate, methoxyethoxyethyl acrylate, 1-butoxypropyl acrylate, cyclohexyloxymethyl acrylate, methoxymethoxyethyl acrylate, benzyloxymethyl acrylate, furfuryl acrylate, 2-butoxyethyl acrylate, 2-ethoxy
  • component D is selected from the acrylic esters, more preferably from the short-chain alkyl acrylates having a C 1 - to C 6 -alkyl chain. Most preferred are methyl acrylate and ethyl acrylate.
  • Component B is of the general formula (VI)
  • R 3 is independently H or a branched or unbranched, saturated or unsaturated organic radical having 1 to 12 carbon atoms, and
  • R 4 is independently a branched or unbranched, saturated or unsaturated organic radical having 2 to 12 carbon atoms and 1 to 3 tertiary amino groups, which may optionally also have 1 to 3 primary and/or secondary amino groups.
  • component B in which x assumes the value of 2 are butylamine, hexylamine, dibutylamine, diethylamine, dipropylamine, benzylamine, N-benzylmethylamine and N-phenylbenzylamine.
  • component B in which x assumes the value of 1 are N,N-dimethylaminoethylamine, N,N-dimethylaminopropylamine, N,N-diethylaminoethylamine, N,N-diethylaminopropylamine, tris[2-(methylamino)ethyl]amine, N,N-dimethyldipropylenetriamine, N,N-bis(3-aminopropyl)methylamine, tris(3-aminopropyl)amine, tris(2-aminoethyl)amine, 2-(2-methylaminoethyl)pyridine, 2-aminomethylpyridine, 4-aminomethylpyridine, 1-(3-aminopropyl)imidazole and N,N,N′-trimethylenediamine.
  • component B in which x assumes the value of 0 is bis(3-dimethylaminopropyl)amine.
  • Component C is of the general formula (VII)
  • R 5 is H or a branched or unbranched, saturated or unsaturated organic radical having 1 to 12 carbon atoms
  • R 6 is independently a branched or unbranched, saturated or unsaturated organic radical having 2 to 12 carbon atoms and 1 to 4 hydroxyl groups, which may optionally contain a tertiary amino group.
  • component C in which k assumes the value of 0 are diethanolamine, diisopropanolamine, dipropanolamine, N-(2′-hydroxyethyl)piperazine, 3-((2-hydroxyethyl)amino)-1-propanol.
  • component C in which k assumes the value of 1 are ethanolamine, propanolamine, 4-amino-1-butanol, 3-amino-1-butanol, 1-aminopropan-2-ol, 5-amino-1-pentanol, N-(2-hydroxyethyl)-N-methylpropylene-1,3-diamine, 2-amino-2-ethylpropane-1,3-diol, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-(2-hydroxyethyl)aniline, 1,1,1-tris(hydroxymethyl)methanamine, aminopropyldiethanolamine, glucosamine and 2-(2-aminoethoxy)ethanol.
  • the species of the general formula (III) in which the Z 1 radical has at least one tertiary amino group and one amide group is prepared in two steps.
  • the first step here is the addition of a primary or secondary amino group of a component B and/or C onto the C ⁇ C double bond of a component D in a Michael addition reaction.
  • the corresponding product is a Michael addition product and is referred to hereinafter as intermediate I.
  • These reactions are preferably effected within a temperature range from 0 to 100° C., more preferably from 10 to 80° C. and especially preferably from 15 to 50° C.
  • Primary amino groups are capable of reacting twice in a Michael addition.
  • the primary amino group of a component B or C first adds on to the C ⁇ C double bond of a component D to form a secondary amino group.
  • This secondary amino group is capable of reacting in a further Michael addition with a C ⁇ C double bond of a component D to form a tertiary amino group.
  • the double Michael addition product of a component B or C with two independently selected components D is also an intermediate I as described above.
  • At least one of the C ⁇ O double bonds present in the intermediate I is reacted with a primary or secondary amino group of a component B or C in an amidation reaction to form a species of general formula (III).
  • the C ⁇ O double bond present in the intermediate is in the form of a carboxylic ester group.
  • These reactions are preferably effected within a temperature range from 50 to 180° C., more preferably from 70 to 160° C. and especially preferably from 80 to 150° C.
  • the intermediate I has more than one C ⁇ O double bond selected from the group of the carboxylic acids, the carboxylic esters and the carbonyl halides, these can also be reacted in an amidation reaction with a primary or secondary amino group to give an amide group.
  • the cleavage products formed in the amidation reaction for example alcohol formed in the case of the preferred carboxylic ester hydrolysis, are removed from the reaction mixture during or after the reaction. In addition, any solvent used in the reaction is removed from the reaction mixture.
  • components B of formula (VI) and/or C of the general formula (VI I) for preparation of a species of general formula (III) in which Z 1 has at least one tertiary amino group and at least one amide group is not subject to any further restriction and is merely subject to the provision that the resulting product is a species of general formula (III).
  • the product contains 1 to 10 groups reactive toward isocyanate groups, and also at least one tertiary amino group and at least one amide group.
  • the invention also relates to a process for preparing the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein.
  • the polyisocyanate R(NCO) x is used preferably at least in an equimolar ratio to the alcohol Y—(OH) q , where the free NCO groups of the polyisocyanate R(NCO) x are preferably present at least in an equimolar ratio relative to the hydroxyl groups of the alcohol Y—(OH) q .
  • the polyisocyanate R(NCO) x is used in step i) in a molar excess, as a result of which a higher selectivity is achieved in that preferably at least one NCO group of the polyisocyanate is not converted in step i).
  • the unconverted polyisocyanate that remains owing to use in excess is preferably at least partly (but very substantially completely) removed from the reaction mixture, preferably by distillation, in order ultimately to keep the proportion of by-products formed therefrom at a low level.
  • the polyisocyanate worsens the quality of the process product and is considered to be environmentally harmful.
  • the polyisocyanates R(NCO) x used in the process of the invention are diisocyanates R(NCO) 2 and the alcohols Y—(OH) q used are monoalcohols Y—OH.
  • selectivity with regard to the preparation of the urethane covered by the general formula (V) which is produced in step i) is increased by using a diisocyanate R(NCO) 2 having two isocyanate groups of different reactivity. More preferably, the diisocyanate R(NCO) 2 having two isocyanate groups of different reactivity is selected from the group consisting of toluene 2,4-diisocyanate and isophorone diisocyanate.
  • the diisocyanate R(NCO) 2 is used relative to the monoalcohol Y—OH in a molar ratio of at least 1.1:1.0, more preferably of at least 2.0:1.0 and most preferably of at least 2.5:1.0. It is most preferred that, in step i), both one or more diisocyanates having isocyanate groups of different reactivity are used and a molar excess of isocyanate component in relation to the monoalcohol Y—OH is used.
  • the isocyanate addition according to the reactivity of the individual coreactants, can be effected within the temperature range which is customary for this kind of reaction from room temperature to about 150° C., preferably to 100° C., more preferably to 70° C.
  • catalysts such as tertiary amines, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N′-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane and the like, and also especially organic metal compounds, such as titanic esters, iron compounds such as iron(III) acetylacetonate, tin compounds, for example tin diacetate, tin dioctoate, tin dilaurate or the dialkyl derivatives of tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like.
  • These catalysts are typically used in amounts of 0.0001 to 0.1 part by weight per 100 parts by weight of diisocyanate.
  • inventive reaction products containing urethane and urea groups that are preparable by the process of the invention or the species of the general formula (I) that are present therein exhibit good dispersing action with regard to a broad spectrum of solids to be dispersed.
  • One way in which this is manifested is that solids having acidic, neutral and basic surfaces can each be effectively dispersed.
  • reaction products containing urethane and urea groups that are preparable by the process of the invention or the species of the general formula (I) that are present therein are of particularly high quality and universally usable as wetting agents and dispersants.
  • the reaction products containing urethane and urea groups that are preparable in accordance with the invention or the species of the general formula (I) that are present therein can be used successfully both in polar and in nonpolar binder systems, and at the same time exhibit excellent compatibility as wetting agents and dispersants or as dispersion stabilizers or as adhesion promoters. This ensures successful use in combination with a wide variety of different binders and coating materials.
  • reaction products containing urethane and urea groups that are preparable by the process of the invention or the species of the general formula (I) that are present therein enable flocculation-free miscibility of pastes, especially pigment pastes, or of the binders produced with these pastes.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein are suitable as dispersion stabilizers, especially also as emulsion stabilizers.
  • reaction products containing urethane and urea groups that are preparable by the process of the invention or the species of the general formula (I) that are present therein distinctly reduces the viscosity of the millbase introduced during the dispersion and, in this way, enables the production of formulations having a high solids content. In this way, for better environmental compatibility, the proportion of (volatile) solvents can be reduced.
  • reaction products containing urethane and urea groups that are preparable by the process of the invention or the species of the general formula (I) that are present therein with good stabilization of pigments or fillers, lower the millbase viscosity of corresponding varnishes, pastes or plastics formulations to such an extent that processing is possible at a high fill level without any adverse effect on the stability of the cured varnishes.
  • organic Y radical it is also possible to produce separating agents which can be used, for example, in the field of plastics production or in composite materials or fiber composite materials.
  • the non-aftertreated or -purified reaction products containing urethane and urea groups that are prepared by the process of the invention typically contain small amounts of products that are not species of the general formula (I) owing to side reactions that occur.
  • Possible side reactions using a diisocyanate R(NCO) x and a monoalcohol Y—OH are, for example, the double reaction of a diisocyanate R(NCO) 2 with a monoalcohol Y—OH to form a diurethane of the general formula Y—O—CO—NH—R—NH—CO—O—Y and the double reaction of a diisocyanate R(NCO) 2 with a species of the general formula (IIa) to form a diurea of the general formula A-CO—NH—R—NH—CO-A.
  • inventive reaction products containing urethane and urea groups may also contain a small amount of the unconverted urethane of the formula (V).
  • the use of appropriate amounts of a species of the general formula (IIa) in step ii) or optionally of a component of the general formula (III) in step iii) of the process of the invention allows the proportion of the urethane of the general formula (V) generally to be reduced almost to zero, which is usually advantageous in respect of the quality, especially for preparation of products of maximum homogeneity, and the avoidance of sediment and turbidity in the inventive reaction products containing urethane and urea groups.
  • step ii) or after optional step iii) of the process of the invention are preferably considered to have ended when an NCO content of ⁇ 0.1% is found.
  • inventive reaction products containing urethane and urea groups are environmentally friendly, have good storability and—in a corresponding manner to the inventive species of the general formula (I) as such—exhibit excellent properties as wetting agents and dispersants and as adhesion promoters.
  • the process of the invention can be conducted in neat form or in the presence of suitable solvents, solvent mixtures or other suitable carrier media.
  • suitable solvents or carrier media are all those that are unreactive or whose reactivity toward the coreactants under the reaction conditions chosen is negligible and in which the reactants and the reaction products are at least partly soluble.
  • hydrocarbons such as toluene, xylene, aliphatic and/or cycloaliphatic petroleum fractions, chlorinated hydrocarbons such as chloroform, trichloroethane, cyclic and acyclic ethers such as dioxane, tetrahydrofuran, polyalkylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, esters of mono-, di- or polycarboxylic acids such as ethyl acetate, butyl acetate, butyrolactone, dimethyl 2-methylglutarate, triacetin, phthalates or other plasticizers, di- or polycarboxylic esters, dialkyl esters of C 2 -C 4 dicarboxylic acids that are referred to as “dibasic esters”, alkyl glycol esters such as ethyl glycol acetate, methoxypropyl acetate, ketones such as methyl isobuty
  • the solvents should appropriately be selected such that they are inert with respect to the reactants under the reaction conditions.
  • the solvent(s) or carrier media are selected already taking account of the planned field of use.
  • the process product is to be used, for example, at a location where the presence of volatile organic compounds (VOCs) is undesirable, the formulation should be in very substantially solvent-free form or in carrier materials that are correspondingly regarded as being VOC-free.
  • the solvents used for the synthesis may remain in the reaction mixture or are wholly or partly removed and optionally replaced by other solvents or carrier media.
  • the solvent may be wholly or partly removed, for example, by distillation, optionally under reduced pressure and/or by azeotropic means with addition of water.
  • the active substance (compound of the general formula (I)) may alternatively be isolated by precipitation by means of addition of nonsolvents such as aliphatic hydrocarbons, for example hexane, followed by separation by means of filtration and optionally drying.
  • the active substance obtained by one of these methods can then be partly dissolved in a solvent suitable for the particular field of use or, if appropriate, be used in pure form, for example in powder coatings, or applied to inert supports.
  • the compounds can also be converted to a solid form by further known methods. Examples of such processes are microencapsulation, spray-drying, adsorption on a solid support such as SiO 2 , or the PGSS (particles from gas saturated solutions) method.
  • the XH groups still present in the inventive reaction product containing urethane and urea groups can be converted further in a subsequent reaction, for example reacted with carboxylic anhydrides.
  • the inventive reaction products containing urethane and urea groups serve as intermediates in the preparation of modified, likewise inventive reaction products containing urethane and urea groups.
  • the modified products can be used in the same fields as the as yet unmodified inventive reaction products containing urethane and urea groups.
  • the modification can, for example, increase or adjust the compatibility of the reaction products with respect to particular media.
  • Any tertiary amino groups present which may especially be present in the Z 1 and/or Z 2 radicals, can be converted with oxygen, peroxo compounds such as percarboxylic acids and hydrogen peroxide to amine oxides which can additionally be converted to salts with acids, for example hydrochloric acid.
  • the inventive reaction products containing urethane and urea groups or the species of general formula (I) that are present therein may contain tertiary amino groups, especially via the Z 1 and/or Z 2 radicals. All or some of these may be converted to salts.
  • the tertiary amino groups may, for example, be converted to corresponding ammonium salts with acids such as carboxylic acids, carboxylic acid derivatives, for example carbonyl halides, or phosphoric acids and esters thereof.
  • the inventive reaction products containing urethane and urea groups serve as intermediates in the preparation of likewise inventive reaction products containing urethane and urea groups that have been converted to salts.
  • the products that have been converted to salts can be used in the same fields as the inventive reaction products containing urethane and urea groups that have not been converted to salts. Conversion to salts can, for example, increase or adjust the compatibility of the reaction products with respect to particular media or affect the interaction with solid particles such as pigments and/or fillers.
  • inventive reaction products containing urethane and urea groups or the species of general formula (I) that are present therein contain preferably tertiary amino groups, especially in the Z 1 and/or Z 2 radicals. All or some of these may be converted to corresponding quaternary ammonium salts by reaction with quaternizing reagents.
  • inventive reaction products containing urethane and urea groups serve as intermediates in the preparation of quaternized, likewise inventive reaction products containing urethane and urea groups.
  • the quaternized products can be used in the same fields as the inventive reaction products containing urethane and urea groups that have not been quaternized. Quaternization can, for example, increase or adjust the compatibility of the reaction products with respect to particular media or affect the interaction with solid particles such as pigments and/or fillers.
  • Suitable quaternizing reagents may be chosen, for example, from the group of the alkyl halides and aralkyl halides or aralkyl compounds having leaving groups, such as triflate, methylsulfate or tosylate, which can enter into nucleophilic substitution reactions with tertiary amines, or oxiranes such as alkylene oxides or glycidyl ethers, in the presence of acids or derivatives thereof, such as carboxylic acids, sulfonic acids or phosphoric acids and the esters or halides thereof.
  • leaving groups such as triflate, methylsulfate or tosylate
  • oxiranes such as alkylene oxides or glycidyl ethers
  • quaternizing reagents examples include benzyl chloride, 2- or 4-vinylbenzyl chloride, methyl chloride, methyl iodide, methyl tosylate or dimethyl sulfate. Preference is given to benzyl chloride and 4-vinylbenzyl chloride.
  • a further means of quaternization is the use of glycidyl ethers in the presence of acids.
  • suitable glycidyl ethers are glycidyl methacrylate, alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether and C13/C15 glycidyl ethers (trade name, for example, Grilonit RV 1814) or aryl glycidyl ethers such as cresyl glycidyl ether.
  • Acids suitable for this quaternization reaction are, for example, carboxylic acids such as benzoic acid, acetic acid or lactic acid. Further acids are acidic phosphoric esters having one or two ester groups.
  • the present invention further relates to the use of the above-described inventive reaction products containing urethane and urea groups or of the species of the general formula (I) present therein as an additive, preferably as a wetting agent and/or dispersant and/or dispersion stabilizer and/or adhesion promoter in compositions such as solid blends or coatings, especially varnishes, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, potting compounds, spackling compounds, printing inks and other inks.
  • a wetting agent and/or dispersant and/or dispersion stabilizer and/or adhesion promoter in compositions such as solid blends or coatings, especially varnishes, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, potting compounds, spackling compounds, printing inks and other inks.
  • the invention also relates to the compositions detailed above, such as solid blends or coatings, especially varnishes, plastics, pigment pastes, sealants, cosmetics, ceramics, adhesives, potting compounds, spackling compounds, printing inks and other inks.
  • the solid blends preferably contain particles and/or fibers that have been treated with the above-described inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein.
  • the invention relates to varnishes and plastics comprising the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein find use, for example, as aluminum passivators, dispersants, dispersion stabilizers, wetting agents or adhesion promoters and can be used, for example, in pigmented and/or filler-containing products, for example pigment concentrates or pastes, coating compositions, sealants, plastics, ceramics, cosmetics, adhesives, potting compounds, spackling compounds, printing inks and/or other inks. Preference is given to pigment concentrates which can be mixed with appropriate letdown systems, by means of which pigmented varnishes are produced.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein may be used, for example, in the production or processing of varnishes, printing inks, other inks, for example for inkjet printing, paper coating, leather and textile dyes, pastes, pigment concentrates, ceramics, adhesives and sealants, potting compounds, plastics and cosmetic formulations, especially when these contain solids such as pigments and/or fillers (including fibrous fillers).
  • molding compounds based on synthetic, semisynthetic or natural macromolecular substances, such as polyvinyl chloride, saturated or unsaturated polyesters, polyurethanes, polystyrenes, polyacrylates, polyamides, epoxy resins, polyolefins such as polyethylene or polypropylene.
  • synthetic, semisynthetic or natural macromolecular substances such as polyvinyl chloride, saturated or unsaturated polyesters, polyurethanes, polystyrenes, polyacrylates, polyamides, epoxy resins, polyolefins such as polyethylene or polypropylene.
  • these can be used for production of potting compounds, casting compounds, PVC plastisols, gelcoats, polymer concrete, printed circuit boards, industrial varnishes, wood and furniture varnishes, motor vehicle paints, marine paints, anticorrosion paints, can and coil coatings or decorating paints and architectural paints.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein can be used not just in letdown systems for pigmented varnishes. It is likewise possible to use them in a wide range of formulations or products, such as resins, oils, greases, lubricants, rubber materials, sealants, printing inks, other inks, adhesives, waxes or coating compositions.
  • the concentrates can also be used in formulations which are produced in the personal care industry or in electrical applications in the electronics industry, in the marine industry, in the context of medical applications, in the construction industry or in the automobile industry. Examples include electronic paper, such as the display in E-books, the encapsulation of microelectronic chips and printed circuit boards, underwater skin coatings for ships, such as antifouling coatings, silicone tubes or sliding additives for brake components.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein can advantageously also be used in the production of color filters for liquid-crystal displays, liquid-crystal screens, color resolution devices, sensors, plasma screens, SED-based displays (Surface conduction Electron emitter Display), and for MLCCs (multilayer ceramic compounds).
  • MLCC technology is employed in the production of microchips and printed circuit boards.
  • cosmetic preparations can serve, for example, for production of cosmetic formulations such as makeup, face powder, lipsticks, hair dyes, creams, nail varnishes and sunscreen preparations. These may be in the customary forms, for example in the form of W/O or O/W emulsions, solutions, gels, creams, lotions or sprays.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein can advantageously be used in dispersions used for production of these formulations.
  • These may comprise the carrier media that are customary for these purposes in cosmetics, such as water, castor oils or silicone oils, and solids such as organic and inorganic pigments, such as titanium dioxide or iron oxide.
  • the product comprising the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein and also pigments and/or fillers is a varnish, or a pigment concentrate for coating compositions.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein in any pigment-containing and/or filler-containing products.
  • the pigment concentrates are compositions which, as well as the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein, comprise, for example, organic solvents and at least one pigment.
  • organic solvents especially contain only small proportions, if any, of organic polymers as binders.
  • binders of this kind are advantageously present in the corresponding letdown systems and are described hereinafter.
  • Organic solvents used are especially the typical organic solvents that are known to the person skilled in the art and are used in the field of the coatings and paints industry, such as aliphatic solvents, cycloaliphatic solvents, aromatic solvents such as toluene, xylene, solvent naphtha, ethers, esters and/or ketones, for example butyl glycol, butyl diglycol, butyl acetate, methyl isobutyl ketone, methyl ethyl ketone and/or solvents such as methoxypropyl acetate, diacetone alcohol.
  • Pigments used are the pigments known to those skilled in the art. Frequently, combinations of various pigments are used to obtain the desired properties.
  • Examples of pigments are monoazo, diazo, triazo and polyazo pigments, oxazine pigments, dioxazine pigments, thiazine pigments, diketopyrrolopyrroles, phthalocyanines, ultramarine and other metal complex pigments, indigoid pigments, diphenylmethane pigments, triarylmethane pigments, xanthene pigments, acridine pigments, quinacridone pigments, methine pigments, anthraquinone, pyranthrone pigments and perylene pigments and other polycyclic carbonyl pigments, inorganic pigments such as carbon black pigments and/or pigments based on carbon black, graphite, zinc, titanium dioxide, zinc oxide, zinc sulfide, zinc phosphate, barium sulfate, lithopone, iron
  • nanoscale organic or inorganic solids having particle sizes below 100 nm in at least one dimension, such as certain types of carbon black or other allotropic forms of carbon, such as single-wall CNTs, multiwall CNTs and graphene.
  • the particle size is determined, for example, by means of transmission electron microscopy, analytical ultracentrifugation or methods of light scattering. Mention should likewise be made of particles consisting of a metal or semimetal oxide or hydroxide, and also particles consisting of mixed metal and/or semimetal oxides or hydroxides.
  • the oxides and/or oxide hydroxides of aluminum, silicon, zinc, titanium, etc. can be used to produce such extremely finely divided solids.
  • oxide or hydroxide or oxide-hydroxide particles can be produced by a wide variety of different processes, for example ion exchange processes, plasma processes, sol-gel processes, precipitation, comminution (for example by grinding) or flame hydrolysis. All the aforementioned pigments may be in surface-modified form and have basic, acidic or neutral groups at the surface.
  • red pigments are C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200,
  • blue pigments are C. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78,and 79.
  • green pigments are C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 or 59.
  • Examples of yellow pigments are C. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184,
  • violet pigments are C. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
  • orange pigments are C. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, and 79.
  • black pigments are C. I. Pigment Black 7, 11, 30, 33.
  • the respective products, especially the coating compositions comprise fillers
  • these are, for example, the fillers known to those skilled in the art.
  • pulverulent or fibrous fillers are, for example, those formed from pulverulent or fibrous particles of aluminum oxide, aluminum hydroxide, silicon dioxide, kieselguhr, siliceous earth, quartz, silica gel, talc, kaolin, mica, perlite, feldspar, ground shale, calcium sulfate, barium sulfate, calcium carbonate, calcite, dolomite, glass or carbon.
  • the fibers used may be organic and/or inorganic in nature and may likewise be used as reinforcing agents. Further examples of pigments or fillers can be found, for example, in U.S. Pat. No. 4,795,796. It is likewise also possible for flame retardants, if the compounds of the invention are not already being used in customary additive amounts for this purpose, such as aluminum hydroxide or magnesium hydroxide, and flatting agents, such as silicas, to be dispersed and stabilized particularly efficiently by means of the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein are especially also suitable for production of solids concentrates, such as pigment concentrates.
  • the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein are initially charged in a carrier medium, such as organic solvents, plasticizers and/or water, and the solids to be dispersed are added while stirring.
  • these concentrates may comprise binders and/or other auxiliaries.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein to produce free-flowing solids concentrates from pigment presscakes. This is done by mixing the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein into the presscake, which may still comprise organic solvents, plasticizers and/or water, and dispersing the mixture thus obtained.
  • the solids concentrates produced in various ways can then be incorporated into different substrates, for example alkyd resins, polyester resins, acrylate resins, polyurethane resins or epoxy resins.
  • Pigments can alternatively be dispersed in a solvent-free manner directly into the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein, and are then particularly suitable for pigmentation of thermoplastic and thermoset plastics formulations.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein to provide products that increase the adhesion of coatings to substrates.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein are mixed into the appropriate refinish coatings or overcoating paints (for example based on air-drying 2-component PU formulations or alkyd systems).
  • the coating of a substrate for example of an old paint or of a metal or plastic workpiece, is then effected under standard conditions, the use of the adhesion promoter making it possible to achieve a distinct improvement in adhesion on the substrate.
  • the adhesion can generally be determined by means of the scratch test according to DIN 53230 or cross-cutting DIN EN ISO 2409, pull-off method according to DIN EN 24624, ball impact test, Erichsen test, mandrel bending test or steam jet test.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein it is not necessary to subject either the formulation or the curing procedure to significant alterations.
  • there any impairment in the most important properties of the finished varnish layer such as degree of crosslinking, solvent resistance, gloss, leveling, resulting from the use of the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein.
  • the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein are used in such amounts that, in the product of ultimate interest for further use, there is preferably a proportion of the wetting agent and dispersant of the invention or of the adhesion promoter of the invention, of the inventive reaction products containing urethane and urea groups or of the species of the general formula (I) present therein of 0.01% to 10% by weight, based on the total amount of the respective product. Alternatively, higher proportions are possible.
  • the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein are used in an amount of preferably 0.5% to 100% by weight. If solids that are difficult to disperse are used, the amount of wetting agent and dispersant of the invention used, the inventive reaction products containing urethane and urea groups or the species of the general formula (I) present therein, may quite possibly be higher. The amount is generally dependent on the surface area of the substance to be dispersed which is to be covered. A factor of significance may thus, for example, be what kind of pigment is involved.
  • Typical dosages of the wetting agent and dispersant i.e. the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein, are, for example, 1% to 20% by weight for inorganic pigments and 10% to 50% by weight for organic pigments, based in each case on the solids to be dispersed, especially the pigment. In the case of very finely divided pigments (for example some carbon blacks), even added amounts of 30% to 90% or may be advisable.
  • Criteria employed for sufficient pigment stabilization may, for example, be gloss and transparency of the coating compositions or the degree of floating.
  • the dispersion of the solids can be effected in the form of an individual dispersion or else as a mixed dispersion with multiple pigments at the same time, the best results generally being achievable in individual dispersions.
  • opposing charges on the surfaces of the solids may result in increased agglomeration in the liquid phase.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein it is frequently possible to achieve the same charge, generally a positive charge, of all particles and hence to avoid instabilities resulting from differences in charge.
  • the dispersants i.e. the inventive reaction products containing urethane and urea groups or the species of general formula (I) that are present therein, achieve their optimal effect when added to the millbase, especially when the solid to be dispersed is at first mixed solely with the additive and optionally solvents (“premix”), since the additive can then be preferably adsorbed onto the surface of the solids without having to compete with the binder polymers. In practice, however, this course of action is necessary only in exceptional cases.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein can also be used subsequently (as what are called “post-additives”), for example in order to solve floating or flocculation problems in a batch that has already been let down. In general, however, elevated additive dosages are required in this case.
  • the products may additionally comprise an organic polymer as a further binder. Binders of this kind are known to those skilled in the art.
  • This at least one further binder may be introduced, for example, via a letdown system which is mixed, for example, with a pigment concentrate comprising the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein, such that the product in question is a pigmented varnish.
  • a product is considered to be a system which comprises a polymeric resin or organic polymer as binder and hence is capable of forming a solid organic, polymeric matrix under suitable curing conditions (for example a coating composition).
  • a product likewise refers to a system which, through simple mixing with a component comprising a binder, is capable of forming such an organic polymeric matrix (for example a pigment concentrate).
  • Nonexclusive examples of materials used include the alkyd resins, polyester resins, acrylate resins, polyurethane resins, cellulose nitrates, cellulose acetobutyrates, melamines, chloro rubbers and/or epoxy resins that are known to those skilled in the art.
  • Examples of water-based coatings are cathodic or anodic electrocoats, for example for automobile bodywork. Further examples are renders, silicate paints, disperse dyes, water-based varnishes based on water-thinnable alkyds, alkyd emulsions, hybrid systems, 2-component systems, polyurethane dispersions and acrylate dispersions.
  • Both 1-component systems and 2-component systems are possible, in which latter case there are generally also polyisocyanates, melamine resins and/or polyamide resins present as the typical crosslinking agents familiar to the person skilled in the art in a second component.
  • a further variant concerns a 2-component (2K) coating composition or a 2K varnish comprising an epoxy resin in the binder component and a polyamide resin in the crosslinker component.
  • the coating compositions that are preferred as products may be water-based or solvent-based.
  • Water-based is understood to mean that the coating composition comprises mainly water as solvent. More particularly, in the case of a water-based coating composition, preferably not more than 10% by weight of organic solvents, based on the total amount of solvents, is present in the coating composition.
  • a solvent-based coating composition is considered to be one that contains not more than 5% by weight, preferably not more than 2% by weight, of water, based on the total amount of solvents.
  • Useful further product components include, for example, photoinitiators, defoamers, wetting agents, film-forming auxiliaries, such as cellulose derivatives (for example cellulose nitrates, cellulose acetates, cellulose acetobutyrate), reactive diluents, leveling agents, dispersants and/or rheology control additives.
  • cellulose derivatives for example cellulose nitrates, cellulose acetates, cellulose acetobutyrate
  • reactive diluents for example cellulose nitrates, cellulose acetates, cellulose acetobutyrate
  • leveling agents for example cellulose nitrates, cellulose acetates, cellulose acetobutyrate
  • dispersants for example, dispersants and/or rheology control additives.
  • the production of the pigment concentrates and coating composition that are preferred as products is effected via methods familiar to those skilled in the art.
  • the known methods are used, for example stepwise addition with stirring and mixing of the constituents of the coating composition in customary mixing units, such as stirred tanks or dissolvers.
  • coatings or varnish layers are produced via techniques of application to a substrate that are familiar to those skilled in the art and subsequent curing methods.
  • Application is effected, for example, by the known injecting, spraying, painting, rolling, pouring, impregnating and/or dipping methods.
  • the application of the coating composition to a substrate is followed by curing or drying by standard methods.
  • the coating composition applied may be curable by physical drying, by thermal means and/or with application of actinic radiation (radiative curing), preferably UV radiation and electron beams.
  • Radiative curing can be effected, for example, in the range from about 10° C. to about 400° C., according to the nature of the coating composition and/or of the substrate.
  • the duration of curing is also individually dependent, for example, on the nature of the curing method (thermal or actinic), the nature of the coating composition used and/or the substrates.
  • the substrate here may be moving or else at rest.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein may also be used as adhesion promoters.
  • inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein may also be used as viscosity reducers and compatibilizers in synthetic resins.
  • synthetic resins of this kind are what are called the “sheet molding compounds” (SMCs) and “bulk molding compounds” (BMCs), which consist of unsaturated polyester resins with a high filler and fiber content. The production and processing thereof is described by way of example in U.S. Pat. No. 4,777,195.
  • PS polystyrene
  • the inventive reaction products containing urethane and urea groups or the species of the general formula (I) that are present therein can bring about compatibilization between PS and unsaturated polyester resin, which increases the storage stability and processing reliability of such mixtures.
  • phase transfer effects for example, in incompatible polyol mixtures, polyol-isocyanate mixtures or polyol-blowing agent mixtures (as used, for example, in polyurethane production).
  • the present invention is additionally elucidated hereinafter by examples which follow.
  • the stated molecular weights are number-average values.
  • the molecular weights or number-average molecular weights M n in the event that titratable hydroxyl or amino groups are present, are determined by end group determination via the finding of the OH number or the amine number.
  • the number-average molecular weight is determined by means of gel permeation chromatography against a polystyrene standard.
  • the sample (2.0 ⁇ 0.1 g of test substance) is weighed into an aluminum dish that has been dried beforehand and dried in a drying cabinet at 150° C. for 10 minutes, cooled down in a desiccator, and then re-weighed. The residue corresponds to the solids content.
  • the OH number is determined according to DIN ISO 4629 by acetylation with an excess of acetic anhydride. Subsequently, the excess acetic anhydride is hydrolyzed to acetic acid by addition of water and back-titrated with ethanolic KOH solution. The OH number indicates the amount of KOH in mg equivalent to the amount of acetic acid bound in the acetylation of 1 g of substance.
  • the amine number is understood to mean the amount of KOH in mg corresponding to the amine content of 1 g of substance.
  • the amine number is determined according to DIN 16945 by potentiometric titration with 0.1 N perchloric acid in acetic acid.
  • DMAE N,N-dimethylaminoethanol manufacturer: BASF DEEA N,N-diethylethanolamine
  • BASF DMEA N,N-dimethylethanolamine manufacturer: BASF GLY glycerol
  • Merck Jeffcat DPA N-(3-dimethylaminopropyl)-N,N-diisopropanol- 1-ylamine manufacturer: Huntsman Corp.
  • X g of the alcohol Y—(OH) q which is anhydrous, and alkali-free in the case of polyethers, are metered in gradually such that the temperature does not exceed 55° C. After the metered addition, the mixture is stirred at 55° C. for a further 3 hours.
  • the excess TDI is removed from the reaction mixture by means of a thin-film evaporator at 150° C.
  • the residual TDI content is ⁇ 1%.
  • the urethanes of the general formula (V) are identified by serial numbers preceded by M in the table below.
  • MPEG 350 methoxy polyethylene glycol, Mn 350
  • DBTL dibutyltin dilaurate
  • the OH number of the reaction product is 72 mg KOH/g.
  • 35 g of an alpha,omega-dihydroxyalkyl-functional dimethylpolysiloxane with M n about 900 g/mol are reacted with 75 g of epsilon-caprolactone.
  • the mixture with addition of 0.035 g of DBTL is left to react at 160° C. in an N 2 atmosphere for about 8 hours.
  • the reaction has ended when there is a solids content of >98%.
  • the alpha,omega-hydroxyalkyl-functional dimethylpolysiloxane as starter alcohol is obtained in a known manner, by addition of suitable unsaturated alcohols (for example the allyl alcohol used in this example) onto dimethylpolysiloxanes bearing terminal silane units.
  • a four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen inlet tube is initially charged with x g of urethane M of the formula (V) and heated to 80° C. while stirring under nitrogen.
  • y 1 g of a component of the general formula (IIa) or of the mixture of y 1 g of a component of the general formula (IIa) and y 2 g of a component of the general formula (III) are added and the reaction temperature is raised to 120° C. Turbidity may arise, which dissolves in the course of the reaction.
  • the progress of the reaction is followed by means of titrimetric determination of the NCO number to EN ISO 9369.
  • a small amount y 2 (in g) of an optional component of the general formula (III) can also be added after the main reaction, in order to fully convert residual amounts of isocyanate and to obtain particularly storage-stable products. Dilution with MPA is optionally possible during or after the reaction.
  • reaction products containing urethane and urea groups comprising at least one species of the general formula (I), are identified hereinafter by serial numbers preceded by MA.
  • a reaction vessel provided with a stirrer, thermometer, reflux condenser and nitrogen inlet tube is initially charged with x g of a polyisocyanate R(NCO) x together with y 3 g of an alcohol Y—(OH) q , which are heated at 50° C. while stirring under nitrogen.
  • the reaction temperature is increased to 70° C.
  • y 1 g of a species of the general formula (IIa) are added and the reaction temperature is raised to 95° C.
  • the progress of the reaction is still followed by means of titrimetric determination of the NCO number to EN ISO 9369.
  • the conversion of the polyisocyanate R(NCO) x is completed or, if appropriate, further aminic bonding groups are introduced by adding to the mixture—in the case of the presence of residual NCO groups after the reaction with the species of the general formula (IIa)—y 2 g of a component of the general formula (III).
  • the reaction has ended when, by titrimetric determination of the NCO number to EN ISO 9369, an NCO value of ⁇ 0.01 is determined. Dilution with MPA is optionally possible during or after the reaction.
  • inventive reaction products containing urethane and urea groups comprising at least one species of the general formula (I), as wetting and dispersing additives for production of pigment concentrates and use thereof in paint systems.
  • Paraloid B-66 thermoplastic acrylate resin manufacturer: DOW Chemicals Vinnol E 15/45 copolymer resin based on vinyl chloride and vinyl acetate, manufacturer: Wacker Chemie NC E 510 nitrocellulose, manufacturer: Dow Wolff Cellulosics GmbH Vialkyd AC 433 75% alkyd resin, manufacturer: Allnex Epikote 1001 75% epoxy resin based on bisphenol A, manufacturer: Hexion Aradur 115 ⁇ 70 polyamidoamine, manufacturer: Huntsman Joncryl 500 hydroxy-functional acrylic resin, manufacturer: BASF Laropal A 81 aldehyde resin, manufacturer: BASF Dynapol LH 830 (60%) polyester resin in solvent naphtha and butylglycol, manufacturer: Evonik Dynapol 1203 (50%) nonionic protected sulfonic acid catalyst, 50% in xylene, manufacturer: Evonik Cymel 303 amino crosslinker, manufacturer: Allnex Nacure 2500 p-toluenesulfonic acid, manufacturer
  • the Paraloid B-66 dispersion resin, solvent, dispersing additive and pigment were weighed into 100 mL glass bottles so as to obtain 50 g of millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.
  • TPA 1 TPA 2 TPA 3 black (red) (violet) Paraloid B-66 (50% in xylene) 24.0 24.0 24.0 Raven Ultra 5000 III 6.0 Paliogen Red L 3880 HD 8.0 Hostaperm RL-NF 5.0 Dispersant (100%/50%) 4.2/8.4 2.0/4.0 2.0/4.0 n-Butanol 5.0 5.0 5.0 PMA by solids content of the 11.0/9.0 14.0/12.0 dispersing additive (100%/50%) Butyl acetate by solids content of the 10.8/6.6 dispersing additive (100%/50%) Total pigment content (%) 12 16 10 Dispersant (% s.o.p.) 70 25 40
  • the millbase viscosity of the TPA dispersions was determined with a Rheological Stresstech Rheometer (plate/cone, 25 mm, 1°) at 23° C.
  • TPA 1 black
  • TPA 2 red
  • TPA 3 violet
  • inventive dispersing additives MA19, MA22 and MA59 have a significant viscosity-reducing effect compared to the prior art MA56* to MA58* in TPA dispersions of 3 different pigments, which is manifested even at low shear rates.
  • Paraloid B-66, solvent and leveling additive were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.
  • TPA letdown system and the TPA-based pigment dispersion were weighed into a PE cup and mixed by spatula. Subsequently, all the final TPA letdown systems were homogenized in an ANDALOK shaker for 10 min.
  • the pigmented TPA letdown systems were bar-coated onto PE film (50 ⁇ m or 100 ⁇ m) and dried at 22° C. for 24 h. Subsequently, the haze and gloss were measured with a BYK micro haze plus instrument at an angle of 20°. In each case, low values for haze and high values for gloss are considered to be positive results. In addition, the optical color intensity and transparency through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable).
  • TPA-B1 (red) Masstone Masstone Masstone 100 ⁇ m 100 ⁇ m 100 ⁇ m PE film Dispersing additive PE film PE film Transparency/ in the millbase Haze Gloss 20° color intensity MAQ5* 87 60 5 MA55* 47 67 4 MA58* 20 73 4 MA22 11 78 2 MA59 18 77 1-2 MA47 12 78 2 TPA-B2 (violet) Masstone Masstone Masstone 100 ⁇ m 100 ⁇ m 50 ⁇ m PE film Dispersing additive PE film PE film Transparency/ in the millbase Haze Gloss 20° color intensity MAQ5* 131 52 5 MA55* 50 71 4 MA22 38 74 3 MA59 36 75 1-2 MA47 45 72 3 *not in accordance with the invention
  • inventive dispersing additives MA22, MA59 and MA47 exhibit lower haze, better gloss values and higher transparency and color intensity compared to the prior art MAQ5*, MA55* and MA58* for TPA-based varnish systems.
  • the Laropal A81 dispersion resin (60 parts) was weighed into a 2.5 L PE bucket together with PMA (40 parts) and homogenized by means of a Dispermat CV (65 mm toothed disk) at 2000 rpm for 30 min. Subsequently, the solution of the dispersion resin, solvent, dispersing additive and pigment was weighed into 100 mL glass bottles so as to obtain 50 g of millbase. Subsequently, 50 g of glass beads (1 mm) were weighed in.
  • the millbase viscosity of the Laropal A81 dispersions was determined with a Rheological Stresstech Rheometer (plate/cone, 25 mm, 1°) at 23° C.
  • inventive dispersing additives MA22, MA35 and MA59 have a significant viscosity-reducing effect compared to the prior art MA54*, MA57* and MA58* in Laropal A81 dispersions of 3 different pigments, which is manifested even at low shear rates.
  • Binder, solvent and substrate wetting agent were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.
  • Binder, solvent and substrate wetting agent were weighed into a 2.5 L PE bucket and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.
  • the epoxy component and the amine component of the 2-component varnish are weighed out separately in a 2.5 L PE bucket and in an 800 mL PE beaker respectively, and homogenized with a Dispermat CV (65 mm toothed disk) at 2000 rpm for 5 min.
  • the Laropal A81-based pigment dispersions and the respective clearcoats were weighed into a PE cup and mixed by hand with a spatula.
  • the pigment dispersion was incorporated into the epoxy component prior to the amine component.
  • all pigmented varnishes were homogenized in an ANDALOK shaker for 10 min.
  • NC1-B3 blue
  • NC1 16.0 LA 3 blue
  • 4.0 Pigment content 3.0 (%)
  • the pigmented nitrocellulose varnish NC1-B3 (blue) was bar-coated onto PE film (50 ⁇ m) and dried at 22° C. for 24 h. Then the optical transparency and color intensity through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable). The colorimetric assessment of the drawdowns was conducted with a BYK-Gardner color guide D65/10° in the CIELab color space (L, a, b).
  • the pigmented baking varnishes JC1-B1 to JC1-B3 were bar-coated onto PE film (50 ⁇ m), flashed off at 22° C. for 15 min and baked at 150° C. for 20 min. Subsequently, haze and gloss were measured with a BYK micro haze plus instrument at an angle of 20°. In each case, low values for haze and high values for gloss are considered to be positive results. In addition, the optical transparency and color intensity through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable).
  • the pigmented 2-component epoxy varnish 2KE1-B1 was bar-coated onto PE film (50 ⁇ m) and dried at 22° C. for 24 h.
  • the formulation 2KE1-B4 was poured onto a PE film and then likewise dried at 22° C. for 24 h.
  • haze and gloss were measured with a BYK micro haze plus instrument at an angle of 20°. In each case, low values for haze and high values for gloss are considered to be positive results.
  • the optical transparency and color intensity through the drawdowns onto PE film was assessed using grades 1 (excellent) to 5 (unacceptable).
  • the components of the pigment concentrates PKR1 to PKR5 based on the inorganic red pigment BAYFERROX red 130M were each weighed into a PE cup and dispersed by means of a Dispermat CV with a toothed disk at a peripheral speed of 18 m/s at 40° C. for 30 min.
  • the components of the pigment concentrates PKG1 to PKG5 based on Heliogen Green L8735 were each weighed into a PE cup and dispersed by means of a Dispermat CV with a toothed disk at a peripheral speed of 23 m/s at 40° C. for 40 min.
  • the components of the pigment concentrates PKS1 to PKS5 based on Special black 100 were each weighed into a PE cup and dispersed by means of a Dispermat CV with a toothed disk at a peripheral speed of 23 m/s at 40° C. for 60 min. Subsequently, the black pigment dispersions were homogenized with 11.7 g of Dynapol LH 830 (60%) and 5.0 g of butyldiglycol acetate to give the finished pigment concentrates.
  • the pigment concentrates were analyzed by means of a rotary viscometer (Stress Tech Instrument, cone-plate geometry, cone diameter 2.5 cm, cone angle 1°, temperature 21° C.) at various shear rates (1 s ⁇ 1 , 10 s ⁇ 1 , 100 s ⁇ 1 ).
  • letdown system part 1 The components of letdown system part 1 were each weighed into large PE beakers and dispersed by means of a Dispermat CV with a toothed disk at a peripheral speed of 18 m/s at 40° C. for 20 min. Subsequently, the white dispersions were homogenized with the part 2 components to give the finished letdown systems.
  • the pigment concentrates PKR1, PKG1 and PKS1 were each formulated with the corresponding white base ASW1 using the same dispersing additive.
  • the final test systems TSRW1 (PKR1+ASW1), TSGW1 (PKG1+ASW1) and TSSW1 (PKS1+ASW1) contain, for example, DISPERBYK-170 only as prior art dispersing additive. The same applies analogously to the other inventive examples in the table below.
  • the final test systems are formulated by weighing white base and pigment concentrate in each case together into a sealable vessel. The mixture is homogenized in a Skandex shaker for ten minutes. Subsequently, the varnishes are applied to aluminum sheet by means of a spiral coating bar in a wet film layer thickness of 80 ⁇ m. In a coil oven, the varnishes are baked at 320° C. for 33 seconds with peak metal temperature 232° C. A dry layer thickness of about 18 ⁇ m is achieved.
  • a rubout test is also conducted in order to determine the difference in shade ( ⁇ E) between rubbed and unrubbed surface within the rub.
  • ⁇ E difference in shade
  • a portion of the final test systems that have been homogenized on the Skandex shaker are applied again to aluminum sheet by means of a spiral coating bar in a wet film layer thickness of 80 ⁇ m.
  • a portion of the varnish applied is rubbed (sheared) in horizontal direction in each case using a finger.
  • the varnishes are baked in a coil oven at 320° C. for 33 seconds with peak metal temperature 232° C.
  • gloss is measured at an angle of 20° with a BYK micro haze plus.
  • TSRW1-5 TSGW1-5 TSSW1-5 Bayferrox red Heliogen Green Special black 130M L8735 100 DISPERBYK-170* 55 79 80 (30%) MAS6 (40%) 76 84 86 MAS8 (40%) 75 92 85 MAS9 (40%) 72 88 86 MAQ5* (40%) 65 66 80

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EP3320011A1 (fr) 2018-05-16
US20220282021A1 (en) 2022-09-08
CN107709393A (zh) 2018-02-16
WO2017005924A1 (fr) 2017-01-12
US11879032B2 (en) 2024-01-23
EP3320011B1 (fr) 2019-09-25

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