WO2016082058A1 - Dispersants à base d'uréthane - Google Patents

Dispersants à base d'uréthane Download PDF

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Publication number
WO2016082058A1
WO2016082058A1 PCT/CN2014/001051 CN2014001051W WO2016082058A1 WO 2016082058 A1 WO2016082058 A1 WO 2016082058A1 CN 2014001051 W CN2014001051 W CN 2014001051W WO 2016082058 A1 WO2016082058 A1 WO 2016082058A1
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WO
WIPO (PCT)
Prior art keywords
dispersant
isocyanate
group
independently selected
mono
Prior art date
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PCT/CN2014/001051
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English (en)
Inventor
Hung-Yi Lin
Chun-Hung YEN
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Deuchem (Shanghai) Chemical Co., Ltd.
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Filing date
Publication date
Application filed by Deuchem (Shanghai) Chemical Co., Ltd. filed Critical Deuchem (Shanghai) Chemical Co., Ltd.
Priority to PCT/CN2014/001051 priority Critical patent/WO2016082058A1/fr
Priority to EP14843193.5A priority patent/EP3046661A4/fr
Priority to CN201510144172.0A priority patent/CN106146796A/zh
Publication of WO2016082058A1 publication Critical patent/WO2016082058A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment

Definitions

  • the dispersant comprises an efficiently multiple anchoring moieties having amide, urea and urethane group which are concentrating distributed in dispersant molecule, and attached by solvent solubilizing chain structure.
  • the chemical structures described hereinbefore are suitable more particularly for preparing pigment concentrates and also for stabilizing in binders, coating materials, ink compositions, plastics and polymeric mixtures. As wetting and dispersing agents they reduce the viscosity of such system, improve the storage stability and fluid properties, and may also enhance the color strength.
  • a multiplicity of different urethane or polyurethane dispersants contain poly (ethylene oxide) chain which be present in lateral and/or terminal chains attached to the polyurethane backbone and collocate with versatile anchoring groups.
  • WO 97/19120 consider an water-dispersible unsaturated polyurethane dispersant which comprises pendant unsaturated alkyl group, pendant sulphonic acid salt and polyalkylene oxide. It discloses that the polyurethane is suitable for preparation of stably aqueous dispersion of hydrophobic polymer and pigment dispersions.
  • U.S. Pat. No. 2009/0221745 A1 described a polyepoxide/amine type dispersant which based on polyepoxide main chain with small amine molecule (benzylamine or ethanolamine) as anchor to interact with pigment surface and polyether amine (Trademark, from HUNTSMAN) as solubilizing tail to extend in solvent and binder medium to provide stabilization mechanism.
  • the wetting and dispersing agent is highly compatible with general binder and solvent system.
  • U.S. Pat. No. 8017686 B2 mention a novel polyurethane dispersant binder which having a polyurethane backbone having both pendant hydrophilic and hydrophobic polyalkylene oxide based side groups.
  • the content of polyalkylene oxide in the polyurethane dispersant resin is at least 45%.
  • the reference describes that pigment concentrates can easily incorporate into coating compositions where pigment solid are stably dispersed.
  • the dispersant resin is applicable for use with wide spectrum range of different pigments, especially for the tricky cases which are difficult to disperse well like DPP red BO (by Ciba) , Heliogene Blue L7101F (by BASF) and Quindo Violet RV929 (by Bayer) .
  • U.S. Pat. No. 8664331 B2 also discloses a type of polyurethane dispersant which contain large amounts of ethylene oxide repeat units from 35%to 90%by weight based on total weight of the polymer in lateral chain.
  • the carboxylic acid group as anchoring part is incorporated into the polyurethane backbone.
  • the dispersants mention above achieve many superior performance, water-dispersable, wide range compatibility with binder system and versatile pigments, lower viscosity of millbase and long-term stability of dispersion system.
  • organic solvent present in the synthesis processes of urethane or polyurethane type dispersant and it will easily lead cross-link problems if the superior anchoring group which is multifunction such as polyamine derivatives involved. Consequently, there exists a gap of urethane or polyurethane type dispersant between wetting performance and environmental-friendly issues.
  • PAA Polyacrylic acid
  • NaPAA sodium salt of polyacrylic acid
  • Related derivatives which are disclosed in U.S. Pat. No. 3945843 A and U.S. Pat. No. 4767644 A are another approach for organic solvent-free dispersant. But the wetting power of this type dispersants is always deficient for organic pigment due to the dis-matching of polarity. Therefore, it always combines with surfactant-like dispersant to enhance the wetting efficiency.
  • the present disclosure provides for dispersant comprising segments derived from: (1) one or more polyisocyanates having at least 2 isocyanate groups, (2) a mono-functional compound having an isocyanate reactive functional moiety; and (3) a polyamine having an amine functionality of two or more.
  • the dispersant is water soluble.
  • 50%-90%equivalent of the isocyanate groups of polyisocyanate are linked to the mono-functional compound and 10-50%equivalent of the isocyanate groups are linked to the polyamine.
  • the mono-functional compound is independently selected from an aliphatic compound, a cycloaliphatic compound and an aromatic compound, and combinations thereof. In some embodiments, the mono-functional compound contains at least one group independently selected from the group consisting of: -O-or-COO-and combinations thereof. In some instances, the mono-functional compound has a molecular weight ranging from 350 to 5000. In certain embodiments, the mono-functional compound is independently selected from poly (C 2-4 -alkylene oxide) containing 60%-99%ethylene oxide groups; a polyester oligomer; and combinations thereof. In some such embodiments, the polyester oligomer contains segments derived from a dicarboxylic acid and a glycol.
  • the polyisocyanate is a diisocyanate independently selected from toluene diisocyanate, isophorone diisocyanate (IPDI) , hexamethylene diisocyanate, diphenylmethane-4, 4′-diisocyanate, dicyclohexylm ethane-4, 4′-di-is ocyanate, 1,4-bis (2-isocyanato-2-yl) benzene, trimethyl hexamethylene diisocyanate, or mixtures of such diisocyanates.
  • IPDI isophorone diisocyanate
  • hexamethylene diisocyanate diphenylmethane-4, 4′-diisocyanate
  • dicyclohexylm ethane-4 4′-di-is ocyanate
  • 1,4-bis (2-isocyanato-2-yl) benzene trimethyl hexamethylene diisocyanate, or mixtures of
  • the polyisocyanate is independently selected from adducts, isocyanate biurets, isocyanate isocyanurates or mixtures of such polyisocyanates.
  • the polyisocyanate is independently selected from toluene diisocyanate and trimethylol propane adduct, hexamethylene diisocyanate biuret trimer, hexamethylene diisocyanate isocyanurate trimer, isophorone diisocyanate isocyanurate trimer, hexamethylene diisocyanate isocyanurate trimer, and isophorone diisocyanate isocyanurate trimer.
  • the isocyanate reactive functional moiety is independently selected from the group consisting of hydroxyl, amine or imine and combinations thereof.
  • the polyamine is independently selected from the group consisting of polyethylene imine (PEI) , polyvinylamine, polyallylamine oligomer, ethyleneimine oligomer and combinations thereof.
  • the polyamine is independently selected from diethylenetriamine (DETA) , triethylenetetramine (TETA) , tetraethylene pentamine (TEPA) , pentaethylenehexamine (PEHA) , hexaethyleneheptamine (HEHA) and combinations thereof.
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • TEPA tetraethylene pentamine
  • PEHA pentaethylenehexamine
  • HEHA hexaethyleneheptamine
  • the present invention provides for a dispersant composition with a terminal solubilizing group obtained via urethane and urea linkage by a solvent-free synthesis processes. It can be used in water-based coatings and in solvent-based coatings as well. At the same time, the dispersant composition can provide excellent wetting efficiency to obtain color paste with extremely low viscosity and good long-term colloidal stability. It comprises polyamine as anchoring part of dispersant to adsorb on pigment surface, polyisocyanate blocked by monohydroxyl compound to form isocyanate monoadduct as solvent solubilizing group that only one functionality of polyisocyanate have been left.
  • the present disclosure provides a dispersant having segments derived from: (1) one or more polyisoeyanates having at least 2 isocyanate groups, (2) a mono-functional compound having an isocyanate reactive functional moiety; and (3) a polyamine having an amine functionality of two or more.
  • the dispersant may be obtained from the organic solvent-free reaction of: (1) one or more polyisocyanates having at least 2 isocyanate groups, reacted with (2) a mono-functional compound having an isocyanate reactive functional moiety to form an isocyanate monoadduct intermediate.
  • the isocyanate monadduet intermediate is then reacted with (3) a polyamine having an amine functionality of two or more.
  • component (1) may be a polyisocyanate having at least 2 isocyanate groups.
  • the polyisocyanate comprises aliphatic isocyanate, cycloaliphatic isocyanate, aromatic isocyanate, heterocyclic isocyanate, and mixtures thereof.
  • the number of isocyanate groups of such polyisocyanate may range from 2 to 8; 2 to 5; or 2 to 4. In other embodiments, the average number of isocyanate groups ranges from 2 to 5.
  • Suitable examples of a polyisocyanate having two isocyanate functionalities are diisocyanates such as toluene diisocyanate (TDI, 80/20) , isophorone diisocyanate (IPDI) , hexamethylene diisocyanate (HDI) , diphenylmethane-4, 4′-Diisocyanate (4, 4′-MDI) , dicyclohexylmethane-4, 4′-di-isocyanate (HMDI) , 1, 4-bis (2-isocyanato-2-yl) benzene (TXMDI) , trimethyl hexamethylene diisocyanate ( “TMDI” ) , or mixtures of such diisocyanates.
  • diisocyanates such as toluene diisocyanate (TDI, 80/20) , isophorone diisocyanate (IPDI) , hexamethylene diisocyanate (HDI)
  • the polyisocyanate is TDI, IPDI, HMDI and mixtures thereof. In one embodiment, the polyisocyanate is TDI. In one embodiment, the polyisocyanate comprises HDI isocyanurate trimer, and IPDI isocyanurate trimer. Examples of multi-functionalities are Desmodur L which was obtained by the additional product between diisocyantes and polyols, and Desmour N obtained by biuret reaction, Desmodur IL is obtained by cyclization of diisocyanates.
  • component (2) may be a mono-functional compound having an isocyanate reactive functional moiety.
  • the mono-functional compound may be an aliphatic compound, a cycloaliphatic compound, an aromatic compound and combinations thereof, having a molecular weight ranging from 350 g/mole to 5000 g/mole, and may contain one or more ether linkage, ester linkage and mixtures thereof.
  • such mono-functional compound may have a molecular weight ranging from: 550 g/mole to 3000 g/mole; 550 g/mole to 2000 g/mole or 550 to 1000 g/mole.
  • the isocyanate reactive functional moiety of the embodiments of the mono-functional compound are independently selected from a hydroxyl group, an amine group, an imine group and combinations thereof.
  • the mono-functional compound may be a monohydroxyl compound.
  • the monohydroxyl compound may be linear, branched, and mixtures thereof.
  • the monohydroxyl compound may be saturated or unsaturated. In certain embodiments, the monohydroxyl compound is saturated.
  • the mono-functional compound includes poly (C 2-4 -alkylene oxide) compounds. It is desirable for the poly (C 2-4 -alkylene oxide) compound to have a low molecular weight such that it functions effectively as a solubilizing group for dispersant. In some embodiments, the number average molecular weight Mn of the poly (alkylene oxide) chains which are terminally attached to the anchoring part in dispersant structure ranges from 350 g/mole to 5000 g/mole; or 350 g/mole to 3000 g/mole or 350 g/mole to 2000 g/mole.
  • the poly (C 2-4 -alkylene oxide) compound has a number average molecular weight not greater than 5000 g/mole. In another embodiment, the poly (C 2-4 -alkylene oxide) compound has a number average molecular weight not greater than 3000 g/mole. In yet another embodiment, the poly (C 2-4 -alkylene oxide) compound has a number average molecular weight not greater than 2000 g/mole. In such embodiments, the poly (C 2-4 -alkylene oxide) compound has a number average molecular weight of at least 350 g/mole.
  • the mono-functional compound may be a polyester oligomer.
  • Polyester oligomers may be obtained by well-known techniques, such as polycondensation of one or more dicarboxylic acid, glycol, anhydride, hydroxyl carboxylic acid and any other materials can be applied in esterification reaction. Otherwise, ring-opening polymerization of the corresponding lactones such as delta-valerolactone and/or epsilon-caprolactone is also a suitable option.
  • the mono-functional compound reacts with component (1) to form an isocyanate monoadduct intermediate.
  • a polyisocyanate having at least 2 isocyanate groups has the structure of Formula (1) :
  • Q is an aliphatic group, an aromatic group, an aralkyl group, or an aliphatic or an aromatic backbone chain optionally interrupted one or more times by heteroatoms, amide groups, ester groups, carbamate groups, carbonate groups, carbamide groups or combinations thereof;
  • X is a direct bond, alkylene, alkenylene, alkynylene, arylene, cycloalkylene, heterocycloalkylene, heteroarylene, cycloalkyl-alkylene, arylene-alkylene, cycloalkylene-arylene, heterocycloalkylene-alkyl, heteroarylene-alkylene; and r is an integer having a value of from 2 to 8.
  • the isocyanate monoadduct intermediate of the general Formula (2) is formed by the reaction of a mono-functional compound of the form Y-Z with component (1) :
  • Z of the compound Y-Z is a nucleophilic group
  • Y is an aliphatic group, a cycloaliphatic group, an aromatic group or combinations thereof, the compound Y-Z having a molecular weight ranging from 350 g/mole to 5000 g/mole or 350 g/mole to 3000 g/mole or 350 g/mole to 2000 g/mole, and may contain one or more ether linkage, ester linkage or mixtures thereof
  • p is the number of equivalents of the compound Y-Z
  • r is the number of equivalents of NCO groups in the polyisocyanate:
  • a mono-functional compound of the form Y-Z reacts with component (1) to form the isocyanate monoadduct intermediate product of the general Formula (3) :
  • the compound Y-Z is a monohydroxyl compound, Y-OH, which when reacted with component (1) forms the isocyanate monoadduct intermediate product of the general Formula (3.1) :
  • Z is -O-, -NH-or -NR-, wherein R may be alkyl, cycloalkyl, aryl or a combination thereof having from 1 to 10 carbon atoms.
  • Q is derived from biuret (dicarbonimidic diamide) , or 1, 3, 5-triazinane-2, 4, 6-trione or a combination thereof.
  • component (3) may be a polyamine having an amine functionality of two or more.
  • the polyamine includes poly (C 2-6 -alkylene imine) , for example polyethylene imine (PEI) and polyvinylamine for C 2 compounds, polyallylamine for C 3 compounds.
  • the polyamine may be linear or branched.
  • Exemplary aliphatic linear polyamines include primary and secondary amino groups, such as diethylenetriamine (DETA) , triethylenetetramine (TETA) , tetraethylene pentamine (TEPA) , pentaethylenehexamine (PEHA) , hexaethyleneheptamine (HEHA) and similarly higher analog.
  • Exemplary aliphatic branched polyamines include primary, secondary and tertiary amino groups and which have number average molecular weight Mn of the polyamine ranges from 600 to 30000, or from 1000 ⁇ 10000.
  • Examplary polyethyleneimines include linear polyethyleneimines or branched polyethyleneimines.
  • Commercial polyethyethyleneimines are sold by BASF, and by Nippon Shokubai,
  • the dispersant composition is water soluble.
  • the dispersant composition may be made without using organic solvent, such that volatile organic compounds will not be released during the reaction procedure. Therefore, the phenomenon about heat accumulation should be noticed in earlier stage of the reaction.
  • Common catalyst for polyurethane manufacture may be employed to accelerate the reaction rate after heat release, such as tin catalyst.
  • tin catalyst for example, dibutyltin dilaurate, dibutyltin diacetate and diethyltin diacetate can be obtained from NITTO KASEI.
  • Bismuth catalyst is also can be applied, commercial compound for example, series product from KING INDUSTRIES or series product from NITTO KASEI.
  • the reaction of isocyanate monoadduct intermediate with component (3) is carried out by known methods.
  • the urea linkage is formed during these processes, the reaction generally employ without additional catalyst and organic solvent.
  • the molecular architecture based on poly (C 2-6 -alkylene imine) frame will lead to the star-like geometry.
  • the isocyanate monoadduct intermediates as solubilizing part will attach to the anchoring backbone at a terminal position.
  • wetting process it’s transforming of pigment surface state from solid/air surface into solid/liquid interface. High shearing forces are necessary in order to introduce pigment solid into the liquid media. As a consequence, it is usual to use dispersants to lower these dispersing forces and hence to minimize not only the total energy input required into the system but also dispersing time. Furthermore, dispersant also provide stabilization mechanism to prevent reagglomeration.
  • the known dispersants are generally surface active substances which with only small dosages are either applied directly to the solid or added to the liquid medium.
  • the dispersion media even after complete deflocculation of the agglomerates of pigment, instances of reagglomeration may occur after the dispersing operation. In this way, negative effects may occur, such as an increase in viscosity in the liquid system, floating and flooding, or a loss of gloss in ink and coatings.
  • the invention compounds are used as wetting dispersing agents for organic and inorganic pigments or fillers. It is used in amounts of 0.5 ⁇ 50%by weight, based on the solid to be dispersed in the ink and coating compositions. However, larger dosages of dispersant are necessary for high pigment surface cases at dispersing condition.
  • a 1000 mL three neck reaction flask, equipped with a thermometer, a reflux condenser, a heating jacket and a mechanical stirrer, 50.0 parts of toluene diisocyanate (TDI) were placed into the reaction vessel and stirred under nitrogen and ambient temperature.
  • 287.0 parts of Poly (ethylene glycol) methyl ether (DME-1000) were added into reactor dropwisely via the dropping funnel over 1.5 hour.
  • the reaction mixture was heated to 70 °C and the decrease in the NCO%was monitored by titration method in accordance with DIN 53185. When the NCO%of 3.6 %reached, 9.9 parts of diethylenetriamine (DETA) were added drop wise over 1 hour.
  • the mixture was heated to 85 °C and stirred at this temperature for further 3 hours. The heat source was removed. 520.4 parts of water were added to the hot mixture.
  • the product was a clear, light yellow solution with solid content of 40.3%. This is Dispersant 1.
  • IPDI isophorone diisocyanate
  • MPEG-550 Poly (ethylene glycol) methyl ether
  • DETA diethylenetriamine
  • the mixture is heated to 85 °C and stirred at this temperature for an additional 3 hours.
  • the heating source is removed. 416.28 parts of water are added to the hot mixture.
  • the product is a clear, light yellow solution with solid content of 40.0%. This is Dispersant 11.
  • FX 365 is a wetting agent from Elementis Specialties
  • FX 600 is a dispersing agent from Elementis Specialties
  • binder-free pigment concentrates were prepared by adding the dispersants into a 150 mL glass bottle at the concentrations of Table 1. Wetting efficiency and the viscosity were measured.
  • DF 665 is antifoam agent from Elementis Specialties
  • DF 7620 is antifoam agent from Elementis Specialties
  • the mixture was combined with 200 parts of 2 mm diameter zicronium beads. Carbon Black MA 100 and Heliogen Blue D 7079, were also used. Aqueous dispersion were prepared with 25%pigment loadings in black pigment concentrates and 30%pigment loadings in blue pigment concentrates.
  • the glass bottle was placed in a Scandex disperser and the contents milled by oscillatory shaking until particle size less than 5 ⁇ m.
  • the fineness was determined by grind gage.
  • the viscosity of the dispersions was measured on Brookfield viscometer with cone and plate geometry over a range of shear rate. The fineness and viscosity data are shown in Table 2 and Table 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Brouillon : L'invention concerne un dispersant de type uréthane comprenant des segments obtenus à partir de : (1) au moins un polyisocyanate ayant au moins 2,0 groupes isocyanate, (2) un composé mono-fonctionnel ayant un groupement fonctionnel réactif isocyanate; et (3) une polyamine ayant une fonctionnalité amine de 2 ou plus. Le dispersant peut être réalisé dans un processus de production sans solvant. Le dispersant peut être appliqué dans un système de dispersion de pigments à base d'eau.
PCT/CN2014/001051 2014-11-25 2014-11-25 Dispersants à base d'uréthane WO2016082058A1 (fr)

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PCT/CN2014/001051 WO2016082058A1 (fr) 2014-11-25 2014-11-25 Dispersants à base d'uréthane
EP14843193.5A EP3046661A4 (fr) 2014-11-25 2014-11-25 Dispersants à base d'uréthane
CN201510144172.0A CN106146796A (zh) 2014-11-25 2015-03-30 氨基甲酸乙酯分散剂

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CN109880038B (zh) * 2019-03-05 2021-09-28 广州浦利姆环保科技有限公司 水性聚氨酯及其制备方法、水性色浆
US20220135727A1 (en) * 2019-03-12 2022-05-05 Huntsman Petrochemical Llc Dispersants made from isocyanates and amines

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US4670068A (en) 1981-02-19 1987-06-02 Hercules Incorporated Polyfunctional isocyanate crosslinking agents for propellant binders
US4767644A (en) 1986-04-18 1988-08-30 Fuji Photo Film Co., Ltd. Method of making abrasive tape
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WO1997019120A1 (fr) 1995-11-21 1997-05-29 Akzo Nobel N.V. Polyurethanne insature dispersible dans l'eau
US5910556A (en) * 1996-08-30 1999-06-08 Bayer Aktiengesellschaft Dispersing agents for aqueous coatings compositions
CN1368986A (zh) * 1999-08-09 2002-09-11 纳幕尔杜邦公司 由异氰酸酯与聚(乙二醇)烷基醚、聚酯或聚丙烯酸酯和二胺反应形成的颜料分散剂
CN1692975A (zh) * 2004-05-07 2005-11-09 比克化学股份有限公司 适合作为分散剂和分散体稳定剂的加成化合物
US20090221745A1 (en) 2007-01-31 2009-09-03 Byk-Chemie Gmbh Universal Wetting Agents and Dispersants Based on Isocyanate Monoadducts
JP2010189514A (ja) * 2009-02-17 2010-09-02 Toyo Ink Mfg Co Ltd 分散剤、並びに、それを用いた顔料組成物及び顔料分散体
US8017686B2 (en) 2005-08-23 2011-09-13 Akzo Nobel Coating International B.V. Polyurethane dispersant resin
US8664331B2 (en) 2001-11-24 2014-03-04 The Lubrizol Corporation Aqueous urethane dispersants
CN103619894A (zh) * 2011-06-22 2014-03-05 比克化学股份有限公司 制备分散添加剂的方法

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US3945843A (en) 1974-07-22 1976-03-23 Nalco Chemical Company Acrylic acid copolymer as pigment dispersant
US4670068A (en) 1981-02-19 1987-06-02 Hercules Incorporated Polyfunctional isocyanate crosslinking agents for propellant binders
US4767644A (en) 1986-04-18 1988-08-30 Fuji Photo Film Co., Ltd. Method of making abrasive tape
US4929705A (en) * 1988-03-30 1990-05-29 Bayer Aktiengesellschaft New polyisocyanate-polyaddition compounds, a process for their preparation and their use for the dispersion of solids
WO1997019120A1 (fr) 1995-11-21 1997-05-29 Akzo Nobel N.V. Polyurethanne insature dispersible dans l'eau
US5910556A (en) * 1996-08-30 1999-06-08 Bayer Aktiengesellschaft Dispersing agents for aqueous coatings compositions
CN1368986A (zh) * 1999-08-09 2002-09-11 纳幕尔杜邦公司 由异氰酸酯与聚(乙二醇)烷基醚、聚酯或聚丙烯酸酯和二胺反应形成的颜料分散剂
US8664331B2 (en) 2001-11-24 2014-03-04 The Lubrizol Corporation Aqueous urethane dispersants
CN1692975A (zh) * 2004-05-07 2005-11-09 比克化学股份有限公司 适合作为分散剂和分散体稳定剂的加成化合物
US8017686B2 (en) 2005-08-23 2011-09-13 Akzo Nobel Coating International B.V. Polyurethane dispersant resin
US20090221745A1 (en) 2007-01-31 2009-09-03 Byk-Chemie Gmbh Universal Wetting Agents and Dispersants Based on Isocyanate Monoadducts
JP2010189514A (ja) * 2009-02-17 2010-09-02 Toyo Ink Mfg Co Ltd 分散剤、並びに、それを用いた顔料組成物及び顔料分散体
CN103619894A (zh) * 2011-06-22 2014-03-05 比克化学股份有限公司 制备分散添加剂的方法

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CN106146796A (zh) 2016-11-23
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