CN112724349B - Polymer and use thereof - Google Patents

Polymer and use thereof Download PDF

Info

Publication number
CN112724349B
CN112724349B CN201911032025.9A CN201911032025A CN112724349B CN 112724349 B CN112724349 B CN 112724349B CN 201911032025 A CN201911032025 A CN 201911032025A CN 112724349 B CN112724349 B CN 112724349B
Authority
CN
China
Prior art keywords
group
polymer
formula
nitro
polym
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911032025.9A
Other languages
Chinese (zh)
Other versions
CN112724349A (en
Inventor
崔广辉
李德恒
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paint China Co Ltd
Original Assignee
Nippon Paint China Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Paint China Co Ltd filed Critical Nippon Paint China Co Ltd
Priority to CN201911032025.9A priority Critical patent/CN112724349B/en
Publication of CN112724349A publication Critical patent/CN112724349A/en
Application granted granted Critical
Publication of CN112724349B publication Critical patent/CN112724349B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/005—Carbon black
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a polymer synthesized through addition reaction, a preparation method and application thereof, and particularly relates to application of the polymer as a dispersing agent in industries such as solid particles, fillers, liquid coatings, printing ink and the like. The polymers include isocyanate-reactive groups, polymer segments, anchor groups, and the like, having affinity for pigments, carbon black, and the like, allowing for application in a variety of acidic, neutral, and even basic environments.

Description

Polymer and use thereof
Technical Field
The invention belongs to the field of application of dispersing agent materials, relates to a polymer synthesized through addition reaction, a preparation method and application thereof, and particularly relates to application of the polymer as a dispersing agent of solid particles, fillers, liquid coating, printing ink and the like.
Background
In the industries of coatings, inks, and paint abrasives, there is a need for effective dispersants to uniformly distribute particulate solids in aqueous, polar or non-polar organic media (e.g., liquid binders). Poor pigment or ink dispersion results may lead to flocculation, aggregation or sedimentation in organic or aqueous liquid media (e.g., inks, paints or coatings), resulting in reduced gloss, color or hue shift, and poor storage stability.
In order to effectively achieve the dispersing effect, the first stage is the wetting stage, and the wetting and/or dispersing agent must be able to surround the solid surface, interact with the solid surface to eliminate any air or moisture on the solid surface to promote wetting thereof. Some dispersants having anchoring groups may accomplish this, for example, some hydrophilic anchoring groups may include tertiary amino groups, protonated or quaternized amino groups, phosphate groups, carboxylic acid groups, sulfonic acid groups or amide, urethane and/or urea groups, and the like. The second stage is a milling stage, after which the wet stage is de-agglomerated and de-agglomerated by providing mechanical action by high shear milling equipment, and the system is sheared to produce smaller particles, effectively breaking the agglomerates into individual particles. The third stage is the stabilization stage of the dispersion, and the pigment-like dispersion should remain stable during storage after paint formulation or during application and film formation. Stabilization is the creation of particles with repulsive forces sufficient to prevent other particles from coming too close together to form complex agglomerates and flocculation by the stable molecules adsorbed on the pigment surface.
The dispersing effect of the dispersing agent on pigment particles in a suspension medium is mainly realized through three mechanisms of an electrostatic stabilization mechanism, a steric stabilization mechanism and an electrostatic steric stabilization mechanism. Electrostatic stabilization only works in aqueous systems, where two particles of the same charge are brought into close proximity to each other, and the resulting charged particles of coulomb repulsion hold the system stable. The stabilization of the steric hindrance depends on whether the resin layer or polymer segment adsorbed on the pigment surface is sufficiently dissolved.
In the prior art, for example, U.S. patent publication No. US 8,795,831 B2 discloses a compound that can be used as a dispersant and/or dispersion stabilizer in both polar and non-polar adhesive systems. The compound is synthesized by taking polyisocyanate as a core, a compound containing groups reactive to isocyanate is taken as a stable chain, one of anchoring groups with at least two functional groups can react with isocyanate, and the other is an organic basic group. Although the dispersant may be used to make pigment concentrates, paints, slurries and/or molding compositions containing pigments and/or fillers, because it is basic, in some damaging applications, such as in acid catalyzed systems, the anchor groups themselves will react with acidic materials, reducing affinity to particles such as pigments, and the dispersibility is poor.
U.S. patent publication number US 10100152B 2 discloses a polymer chain comprising at least one fused aromatic imide pendant group useful as a dispersant, particularly in ink compositions, that can have a reduced particle size and a reduced particle size distribution. However, the polymer chains described in this patent have a relatively low molecular weight, typically less than 5000g/mol, and therefore provide limited ability to provide steric stabilization, and the dispersion obtained with the dispersant has poor dispersion stability.
In view of this, it is a problem to be solved by those skilled in the art to develop a new polymer to eliminate the above-mentioned drawbacks and deficiencies of the prior art.
Disclosure of Invention
In order to overcome the above problems in the prior art, the present invention provides a polymer and use thereof, which is particularly useful as a dispersant for pigments, fillers, etc. by addition reaction, and particularly, in an acidic system, an anchor group does not react with an acidic substance, and activity can be greatly improved and/or solubility or compatibility can be enhanced.
In a first aspect of the invention, there is provided a polymer of formula I:
[ (Q) y-Polym-(B)e]m-A-[(C)f-L-(T)x ] n type I
Wherein, the radicals B and C are each independently selected from the group consisting of-NH-CO-NH-, -NH-CO-N <, -NH-COO-, -NH-COS-, and,
-NH-CO-or-N < (CO-) 2, and B and C are the same or different;
A is a polyisocyanate residue;
l is a straight or branched alkyl, cycloalkyl, or aromatic group containing 1-20 carbons;
q is a straight or branched alkyl, or cycloalkyl group containing 1 to 20 carbons;
T is a group selected from the group consisting of: -NO 2、-CN、-SO3 M, -Cl, -Br, or-COOM, wherein M is a cation containing a positive monovalent charge;
Polym is a polymer chain having a molecular weight of less than 10000 g/mol;
e. f, m, n, x or y are each 1,2 or 3.
Further, the polymer chain Polym is selected from polyester, polyether, polyurethane or polysiloxane.
Further, the polymer chain Polym is selected from the group consisting of homopolymers or copolymers of: ethylene oxide, propylene oxide, butylene oxide, styrene oxide, or combinations thereof.
Further, the polymer chain Polym comprises blocks of 20% -80% of the repeating units being ethylene oxide and blocks of 20% -80% of the repeating units being propylene oxide.
Further, the molecular weight of the polymer chain Polym is 1000-5000g/mol.
Further, the L is an aromatic group, and the aromatic group is selected from: phenyl, naphthyl, anthryl, phenanthryl or fluorenyl.
Further, M is selected from group ：H+、Na+、K+、Li+、NH4 +、NH3 +-、NH2 +- or NH + <.
Further, the molecular weight of the polymer is greater than 5000g/mol.
Further, the polymer may be dissolved in water or an organic solvent.
In a second aspect of the invention there is provided a process for preparing a polymer according to the first aspect of the invention comprising the steps of:
(1) Providing one or more polyisocyanates;
(2) Providing one or more compounds of formula II:
(S) h-L-(T)x formula II
Wherein S is a group reactive with isocyanate groups, selected from the group consisting of-NH 2, -NH-, -OH, -COOH SH, anhydride groups and acid halides;
T is a group selected from the group consisting of: -NO 2、-CN、-SO3 M, -Cl, -Br, or-COOM groups, wherein M is a positive monovalent charge containing cation;
L is a linear or branched or cyclic alkyl group containing 1 to 20 carbons, or an aromatic group;
h is 1,2 or 3, x is 1,2 or 3;
(3) Providing a compound of formula III
(P) i-Polym-(Q)y formula III
P is a group reactive with isocyanate groups, selected from the group consisting of-NH 2, -NH-, -OH, -COOH SH, anhydride groups and acid halides;
q is a straight or branched alkyl, or cycloalkyl group containing 1 to 20 carbons;
Polym is a polymer chain having a molecular weight of less than 10000 g/mol;
i is 1,2 or 3, y is 1,2 or 3;
(4) The polyisocyanate, the compound of formula II and the compound of formula III undergo an addition reaction to produce the polymer according to the first aspect of the invention.
Further, after reaction of S with isocyanate groups, the group C is obtained.
Further, after the reaction of P and isocyanate groups, the group B is obtained.
Further, in S or P, the acid anhydride group is selected from: phthalic anhydride group, 1, 8-naphthalene dicarboxylic anhydride group, 1, 2-naphthalene dicarboxylic anhydride group, 2, 3-naphthalene dicarboxylic anhydride group or 3, 4-naphthalene dicarboxylic anhydride group.
Further, the anhydride group is substituted with the group: -NO 2、-CN、-SO3 M, -Cl, -Br or-COOM groups, wherein M is a cation containing a positive monovalent charge.
Further, L is an aromatic group selected from: phenyl, naphthyl, anthryl, phenanthryl or fluorenyl.
Further, the polyisocyanate comprises at least 2 isocyanate groups per molecule.
Further, the polyisocyanate is selected from the group consisting of: isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, poly (hexamethylene diisocyanate), trans-1, 4-cyclohexylene diisocyanate, 1, 4-diisocyanatobutane, 1, 8-diisocyanatooctane, or 4,4' -methylenebis (phenylisocyanate).
Further, the polyisocyanate is selected from:ultra N 3300、ultra N 3600、N 3800、N 3900、 L75, or a combination thereof.
Further, in the compounds of formula II, T is a neutral or acidic group.
Further, in the compound of formula II, T is nitro.
Further, the compound of formula II is selected from the group consisting of: 4-nitro-o-phenylenediamine, 2-nitro-1, 4-phenylenediamine, 6-nitro-3, 4-dihydro-2H-benzo [ b ] [1,4] oxazine, 7-nitro-3, 4-dihydro-2H-1, 4-benzoxazine, 5-nitro-m-xylene-alpha, alpha' -diol, 3-nitro-N-methylaniline, 2-nitro-2-phenylpropane-1, 3-diol, 2-nitro-1-propanol, 3-nitro-L-tyrosine, 3-nitro-1, 8-naphthalic anhydride, 4-nitro-2- (trifluoromethyl) aniline, 6-nitro-3- (phenylacetylamino) benzoic acid, 4-aminobenzyl cyanide, 2-aminobenzyl cyanide, 4-acetamido-2-aminobenzenesulfonic acid, N- (2-acetamido) -2-aminoethanesulfonic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 1-amino-4-bromoanthraquinone-2-sulfonic acid sodium salt, 1-amino-4-bromoanthraquinone-2-sulfonic acid, 2-amino-4-chlorophenol-6-sulfonic acid, 5-amino-2-chlorotoluene-4-sulfonic acid, 2-amino-3, 5-dimethylbenzenesulfonic acid, 6-amino-4-hydroxy-2-naphthalenesulfonic acid, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3-amino-1, 5-naphthalenedisulfonic acid, 3-amino-2, 7-naphthalenedisulfonic acid, 3-amino-1, 5-naphthalenedisulfonic acid disodium salt, 4-amino-1-naphthalenesulfonic acid, 2-amino-1-naphthalenesulfonic acid, 5-amino-2-naphthalenesulfonic acid, 6-amino-1-naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 7-anilino-4-hydroxy-2-naphthalenesulfonic acid, aniline-2, 5-disulfonic acid monosodium salt, 4-anisidine-2-sulfonic acid, 4-anisidine-3-sulfonic acid, 1-amino-2-bromonaphthalene, 1-amino-4-bromonaphthalene, 5-amino-2, 3-dicyano-1, 4-quinone, 6-amino-2-naphthalenecarboxylic acid, 4-bromonaphthalene, benzoic acid, 4-benzoic acid, benzoic acid or sodium benzoate.
Further, the compound of formula III is selected from the group consisting of:
Polyglykol 2000、Polyglykol 4000、Polyglykol M 2000、Polyglykol M 3000、Polyglykol M5000、M41/2000、D01/2000、D-2005、 d-2070, or a combination thereof.
In a third aspect of the invention there is provided the use of a polymer as described in the first aspect of the invention as a dispersant or wetting agent.
In a fourth aspect of the invention there is provided a liquid composition in the form of a dispersion comprising a fine particulate solid material selected from pigments and fillers, dispersed in a polymer according to the first aspect of the invention.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1. In the preparation process of the polymer provided by the invention, functional groups with affinity to pigments and the like are used, so that the dispersant provided by the invention can be applied to various environments of acidity, neutrality and alkalinity and has stronger adaptability to application environments compared with other alkaline dispersants.
2. The polymers provided by the invention have relatively high molecular weights, typically greater than 5000g/mol, and thus contribute to improved dispersion stability.
Detailed Description
However, the present invention should be understood not to be limited to such an embodiment described below, and the technical idea of the present invention may be implemented in combination with other known technologies or other technologies having the same functions as those of the known technologies.
Each aspect or embodiment defined herein may be combined with any other aspect or embodiment unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature or features indicated as being preferred or advantageous.
Description of the terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, when used in reference to a specifically recited value, the term "about" means that the value can vary no more than 1% from the recited value. For example, as used herein, the expression "about 100" includes 99 and 101 and all values therebetween (e.g., 99.1, 99.2, 99.3, 99.4, etc.).
As used herein, the term "comprising" or "including" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …", or "consisting of …".
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the inventive subject matter. In the present application, the singular is used to include the plural unless specifically stated otherwise. It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. It should also be noted that the use of "or" means "and/or" unless stated otherwise. Furthermore, the terms "comprising" or "including" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …", or "consisting of …".
Unless specifically defined, the terms used herein in analytical chemistry, organic synthetic chemistry, and related descriptions of pharmaceutical and pharmaceutical chemistry are known in the art.
When substituents are described by conventional formulas written from left to right, the substituents also include chemically equivalent substituents obtained when writing formulas from right to left. For example, -CH 2 O-is equivalent to-OCH 2 -.
The section headings used herein are for purposes of organizing articles only and should not be construed as limiting the subject matter. All documents or portions of documents cited in this disclosure, including but not limited to patents, patent applications, articles, books, operating manuals, and treatises, are hereby incorporated by reference in their entirety.
Certain chemical groups defined herein are preceded by a simplified symbol to indicate the total number of carbon atoms present in the group. For example, C1-C6 alkyl refers to an alkyl group as defined below having a total of 1 to 6 carbon atoms. The total number of carbon atoms in the reduced notation does not include carbon that may be present in a substituent of the group.
In addition to the foregoing, when used in the specification and claims of the present application, the following terms have the meanings indicated below, unless otherwise specified.
In the present application, the term "halogen" refers to fluorine, chlorine, bromine or iodine.
"Hydroxy" refers to an-OH group.
"Nitro" means-NO 2.
"Cyano" refers to-CN.
In the present application, as part of a group or other groups (e.g., as used in halogen substituted alkyl groups and the like), the term "alkyl" refers to a straight or branched hydrocarbon chain radical that is fully saturated, consisting of only carbon and hydrogen atoms, having, for example, 1 to 7 carbon atoms, and being attached to the remainder of the molecule by a single bond, including, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, 2-dimethylpropyl, n-hexyl, heptyl, and the like.
In the present application, the term "alkenyl" as part of a group or other group means a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, containing at least one double bond, having, for example, 2 to 8 (preferably 2 to 6) carbon atoms and being linked to the rest of the molecule by a single bond, such as, but not limited to, ethenyl, propenyl, allyl, but-1-enyl, but-2-enyl, pent-1, 4-dienyl, and the like. As used herein, "C 2-C6 straight or branched alkenyl" includes a single double bond, or multiple, discontinuous double bonds. In the present application, the term "alkynyl" as part of a group or other group refers to a straight or branched hydrocarbon chain group consisting of only carbon and hydrogen atoms, containing at least one triple bond, optionally containing at least one double bond, having, for example, 2 to 6 carbon atoms, and being attached to the remainder of the molecule by a single bond, such as, but not limited to, ethynyl, prop-1-ynyl, but-1-ynyl, pent-1-en-4-ynyl, and the like. As used herein, "C 2-C6 straight or branched chain alkynyl" includes a single triple bond, or multiple, discontinuous triple bonds.
In the present application, the term "aromatic group" means a conjugated hydrocarbon ring system group having 6 to 18 carbon atoms (preferably having 6 to 10 carbon atoms) as part of a group or other groups. For the purposes of the present application, aryl groups may be monocyclic, bicyclic, tricyclic or more ring systems, and may also be fused to cycloalkyl or heterocyclyl groups as defined above, provided that the aryl groups are linked to the remainder of the molecule by single bonds via atoms on the aromatic ring. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, and the like.
In the present application, the term "heteroaryl" as part of a group or other group means a 5-to 16-membered conjugated ring system group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms) and 1 to 6 heteroatoms selected from nitrogen, oxygen and sulfur in the ring. Unless otherwise specifically indicated in the present specification, heteroaryl groups may be monocyclic, bicyclic, tricyclic or more ring systems, and may also be fused to cycloalkyl or heterocyclyl groups as defined above, provided that heteroaryl groups are attached to the remainder of the molecule via an atom on an aromatic ring by a single bond. The nitrogen, carbon, or sulfur atoms in the heteroaryl group may optionally be oxidized; the nitrogen atom may optionally be quaternized. For the purposes of the present application, heteroaryl groups are preferably stable 5-to 12-membered aromatic groups comprising 1 to 5 heteroatoms selected from nitrogen, oxygen and sulfur, more preferably stable 5-to 10-membered aromatic groups comprising 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur or 5-to 6-membered aromatic groups comprising 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur. Examples of heteroaryl groups include, but are not limited to, thienyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, oxadiazolyl, isoxazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, benzimidazolyl, benzopyrazolyl, indolyl, furanyl, pyrrolyl, triazolyl, tetrazolyl, triazinyl, indolizinyl, isoindolyl, indazolyl, isoindazolyl, purinyl, quinolinyl, isoquinolinyl, naphthyridinyl, quinoxalinyl, pteridinyl, carbazolyl, carbolinyl, phenanthridinyl, phenanthrolinyl, acridinyl, phenazinyl, isothiazolyl, benzothiazolyl, benzothienyl, oxatriazolyl, cinnolinyl, quinazolinyl, thiophenyl, indolizinyl, phenanthroline, isoxazolyl, phenoxazinyl, phenothiazinyl, 4,5,6, 7-tetrahydrobenzo [ b ] thienyl, naphthyridinyl, [1,2,4] triazolo [4, 3-triazolo [1, 4] pyridazine, 3-1, 4-imidazo [1, 4] triazolo [1, 4, 3-triazolo [1, 4] pyridazine, 3-1, 4-imidazo [ 2, 4-a ] and the like.
In the present application, "optionally" or "optionally" means that the subsequently described event or condition may or may not occur, and that the description includes both cases where the event or condition occurs and where it does not. For example, "optionally substituted aryl" means that the aryl group is substituted or unsubstituted, and the description includes both substituted aryl groups and unsubstituted aryl groups. The "optional" substituents described in the claims and the description section of the application are selected from alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, cyano, nitro, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl.
The terms "moiety", "structural moiety", "chemical moiety", "group", "chemical group" as used herein refer to a particular fragment or functional group in a molecule. Chemical moieties are generally considered to be chemical entities that are embedded or attached to a molecule.
When an olefinic double bond is contained in the compounds of the present invention, the compounds of the present invention are intended to include both E-and Z-geometric isomers unless otherwise specified.
The term "anhydride group" refers herein to a group of atoms according to the formula: … -C (=o) -O-C (=o) - …
The term "residue" may refer to a portion of a monomer or other chemical unit that has been incorporated into a polymer or other macromolecule. For example, it may be a carbon-containing residue, i.e., a residue containing at least one carbon atom, or it may contain various heteroatoms, or it may be linked to another molecule via a heteroatom including oxygen, nitrogen, sulfur, phosphorus, and the like. Examples of residues include, but are not limited to, alkyl or substituted alkyl, alkoxy or substituted alkoxy, mono or di substituted amino, amide groups, and the like. The organic residue may preferably contain 1 to 18 carbon atoms, 1 to 15 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. In another aspect, the organic residue may comprise 2 to 18 carbon atoms, 2 to 15 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms.
As used herein, the compound of formula II contains functional groups reactive with isocyanate that are capable of being incorporated into the core of the dispersant product during synthesis; the T group (for example, nitro group) contained therein can be used as an anchor group (anchor group) for pigments and the like, and an effective dispersion process can be achieved when the pigment is never used as a dispersant.
As used herein, the compound of formula III stabilizes the dispersant system by steric stabilization, not only with a polymer chain of large molecular weight, to effectively achieve steric stabilization; and functional groups reactive with isocyanate groups, such as hydroxyl, thiol, primary amine, secondary amine, and anhydride. The compound of formula III meeting the conditions is selected from the group consisting of: polyglykol 2000, polyglykol 4000, polyglykol M2000, polyglykol M3000, polyglykol M5000,M41/2000、D01/2000、D-2005、D-2070, or a combination thereof.
Raw materials and reagents
Desmodur N3900: purchased from Bayer Co
M41/2000: purchased from clariant company
L75: purchased from Bayer Co
Examples
Example 1: under inert gas, 3g of Desmodur N3900 are placed in an oil bath at 80℃and then 15.15g are addedM41/2000. 0.93g of 4-nitroaniline was added to the mixture with 0.05ml of dibutyltin Dilaurate (DBTL). At 2.5 hours, an additional 4.15gM41/2000 was added to the reaction flask. After 30 minutes, the reaction was stopped by cooling, and sample 1 was produced.
Example 2: under inert gas, 3g of Desmodur N3900 were placed in an oil bath at 70℃and then 14.5g of Desmodur N were addedM41/2000. 1.23g of 2, 4-dinitroaniline) and 0.05ml of dibutyltin Dilaurate (DBTL) were added together to the mixture and the oil bath was warmed to 80 ℃. After 1 hour, an additional 5.7gM41/2000 was added to the reaction flask until all isocyanate had reacted. After 30 minutes, the reaction was stopped by cooling, and sample 2 was produced.
Example 3: under inert gas, 1.22g of 3-nitro-1, 8-naphthalene dicarboxylic anhydride (3 NNPA) was dissolved in 20g of DMF and 10g of N, N-Dimethylacetamide (DMAC) and placed in an oil bath at 140 ℃. After 3NNPA was dissolved, 3g of Desmodur N3900 and 0.02ml of NaOH solution were added to the reaction mixture. After 1.5 hours, 23.5g of/2000 Is added to the reaction mixture. After 30 minutes, the solvent was removed under vacuum and the reaction was stopped by cooling to prepare sample 3.
Example 4: under inert gas, 1.2g of 3NNPA g of DMAC were dissolved in 20g of DMF and 10g of DMAC and placed in an oil bath at 140 ℃. After 3NNPA was dissolved, 4g was added to the reaction mixtureL75 and 0.02ml NaOH solution. After 1.5 hours, 14.98g ofM41/2000 was added to the reaction mixture. After 30 minutes, the solvent was removed under vacuum and the reaction was stopped by cooling to prepare sample 4.
Example 5: under inert gas, 1.86g of 4-bromo-1, 8-naphthalic anhydride was dissolved in 20g of DMF and 10gDMAC and placed in an oil bath at 140 ℃. After dissolution, 3g of the mixture was added to the reaction mixtureN3900 and 0.02ml NaOH solution. After 1.5 hours, 20.14g ofM41/2000 was added to the reaction mixture. After 30 minutes, the solvent was removed under vacuum and the reaction was stopped by cooling to prepare sample 5.
Comparative example 1:
Under an inert gas atmosphere, 3g of N3900 was added to the reaction flask and the conditions were set in a 60℃oil bath. Then 33.75g ofM41/2000 was added to the reaction mixture. Once the isocyanate was completely consumed in the reaction, the reaction was stopped by cooling, and sample 1C was produced.
Comparative example 2:
Under inert gas conditions, 1.33g of 1, 8-naphthalene dicarboxylic anhydride was dissolved in 20g of DMF and 10g of DMAC, and the conditions were set in an oil bath at 140 ℃. After dissolving 1, 8-naphthalene dicarboxylic anhydride, 3g of the mixture was added to the reaction mixture N3900 and 0.02ml NaOH solution. After 1.5 hours, 20.34g ofM41/2000. After 30 minutes, the solvent was removed under vacuum and the reaction was stopped by cooling to give sample 2C.
Experimental results:
samples 1 to 5, 1C and 2C prepared above were used as dispersants to disperse carbon black pigments. 15 grams of carbon black pigment, 15 grams of each dispersion, 1 gram of defoamer, 2 grams of wetting agent, and 67 grams of deionized water were each prepared.
To prepare the dispersant mill base, the dispersant is dissolved in water, then defoamer and wetting agent are added, stirred, and carbon black pigment is added. After the mill-base was formulated, 350g of ZrO 2 organic beads (bead) were added and placed in a shaker (Das 200) for 4 hours. The milled dispersion was then added to a 2K PU matrix to evaluate color properties. The test was then performed by applying various coatings on the sampling card. The coated sampling card was left to dry at room temperature for 10 minutes and then cured at 80 ℃ for 30 minutes. The cast paint on the sampling card was then tested for color using a BYK Gardner Spectro-Guide gloss color spectrophotometer.
The resulting color of each sample was then analyzed by a spectrophotometer in the format of L, a, b color parameters.
Dispersant numbering L a b
Sample 1C 25.21 -0.48 -0.31
Sample 2C 25.37 -0.45 -0.49
Sample 1 24.50 -0.39 -0.28
Sample 2 24.28 -0.52 -0.33
Sample 3 24.26 -0.33 -0.13
Sample 4 24.09 -0.27 -0.02
Sample 5 24.40 -0.28 -0.31
It can be seen that the dispersant prepared by the invention can form improved dispersion in paint, carbon black and the like, and has obviously improved dispersing effect.
Unless specifically stated otherwise, the appearances of the phrase "first," "second," or the like herein are not meant to be limiting as to time sequence, number, or importance, but are merely for distinguishing one technical feature from another in the present specification. Likewise, the appearances of the phrase "a" or "an" in this document are not meant to be limiting, but rather describing features that have not been apparent from the foregoing. Likewise, modifiers similar to "about" and "approximately" appearing before a number in this document generally include the number, and their specific meaning should be understood in conjunction with the context. Likewise, unless a particular quantity of a noun is to be construed as encompassing both the singular and the plural, both the singular and the plural may be included in this disclosure.
The preferred embodiments of the present invention have been described in the specification, and the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the present invention. All technical solutions that can be obtained by logic analysis, reasoning or limited experiments according to the inventive concept by those skilled in the art shall be within the scope of the present invention.

Claims (16)

1. A polymer of formula I:
[ (Q) y-Polym-(B)e]m-A-[(C)f-L-(T)x]n formula I
Wherein the groups B and C are respectively selected from-NH-CO-NH-, -NH-CO-N <, -NH-COO-, -NH-COS-, -NH-CO-, or-N < (CO-) 2, and B and C are the same or different;
A is a polyisocyanate residue;
l is a straight or branched alkyl, cycloalkyl, or aromatic group containing 1-20 carbons;
q is a straight or branched alkyl, or cycloalkyl group containing 1 to 20 carbons;
T is a group selected from the group consisting of: -NO 2, -Cl, or-Br;
Polym is a polymer chain having a molecular weight of less than 10000g/mol, said polymer chain Polym being selected from polyesters, polyethers, polyurethanes or polysiloxanes;
e. f, m, n, x or y are each 1,2 or 3,
Wherein the molecular weight of the polymer is greater than 5000g/mol;
the preparation method of the polymer comprises the following steps:
(1) Providing one or more polyisocyanates;
(2) Providing one or more compounds of formula II:
(S) h-L-(T)x formula II
The compound of formula II is selected from the group consisting of: 4-nitro-o-phenylenediamine, 2-nitro-1, 4-phenylenediamine, 5-nitro-m-xylene- α, α' -diol, 3-nitro-N-methylaniline, 2-nitro-2-phenylpropane-1, 3-diol, 2-nitro-1-propanol, 3-nitro-L-tyrosine, 3-nitro-1, 8-naphthalenedicarboxylic anhydride, 4-nitro-2- (trifluoromethyl) aniline, 2-amino-4-chlorophenol-6-sulfonic acid, 5-amino-2-chlorotoluene-4-sulfonic acid, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 1-amino-2-bromonaphthalene, 1-amino-4-bromonaphthalene, or 4-bromo-1, 8-naphthalenedicarboxylic anhydride;
(3) Providing a compound of formula III
(P) i-Polym-(Q)y formula III
P is a group reactive with isocyanate groups, selected from the group consisting of-NH 2, -NH-, -OH, -COOH SH, anhydride groups and acid halides;
q is a straight or branched alkyl, or cycloalkyl group containing 1 to 20 carbons;
Polym is a polymer chain having a molecular weight of less than 10000 g/mol;
i is 1,2 or 3, y is 1,2 or 3;
(4) The polyisocyanate, the compound of formula II and the compound of formula III undergo addition reaction to prepare the polymer,
Wherein, S reacts with isocyanate groups to obtain the group C;
wherein, after the reaction of P and isocyanate groups, the group B is obtained.
2. The polymer of claim 1, wherein the polymer chain Polym is selected from the group consisting of homopolymers or copolymers of: ethylene oxide, propylene oxide, butylene oxide, styrene oxide, or combinations thereof.
3. The polymer of claim 2, wherein the polymer chain Polym comprises blocks of 20% to 80% repeat units of ethylene oxide and blocks of 20% to 80% repeat units of propylene oxide.
4. The polymer of claim 1, wherein the polymer chain Polym has a molecular weight of 1000 to 5000g/mol.
5. The polymer of claim 1, wherein L is an aromatic group and the aromatic group is selected from the group consisting of: phenyl, naphthyl, anthryl, phenanthryl or fluorenyl.
6. The polymer of claim 1, wherein the polymer is soluble in water or an organic solvent.
7. A process for preparing the polymer of any one of claims 1-6, comprising the steps of:
(1) Providing one or more polyisocyanates;
(2) Providing one or more compounds of formula II:
(S) h-L-(T)x formula II
Wherein S is a group reactive with isocyanate groups, selected from the group consisting of-NH 2, -NH-, -OH, -COOH SH, anhydride groups and acid halides;
T is a group selected from the group consisting of: -NO 2, -Cl, or-Br;
L is a linear or branched or cyclic alkyl group containing 1 to 20 carbons, or an aromatic group;
h is 1,2 or 3, x is 1,2 or 3;
(3) Providing a compound of formula III
(P) i-Polym-(Q)y formula III
P is a group reactive with isocyanate groups, selected from the group consisting of-NH 2, -NH-, -OH, -COOH SH, anhydride groups and acid halides;
q is a straight or branched alkyl, or cycloalkyl group containing 1 to 20 carbons;
Polym is a polymer chain having a molecular weight of less than 10000 g/mol;
i is 1,2 or 3, y is 1,2 or 3;
(4) The addition reaction of the above polyisocyanates, compounds of formula II, compounds of formula III to give polymers according to any of claims 1 to 6,
Wherein, S reacts with isocyanate groups to obtain the group C;
wherein, after the reaction of P and isocyanate groups, the group B is obtained.
8. The method of claim 7, wherein in S or P, the anhydride group is selected from the group consisting of phthalic anhydride group, 1, 8-naphthalene dicarboxylic anhydride group, 1, 2-naphthalene dicarboxylic anhydride group, 2, 3-naphthalene dicarboxylic anhydride group, and 3, 4-naphthalene dicarboxylic anhydride group.
9. The method of claim 8, wherein the anhydride group is substituted with a group consisting of: -NO 2, -Cl, or-Br.
10. The method of claim 7, wherein L is an aromatic group selected from the group consisting of: phenyl, naphthyl, anthryl, phenanthryl or fluorenyl.
11. The method of claim 7, wherein the polyisocyanate is selected from the group consisting of: isophorone diisocyanate, hexamethylene diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, m-xylylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, poly (hexamethylene diisocyanate), trans-1, 4-cyclohexylene diisocyanate, 1, 4-diisocyanatobutane, 1, 8-diisocyanatooctane, or 4,4' -methylenebis (phenylisocyanate).
12. The method of claim 7, wherein the polyisocyanate is selected from the group consisting of:ultra N3300、ultra N 3600、N 3800、N 3900、 L75, or a combination thereof.
13. The method of claim 7, wherein in the compound of formula II, T is nitro.
14. The method of claim 7, wherein the compound of formula III is selected from the group consisting of:
Polyglykol M 2000、Polyglykol M 3000、Polyglykol
M5000、 m41/2000 or combinations thereof.
15. Use of a polymer according to any of claims 1-6 as a dispersant or wetting agent.
16. A liquid composition in the form of a dispersion comprising a fine particulate solid material selected from pigments and fillers, said fine particulate solid material being dispersed in a polymer according to any one of claims 1 to 6.
CN201911032025.9A 2019-10-28 2019-10-28 Polymer and use thereof Active CN112724349B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911032025.9A CN112724349B (en) 2019-10-28 2019-10-28 Polymer and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911032025.9A CN112724349B (en) 2019-10-28 2019-10-28 Polymer and use thereof

Publications (2)

Publication Number Publication Date
CN112724349A CN112724349A (en) 2021-04-30
CN112724349B true CN112724349B (en) 2024-07-05

Family

ID=75588805

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911032025.9A Active CN112724349B (en) 2019-10-28 2019-10-28 Polymer and use thereof

Country Status (1)

Country Link
CN (1) CN112724349B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146796A (en) * 2014-11-25 2016-11-23 德谦（上海）化学有限公司 Urethanes dispersant
CN106674463A (en) * 2017-02-08 2017-05-17 上海金狮化工有限公司 Polyurethane pigment dispersing agent and method for preparing same

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4670068A (en) * 1981-02-19 1987-06-02 Hercules Incorporated Polyfunctional isocyanate crosslinking agents for propellant binders
US5124217A (en) * 1990-06-27 1992-06-23 Xerox Corporation Magnetic image character recognition processes
US6136950A (en) * 1997-09-23 2000-10-24 Mbt Holding Ag Highly efficient cement dispersants
JP4407128B2 (en) * 2003-01-17 2010-02-03 東洋インキ製造株式会社 Pigment dispersant, pigment composition containing the same, and pigment dispersion
GB0311121D0 (en) * 2003-05-15 2003-06-18 Avecia Ltd Polyurethane dispersants
US8487051B2 (en) * 2005-06-07 2013-07-16 Lubrizol Advanced Materials, Inc. Polyurethane based pigment dispersants which contain reactive double bonds
EP1888662B1 (en) * 2005-06-07 2015-04-15 Lubrizol Advanced Materials, Inc. Polyurethane based pigment dispersants which contain reactive double bonds
WO2007007685A1 (en) * 2005-07-08 2007-01-18 Toyo Ink Manufacturing Co., Ltd. Dispersing agent, method for producing same, and pigment dispersion and ink containing such dispersing agent
JP5054692B2 (en) * 2005-08-23 2012-10-24 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ Dispersible polyurethane resin
JP5171005B2 (en) * 2006-03-17 2013-03-27 富士フイルム株式会社 Polymer compound, method for producing the same, and pigment dispersant
DE102006012999A1 (en) * 2006-03-22 2007-09-27 Byk-Chemie Gmbh Addition compounds as dispersants and dispersion stabilizers
DE102008010687B4 (en) * 2008-02-22 2014-05-15 Byk-Chemie Gmbh Wetting and dispersing agents, their preparation and use
EP2443166A1 (en) * 2009-06-19 2012-04-25 Huntsman International LLC Compound suitable as polymeric dispersant
CN102274702A (en) * 2011-05-10 2011-12-14 山东沃尔德科技发展有限公司 Block macromolecular pigment dispersant, preparation method thereof, and pigment dispersion liquid containing dispersant
CN102432800B (en) * 2011-09-05 2013-05-08 惠州市汉诺新材料有限公司 Water-oil dual-purpose dispersion agent as well as preparation method and application thereof
CN102658057B (en) * 2012-04-16 2014-09-10 王志军 Novel polyurethane dispersant and preparation method thereof
WO2015065829A1 (en) * 2013-11-01 2015-05-07 Lubrizol Advanced Materials, Inc. Dispersants with multiple aromatic imide anchor groups
TW201840635A (en) * 2017-01-26 2018-11-16 美商盧伯利索先進材料有限公司 Polymeric dispersants containing one or two quaternary amine anchoring groups with improved chemical and thermal stability
CN108373530B (en) * 2018-03-06 2020-11-06 英德侗富贵科技材料有限公司 Environment-friendly water-oil universal polyurethane dispersant and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106146796A (en) * 2014-11-25 2016-11-23 德谦（上海）化学有限公司 Urethanes dispersant
CN106674463A (en) * 2017-02-08 2017-05-17 上海金狮化工有限公司 Polyurethane pigment dispersing agent and method for preparing same

Also Published As

Publication number Publication date
CN112724349A (en) 2021-04-30

Similar Documents

Publication Publication Date Title
KR101526527B1 (en) Humectant and dispersant, production and use thereof
EP1458778B1 (en) Aqueous urethane dispersants
KR101358658B1 (en) Polyurethane based pigment dispersants which contain reactive double bonds
KR101526526B1 (en) Humectant and dispersant, production and use thereof
EP1762580B1 (en) Polyurethane dispersants
JP5856861B2 (en) Water-based pigment dispersion, method for producing the same, and ink for inkjet recording
KR101726931B1 (en) Dispersing additives based on phosphoric acid ester derivatives
CN105440238B (en) Addition compounds suitable as dispersants or antisettling agents
DE10159315A1 (en) Compounds suitable as dispersants for pigments
US11879032B2 (en) Reaction products containing urethane groups and urea groups
US10253133B2 (en) Urethane-group-containing reaction products
EP1697470B1 (en) A process for preparing modified particulate solid materials and inks comprising the same
CN112724349B (en) Polymer and use thereof
EP3218423B1 (en) Comb polyurethane dispersants
US4631330A (en) Addition compounds and process for their preparation
US9068092B2 (en) Process for preparing polymers, polymers, dispersions, inks and uses
DK162652B (en) Powder-azopigment preparation having improved rheological properties, process for producing it, and its use
US10544091B2 (en) Reaction products containing amidoamine groups
JPH01172415A (en) Manufacture of resin having high dispersibility
CN114106341A (en) Comb copolymer and preparation method and application thereof
JPH0368910B2 (en)

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant