阅读说明：本技术 颜料分散剂 (Pigment dispersants ) 是由 S·R·萨曼塔 C·J·帕特尔 C·韦德 B·G·R·莫尔 于 2019-08-08 设计创作，主要内容包括：本申请涉及包含聚合物主链和至少一个式(I)的结构部分的聚合型颜料分散剂、制备所述聚合型颜料分散剂的方法和用于涂料和印刷油墨、汽车底色漆、汽车清漆、漆浆、家具涂料和木材涂料的包含所述颜料分散剂的颜料分散体。(The present application relates to polymeric pigment dispersants comprising a polymeric backbone and at least one moiety of formula (I), methods of making the polymeric pigment dispersantsAnd pigment dispersions comprising the pigment dispersants for coatings and printing inks, automotive base paints, automotive varnishes, coating slips, furniture coatings and wood coatings.)

1. A polymeric pigment dispersant comprising a polymeric backbone (P) and at least one moiety of formula (I):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -O-group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -O-group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -O-group; and

whereby the at least one moiety of formula (I) is bonded to the polymer backbone (P) via a-C (═ O) -O-group.

2. The polymeric pigment dispersant according to claim 1, wherein R1 is selected from the group consisting of naphthyl, anthryl and phenanthryl, unsubstituted or substituted by 1,2, 3,4 or 5 substituents independently of one another selected from the group consisting of F, Cl, Br, I, -NO₂、-CN、-OH、-O-C₁-C₆-alkyl, -C (═ O) -C₁-C₆-alkyl, -C (═ O) -O-C₁-C₆-alkyl, -C (═ O) -O-phenyl, -CH₂-C(＝O)-C₁-C₆-alkyl, -C (═ O) -NH (C)₁-C₆) Alkyl, -C (═ O) -NH-phenyl, -C₁-C₆-substituent substitution of alkyl; wherein-C₁-C₆Alkyl is unsubstituted or substituted by 1,2, 3,4 or 5 radicals independently of one another from the group F, Cl, Br, I, -CN, -OH, -O-CF₃、-O-CH₃and-O-C₂H₅Is substituted with the substituent(s).

3. The polymeric pigment dispersant of claim 1 wherein said at least one moiety of formula (I) is formed by reacting at least one compound of formula (II)

Wherein

R2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

with at least one compound of the formula (III)

R1-NH₂ (III)

Wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

optionally in the presence of at least one solvent.

4. A polymeric pigment dispersant according to claim 1 wherein said polymeric backbone (P) is a linear diblock polymer.

5. A polymeric pigment dispersant according to claim 1 wherein said polymeric backbone (P) is a random polymer.

6. The polymeric pigment dispersant of claim 5 wherein said polymeric pigment dispersant is a graft polymer.

7. A method for preparing at least one polymeric pigment dispersant, comprising at least the steps of:

reacting the linear diblock polymer with a compound of formula (IV) at a temperature of 80 ℃ or more to 150 ℃ or less:

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 andr3 taken together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group; and

wherein the linear diblock polymer comprises a first and a second block and is obtained by living radical polymerization, optionally in the presence of a solvent.

8. A method for preparing at least one polymeric pigment dispersant, comprising at least the steps of:

(a) reacting a random polymer with a compound of formula (IV):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

and

(b) reacting the compound obtained in step (a) with at least one lactone monomer at a temperature of from ≥ 30 ℃ to ≤ 190 ℃.

9. A method for preparing at least one polymeric pigment dispersant, comprising at least the steps of:

(a) reacting at least one polyalkylene glycol monoalkyl ether and at least one carboxylic acid anhydride at a temperature of 70 ℃ or more to 140 ℃ or less to obtain a mixture; and

(b) reacting the mixture obtained in step (a) with a random polymer and a compound of formula (IV) at a temperature of 70 ℃ or more to 140 ℃ or less:

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group.

10. A pigment dispersion comprising at least one polymeric pigment dispersant according to any one of claims 1 to 6, at least one solvent and at least one pigment.

11. A coating composition comprising the pigment dispersion according to claim 10 and at least one binder.

12. Use of the pigment dispersion according to claim 10 in printing inks, automotive basecoats, automotive varnishes, lacquers, furniture coatings and wood coatings.

13. An article coated with at least one layer formed from the coating composition according to claim 11.

14. A compound of formula (IV)

Wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

the following compound N-naphthyl-4-carboxy-1, 2-phthalimide is thereby excluded.

15. A compound of formula (IV)

Wherein

R1 is selected from unsubstituted naphthyl or naphthyl substituted by 1,2 or 3-OH; and is

R2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group.

Technical Field

The present invention relates to polymeric pigment dispersants, methods of making the polymeric pigment dispersants, and pigment dispersions containing the pigment dispersants for coatings and printing inks, automotive base paints, automotive varnishes, pastes, furniture coatings, and wood coatings. The invention further relates to a coating composition comprising said pigment dispersion.

Background

Pigment-containing coating compositions are widely used in the automotive industry as corrosion resistant primers and decorative topcoats. The automotive market is trending toward high clear colors and rich shades because color is a major factor in the vehicle commercialization segment of the automotive industry. High transparency and rich color shades are usually achieved in varnishes by very stable fine dispersion of organic pigments to submicron dimensions. However, agglomeration of small sized pigment particles, i.e., less than 100nm, during their application in coatings and during long term storage of coating compositions is a significant challenge in the coating industry. It is desirable that the pigment dispersion remain substantially stable with minimal pigment blocking and viscosity change.

Traditionally, random copolymers used in pigment dispersion compositions contain multiple anchoring and stabilizing segments and their use as dispersants does not provide sufficient stabilization, especially when the particle size is small. Furthermore, the hyperdispersants available on the market have a controlled architecture, which has some limitations, such as their synthesis requiring dedicated equipment and conditions. Alternatively, amines are used as anchor moieties in commercial dispersants to stabilize the pigment particles through acid-base reactions or hydrogen bonding. But the amine reacts with the acid catalyst present in the varnish composition to precipitate the pigment. Accordingly, there is a continuing need to develop pigment dispersions to address the problems of existing pigment dispersion compositions.

In the state of the art, hyperdispersants with controlled architecture and pigment dispersants comprising imide anchor blocks are known and described, for example, in the following references.

U.S.2016/257774 a1 describes a polymeric dispersant composition comprising an acrylic backbone and at least one pendant imide group wherein the carbonyl group of the imide is chemically bonded to a fused aromatic ring.

U.S.6,037,414A describes a polymeric pigment dispersant comprising a graft polymer having an acrylic backbone, polyester side chains, cyclic imide groups and quaternary ammonium groups.

U.S.8,129,466B 2 describes a nanoparticle dispersion comprising a dispersant comprising a triblock polymer having a first block comprising glycidyl (meth) acrylate reacted with naphthoic acid, a second block comprising alkyl (meth) acrylate, and a third block comprising alkyl (meth) acrylate, wherein the third block is different from the second block.

U.S.7,723,425B 2 describes compositions containing modified block copolymer dispersants prepared by Atom Transfer Radical Polymerization (ATRP) and modified with salt-forming groups. The salt-forming groups are selected from specific mono-or polycyclic sulfonic acids or mono-or polycyclic carboxylic acids and phosphonic acids, or alkyl halides containing mono-or polycyclic groups or esters of mono-or polycyclic sulfonic acids.

The methods and compositions disclosed in the prior art have limitations. The compositions described in the above prior art do not provide a high efficiency pigment dispersant that brings about effective deagglomeration and strong interaction with the pigment particles to finely disperse the pigment particles to submicron sizes. The lack of strong interaction with the pigment particles affects the clarity and color desired in the market. Because of the increasing demand for a riky color space with high saturation in the coatings and inks market, there is a need to synthesize novel pigment dispersions which overcome the above-mentioned disadvantages and which comprise stable anchor blocks which can interact with aromatic pigment molecules by pi-pi interactions and hydrogen bonding interactions.

It is therefore an object of the present invention to provide pigment dispersants with a well-defined polymer chain structure and pigment dispersions comprising the pigment dispersants that can be easily synthesized under mild conditions, which provide for efficient dispersion of pigment particles, as evidenced by the lower brightness (as determined by measuring the L value) of the coatings obtained from pigment dispersions containing the polymeric pigment dispersants.

It is another object of the present invention to provide an efficient process for preparing the polymeric pigment dispersant.

SUMMARY

It has surprisingly been found that coating compositions comprising the novel polymeric pigment dispersants as described below provide excellent stabilization of the pigment particles as evidenced by the lower brightness (as determined by measuring the L value) of the coatings obtained from coating compositions comprising the novel polymeric pigment dispersants. It has also been unexpectedly found that the method of making the polymeric pigment dispersants described below is more efficient and less expensive than conventionally known methods of synthesizing polymeric pigment dispersants.

Accordingly, in one aspect, the present invention relates to a polymeric pigment dispersant comprising a polymeric backbone (P) and at least one moiety (moiety) of formula (I):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -O-group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl radicalAnd linear or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -O-group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -O-group; and

whereby the moiety of formula (I) is bonded to the polymer backbone (P) via a-C (═ O) -O-group.

In another aspect, the present invention relates to a method for preparing at least one polymeric pigment dispersant, comprising at least the steps of:

reacting the linear diblock polymer with a compound of formula (IV) at a temperature of 80 ℃ or more to 150 ℃ or less:

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group; and

wherein the linear diblock polymer comprises a first and a second block and is obtained by living radical polymerization, optionally in the presence of a solvent.

In yet another aspect, the present invention relates to a method of preparing at least one polymeric pigment dispersant comprising at least the steps of:

(a) reacting a random polymer with a compound of formula (IV):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

and

(b) reacting the compound obtained in step (a) with at least one lactone monomer at a temperature of from ≥ 30 ℃ to ≤ 190 ℃.

In another aspect, the present invention relates to a method for preparing at least one polymeric pigment dispersant, comprising at least the steps of:

(a) reacting at least one polyalkylene glycol monoalkyl ether and at least one carboxylic acid anhydride at a temperature of 70 ℃ or more to 140 ℃ or less to obtain a mixture; and

(b) reacting the mixture obtained in step (a) with a random polymer and a compound of formula (IV) at a temperature of 70 ℃ or more to 140 ℃ or less:

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group.

In another aspect, the present invention relates to a pigment dispersion comprising at least one polymeric pigment dispersant according to the present invention, at least one solvent and at least one pigment.

In a further aspect, the present invention relates to a coating composition comprising the pigment dispersion according to the invention and at least one binder.

In a further aspect, the present invention relates to the use of the pigment dispersion according to the invention in printing inks, automotive basecoats, automotive varnishes, coating slips, furniture coatings and wood coatings.

In a further aspect, the present invention relates to an article coated with at least one layer formed from a coating composition according to the present invention.

In another aspect, the invention relates to compounds of formula (IV)

Wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight or branched chainSubstitution of the chain C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

the following compound N-naphthyl-4-carboxy-1, 2-phthalimide is thereby excluded.

In another aspect, the invention relates to compounds of formula (IV)

Wherein

R1 is selected from unsubstituted naphthyl or naphthyl substituted by 1,2 or 3-OH; and is

R2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group.

The invention is associated with at least one of the following advantages:

(i) polymeric pigment dispersants having diblock and random polymer architecture are synthesized using conventional polymerization techniques,

(ii) providing a pigment dispersion of pigment particles having a submicron particle size of less than 100nm,

(iii) the compounds of formula (IV) as described below provide good interaction and strong adsorption with the pigment surface through even weak interactions, such as pi-pi and hydrogen bonding interactions,

(iv) the compounds of formula (IV) as described below have an increased solubility in low polar solvents,

(v) the polymer backbone (P) of the present invention provides steric stabilization,

(vi) the polymeric pigment dispersants of the present invention provide high chroma and clear color compared to conventional hyperdispersants, an

(vii) The polymeric pigment dispersants of the present invention do not interact with strong acid catalysts and are therefore compatible with varnish compositions containing organic acid catalysts.

Other objects, advantages and applications of the present invention will become apparent to those skilled in the art from the following detailed description.

Detailed description of the invention

The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. Furthermore, there is no intention to be bound by any theory presented in the preceding technical field, background, brief summary or the following detailed description.

As used herein, the term "comprising" is synonymous with "including" or "containing" and is inclusive or open-ended and does not exclude additional unrecited members, elements, or method steps. It will be recognized that the term "comprising" as used herein includes the term "consisting of.

Furthermore, the terms "(a)", "(b)", "(c)", "(d)" and the like in the description and in the claims are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the subject matter described herein are capable of operation in other sequences than described or illustrated herein. Where the terms "(a)", "(B)" and "(C)" or "(a)", "(B)", "(C)", "(d)", "(i)", "(ii)" etc. relate to steps of a method or use or detection, there is no time or time interval coherence between these steps, that is, these steps may be performed simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between these steps, unless otherwise indicated in the application as set forth above or below.

In the following paragraphs, different aspects of the subject matter are defined in more detail. Each aspect so defined may be combined with any other aspect or aspects 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.

Reference throughout this specification to "one embodiment" or "an embodiment" means that a particular element, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment, but may. Furthermore, the elements, structures, or features may be combined in any suitable manner as would be apparent to one of ordinary skill in the art from this disclosure in one or more embodiments. In addition, although some embodiments described herein include some elements included in other embodiments and not other elements, combinations of elements of different embodiments are intended to be within the scope of the subject matter and constitute different embodiments, as understood by those of skill in the art. For example, in the following claims, any of the claimed embodiments may be used in any combination.

Furthermore, the ranges specified throughout this specification are also inclusive, i.e., a range of 1 to 10 means that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant is entitled to any equivalents in accordance with applicable law.

For the purposes of the present invention, a block polymer or block copolymer is defined as a polymer or copolymer formed when two or more monomers are brought together and form a "block" of repeating units.

For the purposes of the present invention, a random polymer or random copolymer is defined as a polymer or copolymer formed when two or more monomers are added as repeating units in a completely random manner.

For the purposes of the present invention, graft polymers are multiblock copolymers having a linear backbone of one composite and randomly distributed branches of another composite.

The term "copolymer" referred to throughout this specification means that the copolymer comprises a block or random copolymer obtainable by free radical polymerization.

For the purposes of the present invention, the mass average (M) is determined by means of gel permeation chromatography at 40 ℃ using a high performance liquid chromatography pump and a refractive index detector_w) And the number average (M)_n) Molecular weight. The eluent used was tetrahydrofuran, elution rate 1 ml/min. Calibration was performed with polystyrene standards.

For the purposes of the present subject matter, a polar solvent is defined as a solvent having a large dipole moment and containing bonds between atoms that differ widely in electronegativity.

For the purposes of the present invention, the dielectric constant value of a solvent represents a measure of the polarity of the solvent. The higher dielectric constant of the solvent indicates the higher polarity of the solvent.

For the purposes of the present invention, the use of (methyl) in the monomers or repeating units refers to the optional methyl group.

For the purposes of the present invention, transparency or transparency is defined as the property of a material that allows visible light to pass through the material, either completely or partially, without scattering.

For the purposes of the present invention, a pigment is defined as any substance that changes the color of a material by selective absorption or any substance that scatters or reflects light.

For the purposes of the present invention, effect pigments are defined as flakes or platelet-shaped structures which impart a directionally light-reflecting, scattering, absorbing or optically variable appearance to a substrate in or on which the effect pigments are applied.

For the purposes of the present invention, polydispersity or polydispersity index (PDI) is defined as a measure of the molecular mass distribution in a given polymer.

For the purposes of the present invention, "weight percent" or "wt.%" as used in the present invention, refers to the total weight of the coating composition. In addition, the sum of the weight% of all compounds described below in the individual components amounts to 100 weight%.

The measurement techniques mentioned above are well known to the person skilled in the art and therefore do not limit the invention.

Polymeric pigment dispersants

One aspect of the present invention describes a polymeric pigment dispersant comprising a polymeric backbone (P) and at least one moiety of formula (I):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -O-group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -O-group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -O-group; and

whereby the moiety of formula (I) is bonded to the polymer backbone (P) via a-C (═ O) -O-group.

In one embodiment of the invention, R1 in formula (I) above is selected from naphthyl, anthryl and phenanthryl, unsubstituted or substituted by F, Cl, Br, I, -NO₂、-CN、-OH、-O-C₁-C₆-alkyl, -C (═ O) -C₁-C₆-alkyl, -C (═ O) -O-C₁-C₆-alkyl, -C (═ O) -O-phenyl, -CH₂-C(＝O)-C₁-C₆-alkyl, -C (═ O) -NH (C)₁-C₆) Alkyl, -C (═ O) -NH-phenyl, -C₁-C₆-alkyl substitution; wherein-C₁-C₆Alkyl is unsubstituted or substituted by 1,2, 3,4 or 5 radicals independently of one another from the group F, Cl, Br, I, -CN, -OH, -O-CF₃、-O-CH₃and-O-C₂H₅Is substituted with the substituent(s).

In a preferred embodiment of the present invention, R1 in the above formula (I) is naphthyl, which is unsubstituted orIs selected from 1,2, 3,4 or 5 independently of one another from F, Cl, Br, I, -NO₂、-CN、-OH、-O-C₁-C₆-alkyl, -C (═ O) -C₁-C₆-alkyl, -C (═ O) -O-C₁-C₆-alkyl, -C (═ O) -O-phenyl, -CH₂-C(＝O)-C₁-C₆-alkyl, -C (═ O) -NH (C)₁-C₆) Alkyl, -C (═ O) -NH-phenyl, -C₁-C₆-substituent substitution of alkyl; wherein-C₁-C₆Alkyl is unsubstituted or substituted by 1,2, 3,4 or 5 radicals independently of one another from the group F, Cl, Br, I, -CN, -OH, -O-CF₃,-O-CH₃and-O-C₂H₅Is substituted with the substituent(s).

In a preferred embodiment of the present invention, R1 in formula (I) above is selected from naphthyl, anthryl and phenanthryl, each of which is unsubstituted or substituted with 1,2 or 3-OH.

In a preferred embodiment of the present invention, R2 and R3 in formula (I) above, together with the carbon atom to which they are bonded, form a ring selected from phenyl and cyclohexyl, each substituted with one-C (═ O) -O-group.

In another embodiment of the invention, the at least one moiety of formula (I) and the compound of general formula (IV) are each prepared by reacting at least one compound of formula (II)

Wherein

R2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

with at least one compound of the formula (III)

R1-NH₂ (III)

Wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

optionally in the presence of at least one solvent (S1).

In a preferred embodiment of the present invention, the at least one compound of formula (II) described above is selected from phthalic anhydride, hexahydrophthalic anhydride, dodecenylsuccinic anhydride, octadecenylsuccinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and nadic anhydride, each substituted with one-C (═ O) -OH group. In a more preferred embodiment of the present invention, said at least one compound of formula (II) as described above is selected from 1,2, 4-benzenetricarboxylic anhydride and 1, 2-cyclohexanecarboxylic anhydride.

In a preferred embodiment of the present invention, the at least one compound of formula (III) described above is selected from 1-naphthylamine and 7-hydroxy 1-naphthylamine.

In another embodiment of the present invention, the at least one solvent (S1) is a polar solvent having a boiling point of 80 ℃ or more and 160 ℃ or less and a dielectric constant of 11 or more and 30 or less.

In a preferred embodiment of the present invention, the at least one solvent (S1) is a polar solvent having a boiling point of 80 ℃ or more and 130 ℃ or less and a dielectric constant of 11 or more and 25 or less.

In a preferred embodiment of the present invention, the at least one solvent (S1) is selected from the group consisting of methyl N-amyl ketone, methyl ethyl ketone, methyl isoamyl ketone, and isopropyl alcohol.

For the purposes of the present invention, the compounds of the general formula (IV) are more preferably synthesized by the abovementioned reaction in the presence of less polar and lower boiling solvents, such as isopropanol, methyl ethyl ketone, methyl isoamyl ketone and methyl N-amyl ketone.

In one embodiment of the invention, the polymeric pigment dispersant has a number average molecular weight (M) of 1000g/mol or more to 25000g/mol or less as determined by gel permeation chromatography of control polystyrene standards_n). In a preferred embodiment of the present invention, the polymeric pigment dispersant has a number average molecular weight (M) of 1000g/mol or more and 15000g/mol or less_n)。

In one embodiment of the invention, the polymeric pigment dispersant has a polydispersity of ≥ 1.2 to ≤ 20 as determined by gel permeation chromatography of control polystyrene standards. In another embodiment of the invention, the polymeric pigment dispersant has a polydispersity of ≥ 1.2 to ≤ 10 as determined by gel permeation chromatography of control polystyrene standards. In a preferred embodiment of the present invention, the polymeric pigment dispersant has a polydispersity of ≥ 1.2 to ≤ 3.5, as determined by gel permeation chromatography of control polystyrene standards. In the most preferred embodiment of the present invention, the polymeric pigment dispersant has a polydispersity of ≥ 1.2 to ≤ 2.2, as determined by gel permeation chromatography of control polystyrene standards.

In one embodiment of the present invention, the total weight of the at least one moiety of formula (I) is in the range of ≥ 5% by weight to ≤ 50% by weight, based on the total weight of the polymeric pigment dispersant. In a preferred embodiment of the present invention, the total weight of the at least one moiety of formula (I) is in the range of ≥ 5% by weight to ≤ 30% by weight, based on the total weight of the polymeric pigment dispersant.

Linear diblock polymers

In one embodiment of the present invention, the above-mentioned polymer main chain (P) is a linear diblock polymer.

In another embodiment of the invention, the linear diblock polymer is obtained by living radical polymerization.

In one embodiment of the invention, the linear diblock polymer is obtained by living radical polymerization, known as Atom Transfer Radical Polymerization (ATRP).

The ATRP process is described as providing a highly homogeneous product with a controlled structure and is also known as Controlled Radical Polymerization (CRP). The ATRP process is described for the preparation of copolymers useful in a variety of applications, including pigment dispersants in u.s.6,365,666B 1 and u.s.6,642,301B 2. A detailed description of the ATRP process can be found in U.S. Pat. No. 5,807,937A, U.S. Pat. No. 5,763,548A, U.S. Pat. No. 5,789,487A and WO 1998/40415A 1.

For the purposes of the present invention, the linear diblock polymers may be obtained by other polymerization techniques, such as reversible addition-fragmentation chain transfer (RAFT) polymerization, single electron transfer living radical polymerization (SEL-LRP), nitroxide stable radical polymerization (NMRP), living ring-opening metathesis polymerization (ROMP), living anionic and living cationic polymerization.

In yet another embodiment of the present invention, the linear diblock polymer has the formula A-B, wherein

A is a first polymer block obtained by reacting a first mixture comprising at least one glycidyl (meth) acrylate; and

b is a second polymer block obtained by reacting a second mixture comprising at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, polyethylene glycol (meth) acrylates, and polyethylene glycol alkyl ether (meth) acrylates.

In one embodiment of the invention, the linear diblock polymer a-B is obtained by reacting a first polymer block a and a second polymer block B, optionally in the presence of at least one solvent and optionally in the presence of at least one catalyst.

In another embodiment of the present invention, the linear diblock polymer has the formula A-B, wherein

A is a first polymer block obtained by reacting a first mixture comprising at least one glycidyl (meth) acrylate; and

b is a second polymer block obtained by reacting a second mixture comprising at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, polyethylene glycol (meth) acrylates, and polyethylene glycol alkyl ether (meth) acrylates;

optionally in the presence of at least one solvent.

In a preferred embodiment of the present invention, the first polymer block a described above is obtained by reacting a first mixture comprising at least one glycidyl (meth) acrylate.

In a preferred embodiment of the present invention, the above-mentioned second polymer block B is obtained by reacting a second mixture comprising at least one alkyl (meth) acrylate monomer, at least one hydroxyalkyl (meth) acrylate monomer, at least one polyethylene glycol (meth) acrylate monomer and at least one polyethylene glycol alkyl ether (meth) acrylate monomer.

In a preferred embodiment of the present invention, the above-mentioned second polymer block B is obtained by reacting a second mixture comprising at least one alkyl (meth) acrylate monomer and at least one hydroxyalkyl (meth) acrylate monomer.

In one embodiment of the present invention, the above-mentioned alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate and isodecyl (meth) acrylate. In a preferred embodiment of the present invention, the above-mentioned alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate and isobutyl (meth) acrylate.

In one embodiment of the present invention, the above hydroxyalkyl (meth) acrylate is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate.

In one embodiment of the invention, the polyethylene glycol alkyl ether (meth) acrylate is selected from the group consisting of polyethylene glycol methyl ether acrylate, polyethylene glycol ethyl ether acrylate, polyethylene glycol propyl ether acrylate, and polyethylene glycol butyl ether acrylate.

In one embodiment of the invention, the linear diblock polymer has a number average molecular weight (M) of 1000g/mol or more to 25000g/mol or less as determined by gel permeation chromatography of control polystyrene standards_n). In a preferred embodiment of the present invention, the polymeric pigment dispersant has a number average molecular weight (M) of 1000g/mol or more and 15000g/mol or less_n)。

In one embodiment of the invention, the linear diblock polymer has a polydispersity of ≥ 1.2 to ≤ 20 as determined by gel permeation chromatography of control polystyrene standards. In another embodiment of the invention, the linear diblock polymer has a polydispersity of from ≥ 1.2 to ≤ 10 as determined by gel permeation chromatography of control polystyrene standards. In a preferred embodiment of the present invention, the polymeric pigment dispersant has a polydispersity of ≥ 1.2 to ≤ 3.5, as determined by gel permeation chromatography of control polystyrene standards. In the most preferred embodiment of the present invention, the polymeric pigment dispersant has a polydispersity of ≥ 1.2 to ≤ 2.2, as determined by gel permeation chromatography of control polystyrene standards.

In one embodiment of the present invention, the above-mentioned polymer main chain (P) is a block polymer having at least two blocks.

Atactic polymer

In one embodiment of the present invention, the above-mentioned polymer main chain (P) is a random polymer.

In a further embodiment of the invention, the random polymer is obtained by free radical polymerization.

In one embodiment of the invention, the random polymer is obtained by radical polymerization known as Atom Transfer Radical Polymerization (ATRP).

The ATRP process is described as providing a highly homogeneous product with a controlled structure and is also known as Controlled Radical Polymerization (CRP). The ATRP process is described for the preparation of copolymers useful in a variety of applications, including pigment dispersants in u.s.6,365,666B 1 and u.s.6,642,301B 2. A detailed description of the ATRP process can be found in U.S. Pat. No. 5,807,937A, U.S. Pat. No. 5,763,548A, U.S. Pat. No. 5,789,487A and WO 1998/40415A 1.

For the purposes of the present invention, the random polymers may be obtained by other polymerization techniques, such as reversible addition-fragmentation chain transfer (RAFT), ring-opening metathesis polymerization (ROMP) and anionic and cationic polymerization.

In one embodiment of the invention, the random polymer is obtained by reacting a mixture (M) comprising:

(a) glycidyl methacrylate and/or glycidyl acrylate;

(b) at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and cycloalkyl (meth) acrylates;

(c) optionally at least one styrene monomer; and

(d) optionally at least one monomer selected from the group consisting of vinyl monomers, monoethylenically unsaturated monomers bearing a urea or keto group, and benzyl (meth) acrylate,

optionally in the presence of at least one solvent (S2).

In a preferred embodiment of the invention, the random polymer is obtained by reacting a mixture (M) comprising:

(a) glycidyl methacrylate and/or glycidyl acrylate; and

(b) at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and cycloalkyl (meth) acrylates.

In a preferred embodiment of the invention, the random polymer is obtained by reacting a mixture (M) comprising:

(a) glycidyl methacrylate and/or glycidyl acrylate;

(b) at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and cycloalkyl (meth) acrylates; and

(c) at least one styrene monomer.

In one embodiment of the invention, the random polymer is obtained by reacting a mixture (M) comprising:

(a) glycidyl methacrylate and/or glycidyl acrylate;

(b) at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and cycloalkyl (meth) acrylates;

(c) at least one styrene monomer; and

(d) at least one monomer selected from the group consisting of vinyl monomers, monoethylenically unsaturated monomers bearing a urea or keto group, and benzyl (meth) acrylate.

In a preferred embodiment of the invention, the random polymer is obtained by reacting a mixture (M) comprising:

(a) glycidyl methacrylate and/or glycidyl acrylate;

(b) at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and cycloalkyl (meth) acrylates; and

(c) at least one styrene monomer,

in the presence of at least one solvent (S2).

In a preferred embodiment of the invention, the random polymer is obtained by reacting a mixture (M) comprising:

(a) glycidyl methacrylate and/or glycidyl acrylate; and

(b) at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and cycloalkyl (meth) acrylates;

in the presence of at least one solvent (S2).

In one embodiment of the present invention, the above-mentioned alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate and isodecyl (meth) acrylate. In a preferred embodiment of the present invention, the above-mentioned alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate and isobutyl (meth) acrylate.

In one embodiment of the present invention, the above hydroxyalkyl (meth) acrylate is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate.

In one embodiment of the present invention, the above-mentioned cycloalkyl (meth) acrylate is selected from cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate and bornyl (meth) acrylate.

In one embodiment of the present invention, the at least one styrene monomer described above is selected from the group consisting of 4-methylstyrene, 3-methylstyrene, 4-tert-butylstyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-alpha-methylstyrene, 2, 6-dichlorostyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2, 6-difluorostyrene, 3-nitrostyrene and 4-acetoxystyrene.

In one embodiment of the present invention, the at least one vinyl monomer described above is selected from the group consisting of 3-vinylbenzoic acid, 4-vinylbenzoic acid and 4-vinylbenzyl chloride.

In one embodiment of the invention, the monoethylenically unsaturated monomers bearing a urea or keto group are chosen from 2- (2-oxo-imidazolidin-1-yl) ethyl (meth) acrylate, 2-ureido (meth) acrylate, N- [2- (2-oxo-methacrylate)Oxazolidin-3-yl) ethyl]Esters, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2- (acetoacetoxy) ethyl methacrylate, bisAcetone Acrylamide (DAAM), diacetone methacrylamide, N- (. beta. -ureidoethyl) acrylamide and N- (. beta. -ureidoethyl) methacrylamide.

In one embodiment of the present invention, the solvent (S2) is selected from the group consisting of xylene, toluene, methanol, ethanol, n-propanol, isopropanol, butanol, butoxyethanol, acetone, butanone, pentanone, hexanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, amyl acetate, methoxypropyl acetate, tetrahydrofuran, diethyl ether, ethylene glycol, polyethylene glycol, and mixtures thereof. In a preferred embodiment of the present invention, the solvent (S2) is selected from the group consisting of toluene, n-propanol, isopropanol, methyl isobutyl ketone, and mixtures thereof.

In one embodiment of the invention, the random polymer has a number average molecular weight (M) of 1000g/mol or more to 25000g/mol or less as determined by gel permeation chromatography of control polystyrene standards_n). In a preferred embodiment of the present invention, the polymeric pigment dispersant has a number average molecular weight (M) of 1000g/mol or more and 15000g/mol or less_n)。

In one embodiment of the invention, the random polymer has a polydispersity of ≥ 1.5 to ≤ 20 as determined by gel permeation chromatography of control polystyrene standards. In another embodiment of the invention, the random polymer has a polydispersity of ≥ 1.5 to ≤ 10 as determined by gel permeation chromatography of control polystyrene standards. In a preferred embodiment of the present invention, the polymeric pigment dispersant has a polydispersity of ≥ 1.5 to ≤ 5, as determined by gel permeation chromatography of control polystyrene standards. In the most preferred embodiment of the present invention, the polymeric pigment dispersant has a polydispersity of ≥ 1.5 to ≤ 3 as determined by gel permeation chromatography of control polystyrene standards.

Graft polymers

In one embodiment of the present invention, the above polymeric pigment dispersant is a graft polymer.

In one embodiment of the invention, the graft polymers described above and below comprise at least one polyester block.

In a further embodiment of the present invention, the above polyester blocks are obtained from monomer units of a hydroxy-functional aliphatic acid or a hydroxy-functional aromatic acid or a hydroxy-functional araliphatic acid. In a preferred embodiment of the invention, the above polyester blocks are obtained from monomer units of hydroxy-functional aliphatic acids. In one embodiment of the present invention, the above hydroxy-functional aliphatic acid is selected from the group consisting of glycolic acid, lactic acid, 5-hydroxyvaleric acid, 3-hydroxy-butyric acid, 4-hydroxy-valeric acid, 12-hydroxystearic acid and 6-hydroxyhexanoic acid.

In a preferred embodiment of the present invention, the above polyester blocks are obtained in the presence of saturated fatty acids or unsaturated fatty acids. Representative examples of saturated or unsaturated fatty acids are preferably selected from oleic acid, linolenic acid, palmitoleic acid, and tall oil fatty acids.

In another embodiment of the present invention, the polyester blocks described above are obtained from lactone monomer units. In a further embodiment of the invention, the above mentioned lactone is selected from the group consisting of delta-valerolactone, epsilon-caprolactone, beta-methyl-delta-valerolactone, 2-methyl-epsilon-caprolactone, 3-methyl-epsilon-caprolactone, 4-methyl-epsilon-caprolactone, 5-tert-butyl-epsilon-caprolactone, 7-methyl-epsilon-caprolactone, 4, 6-trimethyl-epsilon-caprolactone and beta-propiolactone.

In one embodiment of the present invention, the total weight of the at least one polyester block described above is in the range of ≧ 5 weight percent to ≦ 95 weight percent based on the total weight of the polymeric pigment dispersant. In a preferred embodiment of the present invention, the total weight of the at least one polyester block described above is in the range of ≥ 45 wt.% to ≤ 95 wt.%, based on the total weight of the polymeric pigment dispersant. In the most preferred embodiment of the present invention, the total weight of the at least one polyester block described above is in the range of ≥ 45 wt.% to ≤ 80 wt.%, based on the total weight of the polymeric pigment dispersant.

In one embodiment of the present invention, the above polyester blocks are bonded to the moiety of formula (I) and/or the polymer backbone (P) via a-C (═ O) -O-group.

In another embodiment of the present invention, the graft polymers described above and below comprise at least one polyether block.

In another embodiment of the present invention, said at least one polyether block described above comprises polyoxyethylene groups comprising from 10 to 120 ethylene oxide units. In a preferred embodiment of the present invention, the at least one polyether block described above comprises polyoxyethylene groups comprising from 20 to 60 ethylene oxide units.

In one embodiment of the present invention, the above polyether blocks are bonded to the moiety of formula (I) and/or the polymer backbone (P) via a-C (═ O) -O-group.

One aspect of the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a linear diblock polymer backbone, comprising at least the steps of:

reacting a diblock polymer as described above with a compound of formula (IV) at a temperature of 80 ℃ or more to 150 ℃ or less:

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group; and

wherein the linear diblock polymer comprises a first and a second block and is obtained by the living radical polymerization described above, optionally in the presence of a solvent (S3).

In one embodiment of the present invention, the solvent (S3) is selected from the group consisting of butyl acetate, methyl N-amyl ketone, methyl isoamyl ketone, and isopropanol.

In one embodiment, the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a linear diblock polymer backbone, comprising at least the steps of:

reacting a diblock polymer as described above with a compound of formula (IV) at a temperature of 100 ℃ or more to 130 ℃ or less:

wherein

R1 is selected from naphthyl, anthryl and phenanthryl, each of which is unsubstituted or substituted by 1,2 or 3-OH; and

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group; and

wherein the linear diblock polymer comprises a first and a second block and is obtained by the living radical polymerization described above, optionally in the presence of a solvent (S3).

In a preferred embodiment, the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a linear diblock polymer backbone, comprising at least the steps of:

reacting a diblock polymer as described above with a compound of formula (IV) at a temperature of 100 ℃ or more to 130 ℃ or less:

wherein

R1 is naphthyl, which is unsubstituted or substituted by 1,2 or 3-OH; and

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group; and

wherein the linear diblock polymer comprises a first and a second block and is obtained by the living radical polymerization described above, optionally in the presence of a solvent (S3).

One aspect of the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a random polymer, comprising at least the steps of:

(a) reacting a random polymer as described above with a compound of formula (IV):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group; and

(b) reacting the compound obtained in step (a) with at least one lactone monomer at a temperature of from ≥ 30 ℃ to ≤ 190 ℃.

In one embodiment, the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a random polymer, comprising at least the steps of:

(a) reacting a random polymer as described above with a compound of formula (IV):

wherein

R1 is selected from naphthyl, anthryl and phenanthryl, each of which is unsubstituted or substituted by 1,2 or 3-OH; and

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group; and

(b) reacting the compound obtained in step (a) with at least one lactone monomer at a temperature of from ≥ 100 ℃ to ≤ 140 ℃.

In a preferred embodiment, the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a random polymer, comprising at least the steps of:

(a) reacting a random polymer as described above with a compound of formula (IV):

wherein

R1 is naphthyl, which is unsubstituted or substituted by 1,2 or 3-OH; and

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group; and

(b) reacting the compound obtained in step (a) with at least one lactone monomer at a temperature of from ≥ 100 ℃ to ≤ 140 ℃.

In one embodiment of the present invention, the at least one lactone monomer described above is selected from the group consisting of delta-valerolactone, epsilon-caprolactone, beta-methyl-delta-valerolactone, 2-methyl-epsilon-caprolactone, 3-methyl-epsilon-caprolactone, 4-methyl-epsilon-caprolactone, 5-tert-butyl-epsilon-caprolactone, 7-methyl-epsilon-caprolactone, 4, 6-trimethyl-epsilon-caprolactone and beta-propiolactone.

One aspect of the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a random polymer, comprising at least the steps of:

(a) reacting at least one polyalkylene glycol monoalkyl ether and at least one carboxylic acid anhydride at a temperature of 70 ℃ or more to 140 ℃ or less to obtain a mixture; and

(b) reacting the mixture obtained in step (a) with the above random polymer and a compound of formula (IV) at a temperature of 70 ℃ or more to 140 ℃ or less:

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group.

In one embodiment, the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a random polymer, comprising at least the steps of:

(a) reacting at least one polyalkylene glycol monoalkyl ether and at least one carboxylic acid anhydride at a temperature of from ≥ 100 ℃ to ≤ 140 ℃ to obtain a mixture; and

(b) reacting the mixture obtained in step (a) with the above random polymer and a compound of formula (IV) at a temperature of 100 ℃ or more to 140 ℃ or less:

wherein

R1 is selected from naphthyl, anthryl and phenanthryl, each of which is unsubstituted or substituted by 1,2 or 3-OH; and

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group.

In a preferred embodiment, the present invention relates to a process for preparing at least one polymeric pigment dispersant comprising a random polymer, comprising at least the steps of:

(a) reacting at least one polyalkylene glycol monoalkyl ether and at least one carboxylic acid anhydride at a temperature of from ≥ 100 ℃ to ≤ 140 ℃ to obtain a mixture; and

(b) reacting the mixture obtained in step (a) with the above random polymer and a compound of formula (IV) at a temperature of 100 ℃ or more to 140 ℃ or less:

wherein

R1 is naphthyl, which is unsubstituted or substituted by 1,2 or 3-OH; and

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group.

Another aspect of the invention relates to a pigment dispersion comprising at least one polymeric pigment dispersant according to the invention, at least one solvent (S5) and at least one pigment.

For the purposes of the present invention, the at least one solvent (S5) is chosen from organic solvents. Representative examples of classes of organic solvents include, but are not limited to, alcohols, ketones or ketoalcohols, ethers, esters, and polyols. Representative examples of organic solvents include, but are not limited to, xylene, toluene, methanol, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, dimethyl ether, methyl ethyl ether, ethyl acetate, ethyl lactate, ethylene glycol, diethylene glycol, and butyl-2-hydroxyethyl ether.

For the purposes of the present invention, the at least one pigment is an almost insoluble, finely divided organic or inorganic colorant according to the definition in german standard specification DIN 55944.

Representative examples of organic pigments include, but are not limited to, monoazo pigments such as c.i. pigment brown 25; c.i. pigment orange 5, 13, 36 and 67; c.i. pigment red 1,2, 3,5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49:1, 52:2, 53:1, 53:3, 57:1, 63, 112, 146, 170, 184, 210, 245 and 251; c.i. pigment yellow 1, 3, 73, 74, 65, 97, 151 and 183;

disazo pigments such as c.i. pigment oranges 16, 34 and 44; c.i. pigment red 144, 166, 214 and 242; c.i. pigment yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188; anthanthrone pigments such as c.i. pigment red 168(c.i. vat orange 3); anthraquinone pigments such as c.i. pigment yellow 147 and 177; c.i. pigment violet 31; anthraquinone pigments such as c.i. pigment yellow 147 and 177; c.i. pigment violet 31; anthrapyrimidine (anthraporimidine) pigment c.i. pigment yellow 108(c.i. vat yellow 20); quinacridone pigments such as c.i. pigment reds 122, 202 and 206; c.i. pigment violet 19; quinophthalone pigments, such as c.i. pigment yellow 138; IIOxazine pigments such as c.i. pigment violet 23 and 37;

flavanthrone pigments such as c.i. pigment yellow 24(c.i. vat yellow 1); indanthrone pigments such as c.i. pigment blue 60(c.i. vat blue 4) and 64(c.i. vat blue 6); isoindoline pigments such as c.i. pigment orange 69; c.i. pigment red 260; c.i. pigment yellow 139 and 185; isoindolinone pigments, such as c.i. pigment orange 61; c.i. pigment red 257 and 260; c.i. pigment yellow 109, 110, 173 and 185; isoviolanthrone pigments such as c.i. pigment violet 31(c.i. vat violet 1); metal complex pigments such as c.i. pigment yellow 117, 150 and 153; c.i. pigment green 8; perinone pigments such as c.i. pigment orange 43(c.i. vat orange 7); c.i. pigment red 194(c.i. vat red 15); perylene pigments such as c.i. pigment black 31 and 32; c.i. pigment red 123, 149, 178, 179(c.i. alsoRaw red 23), 190(c.i. vat red 29), and 224; c.i. pigment violet 29; phthalocyanine pigments such as c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16; c.i. pigment green 7 and 36; pyranthrone pigments, such as c.i. pigment orange 51; c.i. pigment red 216(c.i. vat orange 4); thioindigo pigments such as c.i. pigment red 88 and 181(c.i. vat red 1); c.i. pigment violet 38(c.i. vat violet 3); carbon of triaryl groupPigments such as c.i. pigment blue 1, 61 and 62; c.i. pigment green 1; c.i. pigment red 81, 81:1 and 169; c.i. pigment violet 1,2, 3 and 27; c.i. pigment black 1 (nigrosine); c.i. pigment yellow 101 (aldazine yellow) and c.i. pigment brown 22.

Representative examples of inorganic pigments include, but are not limited to, white pigments such as titanium dioxide (c.i. pigment white 6), zinc white, pigmentary grade zinc oxide; zinc sulfide, lithopone; white lead; and white fillers such as barium sulfate and CaCO3, black pigments such as iron oxide black (c.i. pigment black 11), iron manganese black, spinel black (c.i. pigment black 27), carbon black (c.i. pigment black 7); color pigments such as chromium oxide, hydrated chromium oxide green; chromium green (c.i. pigment green 48); cobalt green (c.i. pigment green 50); ultramarine green; cobalt blue (c.i. pigment blue 28 and 36); ultramarine blue, iron blue (c.i. pigment blue 27), manganese blue, ultramarine violet, cobalt violet, manganese violet, red iron oxide (c.i. pigment red 101); cadmium sulfoselenide (c.i. pigment red 108); molybdenum red (c.i. pigment red 104); ultramarine red, brown iron oxide, mixed brown, spinel and corundum phases (c.i. pigment brown 24, 29 and 31), chromium orange; yellow iron oxide (c.i. pigment yellow 42); nickel titanium yellow (c.i. pigment yellow 53; c.i. pigment yellow 157 and 164); chrome titanium yellow; cadmium sulfide and cadmium zinc sulfide (CI pigment yellow 37 and 35); chrome yellow (c.i. pigment yellow 34), zinc yellow, alkaline earth metal chromates; na Pu yellow; bismuth vanadate (c.i. pigment yellow 184); interference pigments, such as metal effect pigments based on coated metal flakes, pearlescent pigments based on mica flakes coated with metal oxides, and liquid crystal pigments.

For the purposes of the present invention, the at least one pigment is selected from metallic pigments and effect pigments. Representative examples of effect pigments include, but are not limited to, red pearlescent mica, white pearlescent mica, green organic mica, yellow mica, blue alkali mica.

For the purposes of the present invention, the at least one pigment may also comprise a mixture of two or more different pigments.

For the purposes of the present invention, the at least one pigment is preferably selected from the group consisting of BASF Perrido Maroon L3920, BASF Perrido Maroon L3990, Sun Chemical Perrido Ma-ron 229-.

In one embodiment of the invention, the weight ratio of polymeric pigment dispersant to the at least one pigment is in the range of ≥ 0.1:1 to ≤ 3: 1.

In a preferred embodiment of the present invention, the weight ratio of polymeric pigment dispersant to the at least one pigment is in the range of ≥ 0.25:1 to ≤ 1.5: 1.

For the purposes of the present invention, the average particle size of the pigment particles is in the range from ≥ 10 nm to ≤ 10 μm in diameter, preferably in the range from ≥ 10 nm to ≤ 5 μm, more preferably in the range from ≥ 10 nm to ≤ 1 μm.

For the purposes of the present invention, pigment dispersions can be prepared by methods known to those of ordinary skill in the art. Representative examples of methods of preparing the pigment dispersion include, but are not limited to, energy intensive mixing or milling using a ball mill or a media mill.

Another aspect of the invention relates to a coating composition comprising the pigment dispersion according to the invention and at least one binder.

For purposes of the present invention, representative examples of binders include, but are not limited to, paints, fillers, and additives. Representative examples of additives include, but are not limited to, surfactants, light stabilizers, ultraviolet absorbers, defoamers, dyes, plasticizers, leveling agents, and antiskinning agents. For the purposes of the present invention, the at least one binder is preferably selected from the group consisting of poly (meth) acrylates, polystyrenes, polyesters, alkyds, polysaccharides and polyurethanes.

In one embodiment of the present invention, the coating composition is a solvent borne composition. For the purposes of the present invention, solvent-borne coating compositions are compositions comprising organic solvents. Representative examples of organic solvents include, but are not limited to, xylene, toluene, methanol, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, dimethyl ether, methyl ethyl ether, ethyl acetate, ethyl lactate, ethylene glycol, diethylene glycol, and butyl-2-hydroxyethyl ether.

In one embodiment of the invention, the coating composition is an aqueous composition. For the purposes of the present invention, a water-borne coating composition is a composition which comprises water as the main solvent. However, from 0 wt% to 10 wt%, preferably from 0 wt% to 5 wt%, most preferably from 0 wt% to 1 wt% of organic solvent may be present in the aqueous coating composition.

In one embodiment of the present invention, the varnish material comprises the above-described coating composition.

In one embodiment of the invention, the pigmented paint material comprises the above-described coating composition.

One aspect of the present invention relates to the use of the pigment dispersions according to the invention in printing inks, automotive base paints, automotive varnishes, lacquers, furniture coatings and wood coatings.

In one embodiment of the present invention, the above pigment dispersion is used as a clearcoat material, a topcoat material and an electrodepositable coating material for industrial coating selected from automotive OEM coating, coating of parts installed in or on automobiles and/or utility vehicles, and automotive refinishing.

Another aspect of the invention relates to an article coated with at least one layer formed from the coating composition according to the invention.

For the purposes of the present invention, the coating composition can preferably be applied to the article by any conventional application method. Representative examples of application methods include, but are not limited to, spray coating, knife coating, spread coating, cast dip coating, dipping, curtain coating, or roll coating. With respect to such application, the substrate to be coated may stand on its own, moving the application unit or apparatus. Alternatively, the substrate to be coated, more particularly the web, may be moved, while the application unit is stationary or suitably moved relative to the substrate. Preferred application methods are air spraying, airless spraying, high speed rotation, electrostatic spraying, alone or in combination with thermal spraying, e.g. hot air spraying.

For the purposes of the present invention, the coating compositions of the present invention may be applied to uncoated or pre-coated articles.

One aspect of the present invention relates to compounds of formula (IV)

Wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

the following compound N-naphthyl-4-carboxy-1, 2-phthalimide is thereby excluded.

Another aspect of the invention relates to compounds of formula (IV)

Wherein

R1 is selected from unsubstituted naphthyl or naphthyl substituted by 1,2 or 3-OH; and

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group.

For the purposes of the present invention, the compounds of the formula (IV) described above and below are also referred to as anchor groups or anchors (anchors). For the purposes of the present invention, the polymeric pigment dispersants described above and below are also referred to as pigment dispersants or hyperdispersants or polymeric dispersants or dispersants. One advantage of the present invention is that it has surprisingly been found that the compounds of formula (IV) of the present invention provide colloidal stabilization to prevent aggregation and/or agglomeration of the microparticles or particles when acting as dispersants. The compounds of formula (IV) as described above and below provide good interaction and strong adsorption with the pigment surface through even weak interactions, such as pi-pi and hydrogen bonding interactions. Furthermore, it is an advantage of the present invention that the polymeric dispersant can be prepared in a cost-effective, simple and efficient process. The compound of formula (IV) as described above and below has improved solubility in low polar solvents to make the synthesis of the polymeric pigment dispersant easier than conventionally known methods. The polymeric pigment dispersants of the present invention provide high chroma and transparent colors compared to conventional hyperdispersants or pigment dispersants.

In a preferred embodiment, the present invention relates to a polymeric pigment dispersant comprising a polymeric backbone (P) and at least one moiety of formula (I):

wherein

R1 naphthyl, which is unsubstituted or substituted by 1,2, 3,4 or 5 substituents independently of one another selected from F, Cl, Br, I, -NO₂、-CN、-OH、-O-C₁-C₆-alkyl, -C (═ O) -C₁-C₆-alkyl, -C (═ O) -O-C₁-C₆-alkyl, -C (═ O) -O-phenyl, -CH₂-C(＝O)-C₁-C₆-alkyl, -C (═ O) -NH (C)₁-C₆) Alkyl, -C (═ O) -NH-phenyl, -C₁-C₆-alkanesSubstituent substitution of the group; wherein-C₁-C₆Alkyl is unsubstituted or substituted by 1,2, 3,4 or 5 radicals independently of one another from the group F, Cl, Br, I, -CN, -OH, -O-CF₃、-O-CH₃and-O-C₂H₅Substituted with the substituent(s);

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -O-group; and

whereby the moiety of formula (I) is bonded to the polymer backbone (P) via a-C (═ O) -O-group.

In a preferred embodiment, the present invention relates to a polymeric pigment dispersant comprising a polymeric backbone (P) and at least one moiety of formula (I):

wherein

R1 is selected from naphthyl, anthryl and phenanthryl, each of which is unsubstituted or substituted by 1,2 or 3-OH;

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -O-group; and

whereby the moiety of formula (I) is bonded to the polymer backbone (P) via a-C (═ O) -O-group.

In a preferred embodiment, the present invention relates to a polymeric pigment dispersant comprising a polymeric backbone (P) and at least one moiety of formula (I):

wherein

R1 is naphthyl, which is unsubstituted or substituted by 1,2 or 3-OH;

r2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -O-group; and

whereby the moiety of formula (I) is bonded to the polymer backbone (P) via a-C (═ O) -O-group.

In a preferred embodiment of the present invention, wherein said at least one moiety of formula (I) is prepared by reacting at least one compound of formula (II)

Wherein

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

with at least one compound of the formula (III)

R1-NH₂ (III)

Wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

obtained by reaction in the presence of at least one solvent.

Detailed description of the preferred embodiments

The following series of embodiments is provided to further illustrate the present disclosure and is not intended to limit the present disclosure to the specific embodiments described below.

1. A polymeric pigment dispersant comprising a polymeric backbone (P) and a moiety of formula (I):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -O-group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -O-group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -O-group; and

whereby the moiety of formula (I) is bonded to the polymer backbone (P) via a-C (═ O) -O-group.

2. A polymeric pigment dispersant according to embodiment 1 wherein R1 is selected from naphthyl, anthryl and phenanthryl, unsubstituted or substituted by 1,2, 3,4 or 5 substituents independently of one another selected from F, Cl, Br, I, -NO₂、-CN、-OH、-O-C₁-C₆-alkyl, -C (═ O) -C₁-C₆-alkyl, -C (═ O) -O-C₁-C₆-alkyl, -C (═ O) -O-phenyl, -CH₂-C(＝O)-C₁-C₆-alkyl, -C (═ O) -NH (C)₁-C₆) Alkyl, -C (═ O) -NH-phenyl, -C₁-C₆-substituent substitution of alkyl; wherein-C₁-C₆Alkyl is unsubstituted or substituted by 1,2, 3,4 or 5 radicals independently of one another from the group F, Cl, Br, I, -CN, -OH, -O-CF₃、-O-CH₃and-O-C₂H₅Is substituted with the substituent(s).

3. The polymeric pigment dispersant according to embodiment 1 wherein R1 is selected from the group consisting of naphthyl, anthryl, and phenanthryl, each of which is unsubstituted or substituted with 1,2, or 3-OH.

4. The polymeric pigment dispersant according to embodiment 1 wherein R2 and R3 together with the carbon atom to which they are bonded form a ring selected from phenyl and cyclohexyl each substituted with a-C (═ O) -O-group.

5. The polymeric pigment dispersant of embodiment 1 wherein the at least one moiety of formula (I) is formed by reacting at least one compound of formula (II)

Wherein

R2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

with at least one compound of the formula (III)

R1-NH₂ (III)

Wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

optionally in the presence of at least one solvent.

6. The polymeric pigment dispersant according to embodiment 5 wherein the at least one compound of formula (II) is selected from phthalic anhydride, hexahydrophthalic anhydride, dodecenylsuccinic anhydride, octadecenylsuccinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and nadic anhydride, each substituted with at least one-C (═ O) -OH group.

7. The polymeric pigment dispersant of embodiment 5 wherein the at least one compound of formula (III) is selected from the group consisting of 1-naphthylamine and 7-hydroxy 1-naphthylamine.

8. The polymeric pigment dispersant of embodiment 5 wherein the at least one solvent is a polar solvent having a boiling point of 80 ℃ or more to 160 ℃ or less and a dielectric constant of 11 or more to 30 or less.

9. The polymeric pigment dispersant of embodiment 8 wherein the at least one solvent is selected from the group consisting of methyl N-amyl ketone, methyl ethyl ketone, methyl isoamyl ketone, and isopropyl alcohol.

10. The polymeric pigment dispersant according to embodiment 1 wherein the polymeric backbone (P) is a linear diblock polymer.

11. The polymeric pigment dispersant of embodiment 10 wherein said linear diblock polymer is obtained by living radical polymerization.

12. The polymeric pigment dispersant of embodiment 10 wherein the linear diblock polymer has the formula a-B, wherein

A is a first polymer block obtained by reacting a first mixture comprising at least one glycidyl (meth) acrylate; and

b is a second polymer block obtained by reacting a second mixture comprising at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, polyethylene glycol (meth) acrylates, and polyethylene glycol alkyl ether (meth) acrylates.

13. The polymeric pigment dispersant of embodiment 12 wherein the alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, and isodecyl (meth) acrylate.

14. The polymeric pigment dispersant of embodiment 12 wherein the hydroxyalkyl (meth) acrylate is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.

15. The polymeric pigment dispersant according to embodiment 12 wherein said polyethylene glycol alkyl ether (meth) acrylate is selected from the group consisting of polyethylene glycol methyl ether acrylate, polyethylene glycol ethyl ether acrylate, polyethylene glycol propyl ether acrylate, and polyethylene glycol butyl ether acrylate.

16. A polymeric pigment dispersant according to embodiment 1 whereinThe polymeric pigment dispersant has a number average molecular weight (M) of 1000g/mol or more to 25000g/mol or less as determined by gel permeation chromatography of a control polystyrene standard_n)。

17. The polymeric pigment dispersant of embodiment 1, wherein the polymeric pigment dispersant has a polydispersity of ≥ 1.2 to ≤ 20 as determined by gel permeation chromatography of control polystyrene standards.

18. The polymeric pigment dispersant of embodiment 1 wherein the total weight of the at least one moiety of formula (I) is in the range of ≥ 5 wt.% to ≤ 50 wt.%, based on the total weight of the polymeric pigment dispersant.

19. The polymeric pigment dispersant according to embodiment 1 wherein the polymeric backbone (P) is a random polymer.

20. The polymeric pigment dispersant of embodiment 19 wherein the random polymer is obtained by free radical polymerization.

21. The polymeric pigment dispersant of embodiment 19 wherein the random polymer is obtained by reacting a mixture (M) comprising:

(a) glycidyl methacrylate and/or glycidyl acrylate;

(b) at least one monomer selected from the group consisting of alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, and cycloalkyl (meth) acrylates;

(c) optionally at least one styrene monomer; and

(d) optionally at least one monomer selected from the group consisting of vinyl monomers, monoethylenically unsaturated monomers bearing a urea or keto group, and benzyl (meth) acrylate,

optionally in the presence of at least one solvent.

22. The polymeric pigment dispersant of embodiment 21 wherein the alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, and isodecyl (meth) acrylate.

23. A polymeric pigment dispersant according to embodiment 21 wherein said hydroxyalkyl (meth) acrylate is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate.

24. The polymeric pigment dispersant of embodiment 21 wherein the cycloalkyl (meth) acrylate is selected from the group consisting of cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecyl (meth) acrylate, isobornyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, and bornyl (meth) acrylate.

25. The polymeric pigment dispersant of embodiment 21 wherein said at least one styrene monomer is selected from the group consisting of 4-methylstyrene, 3-methylstyrene, 4-tert-butylstyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-alpha-methylstyrene, 2, 6-dichlorostyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 2, 6-difluorostyrene, 3-nitrostyrene, and 4-acetoxystyrene.

26. A polymeric pigment dispersant according to embodiment 21 wherein said at least one vinyl monomer is selected from the group consisting of 3-vinylbenzoic acid, 4-vinylbenzoic acid and 4-vinylbenzyl chloride.

27. A polymeric pigment dispersant according to embodiment 21 wherein the monoethylenically unsaturated monomer bearing a urea or keto group is selected from 2- (2-oxo-imidazolidin-1-yl) ethyl (meth) acrylate, 2-ureido (meth) acrylate, N- [2- (2-oxo) methacrylateOxazolidin-3-yl) ethyl]Esters, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2- (acetoacetoxy) ethyl methacrylateDiacetone acrylamide (DAAM), diacetone methacrylamide, N- (. beta. -ureidoethyl) acrylamide and N- (. beta. -ureidoethyl) methacrylamide.

28. The polymeric pigment dispersant according to embodiment 21 wherein the solvent is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, butanol, butoxyethanol, acetone, butanone, pentanone, hexanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, pentyl acetate, methoxypropyl acetate, tetrahydrofuran, diethyl ether, ethylene glycol, polyethylene glycol, and mixtures thereof.

29. The polymeric pigment dispersant of embodiment 19, wherein the random copolymer has a number average molecular weight (M) of 1000g/mol or more to 25000g/mol or less as determined by gel permeation chromatography of a control polystyrene standard_n)。

30. The polymeric pigment dispersant of embodiment 19, wherein the random copolymer has a polydispersity of ≥ 1.5 to ≤ 20 as determined by gel permeation chromatography of control polystyrene standards.

31. The polymeric pigment dispersant of embodiment 19 wherein the polymeric pigment dispersant is a graft polymer.

32. The polymeric pigment dispersant of embodiment 31 wherein said graft polymer comprises at least one polyester block.

33. The polymeric pigment dispersant of embodiment 32 wherein the polyester block is obtained from monomer units of a hydroxy functional aliphatic acid or a hydroxy functional aromatic acid or a hydroxy functional araliphatic acid.

34. The polymeric pigment dispersant of embodiment 32 wherein the polyester block is obtained in the presence of a saturated fatty acid or an unsaturated fatty acid.

35. The polymeric pigment dispersant of embodiment 34 wherein the saturated or unsaturated fatty acid is selected from the group consisting of oleic acid, linolenic acid, palmitoleic acid, and tall oil fatty acid.

36. The polymeric pigment dispersant according to embodiment 33 wherein the hydroxy-functional aliphatic acid is selected from the group consisting of glycolic acid, lactic acid, 5-hydroxyvaleric acid, 3-hydroxy-butyric acid, 4-hydroxy-valeric acid, 12-hydroxystearic acid and 6-hydroxyhexanoic acid.

37. The polymeric pigment dispersant of embodiment 32 wherein the polyester block is obtained from lactone monomer units.

38. The polymeric pigment dispersant of embodiment 37 wherein the lactone is selected from the group consisting of delta-valerolactone, epsilon-caprolactone, beta-methyl-delta-valerolactone, 2-methyl-epsilon-caprolactone, 3-methyl-epsilon-caprolactone, 4-methyl-epsilon-caprolactone, 5-tert-butyl-epsilon-caprolactone, 7-methyl-epsilon-caprolactone, 4, 6-trimethyl-epsilon-caprolactone and beta-propiolactone.

39. The polymeric pigment dispersant of embodiment 32 wherein the total weight of the at least one polyester block is in a range of ≥ 5 wt% to ≤ 95 wt% based on the total weight of the polymeric pigment dispersant.

40. The polymeric pigment dispersant according to embodiment 32 wherein the polyester block is bonded to the moiety of formula (I) and/or the polymer backbone (P) via a-C (═ O) -O-group.

41. The polymeric pigment dispersant of embodiment 31 wherein said graft polymer comprises at least one polyether block.

42. A polymeric dispersant according to embodiment 41, wherein said at least one polyether block comprises polyoxyethylene groups containing from 10 to 120 ethylene oxide units.

43. A polymeric pigment dispersant according to embodiment 41 or 42 wherein the polyether block is bonded to the moiety of formula (I) and/or the polymer backbone (P) via a-C (═ O) -O-group.

44. A method of making at least one polymeric pigment dispersant according to any of embodiments 10-18 comprising at least the steps of:

reacting the linear diblock polymer with a compound of formula (IV) at a temperature of 80 ℃ or more to 150 ℃ or less:

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group; and

wherein the linear diblock polymer comprises a first and a second block and is obtained by living radical polymerization, optionally in the presence of a solvent.

45. A method of making at least one polymeric pigment dispersant according to any of embodiments 19-40 comprising at least the steps of:

(a) reacting a random polymer as defined in any one of embodiments 19 to 21 with a compound of formula (IV):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 with itThe carbon atoms to which they are bonded together form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group;

and

(b) reacting the compound obtained in step (a) with at least one lactone monomer at a temperature of from ≥ 30 ℃ to ≤ 190 ℃.

46. A method of making at least one polymeric pigment dispersant according to any of embodiments 41-43 comprising at least the steps of:

(a) reacting at least one polyalkylene glycol monoalkyl ether and at least one carboxylic acid anhydride at a temperature of 70 ℃ or more to 140 ℃ or less to obtain a mixture; and

(b) reacting the mixture obtained in step (a) with a random polymer as defined in embodiments 19 to 21 and a compound of formula (IV):

wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl, each substituted with one-C (═ O) -OH group.

47. A pigment dispersion comprising at least one polymeric pigment dispersant according to any one of embodiments 1 to 43, at least one solvent, and at least one pigment.

48. The pigment dispersion according to embodiment 47, wherein the weight ratio of the polymeric pigment dispersant to the at least one pigment is in the range of ≥ 0.1:1 to ≤ 3: 1.

49. A coating composition comprising a pigment dispersion according to embodiment 47 or 48 and at least one binder.

50. The coating composition according to embodiment 49, wherein the coating composition is a solvent borne composition.

51. The coating composition according to embodiment 49, wherein the coating composition is an aqueous composition.

52. Use of the pigment dispersion according to embodiment 47 or 48 in printing inks, automotive basecoats, automotive varnishes, lacquers, furniture coatings and wood coatings.

53. An article coated with at least one layer formed from the coating composition according to any one of embodiments 49-51.

54. A compound of formula (IV)

Wherein

R1 is selected from unsubstituted or substituted naphthyl, unsubstituted or substituted anthracenyl, and unsubstituted or substituted phenanthrenyl;

r2 is selected from hydrogen; straight-chain or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group;

r3 is selected from linear or branched substituted C₁-C₁₄Alkyl and straight or branched substituted C₂-C₁₄Alkenyl, each substituted with one-C (═ O) -OH group; or

R2 and R3 together with the carbon atom to which they are bonded form a substituted phenyl or substituted C₃-C₁₀Cycloalkyl or substituted C₄-C₁₀Cycloalkenyl radicals, each substituted by one-C (═ O) -OH groupSubstitution;

the following compound N-naphthyl-4-carboxy-1, 2-phthalimide is thereby excluded.

55. A compound of formula (IV)

Wherein

R1 is selected from unsubstituted naphthyl or naphthyl substituted by 1,2 or 3-OH; and is

R2 and R3 form, together with the carbon atom to which they are bonded, a ring selected from phenyl and cyclohexyl each substituted with one-C (═ O) -OH group.

While the invention has been described in terms of specific embodiments thereof, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within the scope of the invention.

Examples

The invention is illustrated in detail by the following non-limiting examples. More particularly, the test methods specified below are part of the general disclosure of the present application and are not limited to specific examples.

Preparation of the Compound of formula (IV)

The preparation of the compounds of formula (IV) is carried out by reacting the anhydride with the amine in a suitable solvent under reflux conditions followed by precipitation or drying under reduced pressure in vacuo (scheme 1: a to g).

The synthesis of compounds of formula (IV) (anchors C to F) is shown below in schemes 1: a to g.

Scheme 1: a to g

a)

b)

c)

d)

e)

f)

g)

Preparation of N-naphthyl-4-carboxy-1, 2-phthalimide (scheme 1a):

A500-mL round-bottom flask was charged with 100 g (0.52 mol) of trimellitic anhydride (source: Sigma Aldrich), 81.98 g (0.57 mol) of 1-naphthylamine (source: Sigma Aldrich), and 65 g of DMF and refluxed for 2.5 hours. After cooling to room temperature, the mixture was diluted in 300 ml of butyl acetate and precipitated in 500 ml of hexane. The precipitate was filtered off and dried under reduced pressure, which yielded 155 g of a yellow solid product (anchor C).

Preparation of N-naphthyl-4-carboxy-1, 2-phthalimide (scheme 1b):

in a1 liter round bottom flask with Dean-Stark, 100 g (0.52 mole) trimellitic anhydride (source: Sigma Aldrich), 81.98 g (0.57 mole) 1-naphthylamine (source: Sigma Aldrich) and 200 g isopropanol were refluxed for 15 hours. The reaction was followed by NMR spectroscopy. At the end of the reaction, 150 g of isopropanol were distilled off by heating under reflux conditions. The remaining isopropanol was removed by vacuum to yield 212.94 grams (85% solids) of product (anchor C).

Preparation of N-naphthyl-4-carboxy-1, 2-phthalimide (scheme 1c):

in a1 liter round bottom flask with dean-Stark attached, 100 g (0.52 mole) trimellitic anhydride (source: Sigma Aldrich), 81.98 g (0.57 mole) 1-naphthylamine (source: Sigma Aldrich), and 200 g MIAK were refluxed for 2.5 hours while distilling water. The reaction was followed with the amount of water collected in the formulation apparatus. At the end of the reaction, 150 g of MIAK were distilled off by heating under reflux. The remaining solvent was removed under reduced pressure to yield 200 g (91% solids) of the product (anchor C).

Preparation of N- (7-hydroxynaphthyl) -4-carboxy-1, 2-phthalimide (scheme 1d):

a250 ml round bottom flask was charged with 50 g (0.26 mol) of trimellitic anhydride (source: Sigma Aldrich), 46.0 g (0.29 mol) of 7-hydroxy 1-naphthylamine (source: Sigma Aldrich), and 60 g of DMF and refluxed for 3 hours. After cooling to room temperature, the mixture was diluted in 300 ml of butyl acetate and precipitated in 500 ml of hexane. The precipitate was filtered off and dried under reduced pressure, which yielded 85 g (65% solids) of the product (anchor D).

Preparation of N- (7-hydroxynaphthyl) -4-carboxy-1, 2-phthalimide (scheme 1e):

in a 500 ml round bottom flask with dean-stark, 30.17 g (0.16 mol) of trimellitic anhydride (source: Sigma Aldrich), 25 g (0.16 mol) of 7-hydroxy 1-naphthylamine (source: Sigma Aldrich) and 150 g of MIAK were refluxed for 5 hours while distilling water. The reaction was followed with the amount of water collected in the dean-stark apparatus. At the end of the reaction, 50 g of MIAK were distilled off by heating under reflux. The remaining MIAK was removed under reduced pressure to yield 87.57 g (63% solids) of the product (anchor D).

Preparation of diblock polymer pigment dispersants

(I) Preparation of solvent-based diblock prepolymers

The diblock prepolymers (prepolymer 1, prepolymer 2 and prepolymer 3) for the solvent borne dispersants were synthesized by Controlled Radical Polymerization (CRP) in three main steps as described below according to methods familiar to those skilled in the art. The raw material compositions are provided in tables 1-3. The characteristics of the different backbones used for the synthesis of the random type polymeric dispersants are shown in table 4.

Step A5 liter four-necked round bottom flask equipped with a condenser, stirrer and thermocouple was charged with reagents 1-4 (Table 1-2) and purged with nitrogen for 10 minutes. Thereafter, reagent 5 was added and purged for a further 20 minutes. The dark brown mixture was heated to 70 ℃ and held at this temperature for 1.5 hours. The nitrogen purge was continued until the temperature reached 70 ℃.

Step B at the end of step A, the temperature of the reaction mixture was lowered to 60 ℃ and a mixture of reagents 6-9 (Table 1-2) purged with nitrogen for 30 minutes was transferred into the reaction flask through a cannula under slight positive nitrogen pressure. The reaction temperature was increased to 80 ℃ and maintained at 80 ℃ for 9.5 hours.

Step C, at the end of step B, the reaction mixture is exposed to air. A mixture of reagents 10 and 11 (Table 1-2) was added directly to the flask and held at 80 ℃ for 5 hours. Near the end of this process, the green color of the resin disappeared, and the initially yellow amberlyst-748 resin turned into a blue-green color. The solution was filtered through a solid filter funnel to remove amberlyst resin beads. Acetic acid and some solvent were distilled off under reduced pressure until 10% of volatiles were removed.

TABLE 1 Synthesis of prepolymer 1

Wherein

Glycidyl methacrylate and HPMA ═ 2-hydroxypropyl methacrylate, available from Dow Chemical; butyl methacrylate, TsCl ═ p-toluenesulfonyl chloride, acetic acid, and Bpy ═ bipyridine were obtained from Sigma Aldrich; butyl acrylate was obtained from BASF and Amberlyte-748 resin was obtained from Alfa Aesar.

TABLE 2 Synthesis of prepolymer 2

Wherein

Glycidyl methacrylate and HPMA ═ 2-hydroxypropyl methacrylate, available from Dow Chemical; butyl methacrylate, TsCl ═ p-toluenesulfonyl chloride, acetic acid, and Bpy ═ bipyridine were obtained from Sigma Aldrich; butyl acrylate was obtained from BASF and Amberlyte-748 resin was obtained from Alfa Aesar.

TABLE 3 Synthesis of prepolymer 3

Wherein

MIBK ═ methyl isobutyl ketone; glycidyl methacrylate and HPMA ═ 2-hydroxypropyl methacrylate, available from Dow Chemical; TsCl-p-toluenesulfonyl chloride, acetic acid, Bpy-bipyridine and pegmecrylate 480-polyethylene glycol methyl ether acrylate M_n480 from Sigma Aldrich; and amberlyst-748 resin was obtained from Alfa Aesar.

(II) preparation of solvent-borne diblock Polymer dispersant

The diblock prepolymer, prepolymer 2, was reacted with anchors C and D (scheme 1) using catalytic amounts of N, N-dimethyldodecylamine and butyl acetate under reflux conditions (115 deg.C-124 deg.C) until the Epoxy equivalent Weight (Weight per Epoxy) (WPE) reached >15,000 to yield a light brown clear solution, dispersant 1 and dispersant 2 (Table 4), approximately 50% non-volatile (NV).

(III) preparation of control diblock Polymer dispersant

A comparative example of a diblock copolymer was prepared by reacting prepolymer 2 with commercially available N-methylcarboxyl-1, 8-naphthalimide to yield dispersant 4 (table 4) using the same procedure described above for the preparation of solvent-borne diblock polymer dispersants.

(IV) preparation of aqueous diblock Polymer dispersant

Diblock prepolymer 3 was reacted with anchor C (scheme 1) to yield dispersant 3, 65% solids. The mixture was heated under reflux conditions (115 ℃) until the WPE value reached 12,000. The final product was dried in vacuo to remove MIBK. The resulting product was reduced in 50/50(w/w) butyl Cellosolve (feed stock: Eastman Chemical Company) and DI water to give a brown clear solution, approximately 50% non-volatile (NV).

TABLE 4 composition of the final diblock dispersant resin

Outside the scope of the invention

Preparation of random polymeric pigment dispersants

(I) Preparation of glycidyl-functional polyacrylate backbones (acrylic backbones BB-1 and BB-2)

Glycidyl-functional acrylic copolymers useful for the synthesis of random polymeric dispersants are synthesized by random copolymerization of Glycidyl Methacrylate (GMA) with other vinyl monomers and/or (meth) acrylate monomers by free radical polymerization using the conventional state of the art of solution polymerization techniques. The important features of these polyacrylates are described in table 5. 2,2' -azobis (2-methylbutyronitrile) AMBN was used as thermal initiator. The characteristics of the different backbones used to synthesize the comb hyperdispersant are shown in table 5.

Table 5:

wherein

PbW weight portions

GMA ═ glycidyl methacrylate (feed source: Mitsubishi Gas Chemical Company); MMA ═ methyl methacrylate; UMA ═ ureido methacrylate (used as a 25% W/W solution in MMA) (stock: BASF); EHA ═ ethylhexyl acrylate (source: Sigma Aldrich); BzMA ═ benzyl methacrylate (feed source: Geo Specialty Chemical Company); MIBK ═ methyl isobutyl ketone (source: Sigma Aldrich).

(II) preparation of solvent-borne random Polymer dispersant (dispersant 5)

Step-1, synthesizing an anchor grafting intermediate:

according to a method familiar to the person skilled in the art, glycidyl-functional Acrylic copolymer (Acrylic-BB-1) (36.3 g) was reacted with anchor D (30.5 g) in the presence of catalytic amounts of zinc acetylacetonate at 110-115 ℃ until almost all epoxy groups were consumed as confirmed by FTIR spectroscopy. The reaction mass was cooled to ambient conditions and diluted while cooling by the addition of methyl ethyl ketone (60 g).

Step-2, grafting a polyester side chain:

the linear polyester stabilizing chain is "grafted-out" by ring-opening polymerization of the lactone monomer from the anchor-grafted intermediate in step-1 above, according to methods familiar to those skilled in the art. The intermediate was gradually heated to 125 ℃ while distilling off the solvent present in the intermediate. A mixture of epsilon-caprolactone (132.1 g) and delta-valerolactone (29.0 g) was fed into the reactor along with tin (II) 2-ethylhexanoate (0.54 g) while maintaining the temperature between 120 deg.C and 130 deg.C. The reaction is further continued at 125 ℃ until the desired conversion of the lactone is achieved as evidenced by measuring the% NV as compared to the theoretically expected value. After the conversion was achieved, the mass was cooled to 75 ℃ and diluted with n-butyl acetate and stirred until a homogeneous solution was observed. The dispersant had a final% NV of 60.8%.

(III) preparation of solvent-borne random Polymer dispersant (dispersant 6)

Step-1, synthesizing an anchor grafting intermediate:

glycidyl-functional Acrylic copolymer (Acrylic-BB-1) (36.9 g) was reacted with Anchor C (24.05 g) in the presence of catalytic amounts of zinc acetylacetonate at 115 ℃ to 120 ℃ until almost all epoxy groups were consumed according to methods familiar to those skilled in the art. The reaction mass was cooled to ambient conditions and diluted while cooling by the addition of methyl ethyl ketone (10 g).

Step-2, grafting a polyester side chain:

the linear polyester stabilizing chain is "grafted-out" by ring-opening polymerization of the lactone monomer from the anchor-grafted intermediate in step-1 above, according to methods familiar to those skilled in the art. The intermediate was gradually heated to 125 ℃ while distilling off the solvent present in the intermediate. A mixture of epsilon-caprolactone (118.5 grams) and delta-valerolactone (26.0 grams) was fed into the reactor along with tin (II) 2-ethylhexanoate (0.48 grams) while maintaining the temperature between 105 deg.C and 125 deg.C. The reaction is further continued at 120 ℃ until the desired conversion of the lactone is achieved as evidenced by measuring the% NV compared to the theoretically expected value. After the conversion was achieved, the mass was cooled to 75 ℃ and diluted with n-butyl acetate and stirred until a homogeneous solution was observed. The dispersant had a final% NV of 61.7%.

(IV) preparation of aqueous random Polymer dispersant (dispersant 7)

Mixing polyethylene glycol (Carbowax 2000)) (158.2 grams) was loaded into the reactor and heated to 120 ℃ under vacuum and held for 30 minutes. The vacuum was stopped and succinic anhydride (7.5 g) was added and reacted at 118 deg.C-120 deg.C for 3.5 hours. Glycidyl-functional Acrylic copolymer (Acrylic-BB-2) (69.9 g), followed by anchor C (48.4 g) was added in the presence of catalytic amounts of zinc acetylacetonate at 115 deg.C until almost all epoxy groups were consumed (epoxy equivalent weight)>15000 g/eq). The solvent present in the system is distilled off in the course of this by simple distillation. While the reaction mass was cooled to ambient conditions, the mass was diluted by adding a mixture of methyl ethyl ketone (112 g) and 1-propoxy-2-propanol (28 g) while stirring. The dispersant had a final% NV of 66.5%.

TABLE 6 composition of final random polymeric pigment dispersant resin

Evaluation and Observation of polymeric dispersants

To evaluate the polymeric dispersants synthesized according to the above method, solvent-borne and water-borne samples were formulated and milled using Lau Disperser. The sample millbase, color properties and particle size distribution were measured.

The evaluation was performed with a variety of high performance organic pigments for coatings including, but not limited to, BASF Perrido Maroon L3920, BASF Perrido Maroon L39990, Sun Chemical Perrido Maroon 229-. These pigments are available from Sun Chemical, New Jersey, USA and BASF Corporation, New Jersey, USA.

1) Formulation

For the solvent-borne test, 10% Pigment loading was studied at various On-Pigment Dispersant (Dispersant On Pigment) (DoP) concentrations. The concentration of the DoP is-30% -300%. The samples were evaluated in n-butyl acetate (Nexeo Solutions, Warren, Michigan, USA). Table 7 shows a typical formulation for the synthetic dispersant at-50% DoP.

For the aqueous test, 10% pigment loading was studied at various dispersant: pigment (DoP) concentrations. The concentration of the DoP is 25-200%. The samples were evaluated in deionized water and a deionized water/solvent mixture, wherein the solvent component was at least 2.5 wt% of the total formulation. Examples of solvents used include, but are not limited to, propylene glycol n-propyl ether (Nexeo Solutions, Warren, Michigan, USA) and propylene glycol n-butyl ether (Dowanol PNB, The Dow Chemical Company, Midland, Michigan, USA).

2) Grinding

To each formulation was added 0.3mm zirconium stabilized yttria beads (Fox Industries, Fairfield, New Jersey, USA) to grind the pigment. For solvent-based systems, the beads are 100% of the total formulation weight, e.g., 100 grams of formulation is added to 100 grams of beads to give a total of 200 grams. For aqueous systems, the beads are 200% of the total formulation weight, e.g., 100 grams of formulation is added to 200 grams of beads to give a total of 300 grams.

The prepared samples were then placed on a Lau Disperser-Model DAS H-TP 200-K (LAU GmbH, Hemer, Germany) with a cooling system and shaken for 540 minutes or 9 hours while the fan was running. After the run was complete, the sample was filtered to remove beads and stored in an aluminum paint can. The filtered beads are washed with solvent and reused.

Evaluation of stability and color

1) Sample stability

After filtration, the fineness of the millbase was evaluated using a Hegman fineness gauge. A sample is considered acceptable if it exhibits a grind of <6 microns.

2) Color evaluation

The color properties of the solvent-borne pigment dispersions were evaluated in commercially available one-component varnishes from BASF Corp.at 26701Telegraph Rd.Southfield, MI 48033 using Melinex draw paper (Puetz GmbH + C0.Folien KG, Taunussein, Germany) at R10CG 0392D. The pigment (L3920, L3990, 229-.

Once the sample had cooled, the chromatogram was measured using a Byk Mac i spectrophotometer (Byk-Chemie GmbH, Wesel, Germany). A Melinex card with the tinted varnish scratch film was placed on top of the mirror. The Byk Mac i was then placed on top of the Melinex card and mirror and the color data measured using GM CieLab weighted with a d65 light source at 15, 25, 45, 75, and 110 degrees off the mirror. 5 measurements were made for each sample and the duplicate scratch films of a given sample were compared.

This method is used for color evaluation because the higher particle size pigments agglomerate to produce more scattered light, which increases the measured brightness value of the film. Since the 110 ° angle has the most common film path length, it is most sensitive to detecting an increase in scattering. Thus, the value of L (lightness) at an angle of 110 ° is used for the evaluation, thus yielding a dispersion with a lower value of L being more transparent and thus corresponding to an improved distribution or stabilization or dispersion of the pigment particles.

Table 8 provides typical L values at an angle of 110 ° for the formulation systems in table 7.

Table 8:

wherein

L is a lightness value at 110 °;

< dL > is the weight of the difference in L at 110 ℃ between the reference dispersions, i.e., the dispersion compositions containing dispersant 4 (examples 7, 8 and 9, anchor group being N-methylcarboxyl-1, 8-naphthalimide) and the dispersions containing the polymeric pigment dispersants of the present invention (examples 1 to 6)

Discussion of the results

The results in table 8 show that examples 1-6 containing the polymeric pigment dispersant of the present invention exhibit lower values of L. Negative values of < dL > indicate that the polymeric pigment dispersant has a lower value of L than the reference dispersion. This also indicates that the dispersions containing the polymeric pigment dispersants of the present invention are more transparent than the reference dispersions.

Within each pigment type, there is a good correlation between smaller particle size and reduced 110 ° brightness values (related to scattering and opacity). Lower values of L are generally associated with smaller particle sizes.

Advantages of the invention

1) The diblock polymeric dispersant of the present invention provides more efficient deagglomeration than dispersants made from the anchor molecule N-methylcarboxyl-1, 8-naphthalimide, which is also prepared by a Controlled Radical Polymerization (CRP) process, and diblock prepolymer. This indicates that higher chroma and transparent colors can be achieved by high energy micro-milling processes to achieve pigment particles in the less than 100nm size range.

2) The novel anchors (formula IV) of the present invention are compatible with varnish coating compositions containing organic acid catalysts. This is superior to commercial dispersants containing amines which react with acid catalysts and lose dispersing ability.

Test method

Determination of L value

L values were determined using a Byk Mac i spectrophotometer (Byk-Chemie GmbH, Wesel, germany). The color data were measured with a D65 illuminant and the weighted dL or < dL > values were determined using GM CieLab weighting according to standard DIN 6175-2.

Epoxy equivalent Weight (WPE) determination

WPE was determined by titration with hydrogen bromide (HBr) according to ASTM D1652.

Non Volatile (NV) assay

NV was determined according to ASTM D2369 by removing volatile components to 60 minutes in a forced air oven set at 110 ℃.