• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    The present invention is characterized in that the monocyclic or heteronuclear heterocyclic group binds to the highly polar fixed A segment of the block copolymer backbone to facilitate adhesion onto the pigment surface and improves the efficiency of the dispersant of the solvent based paint system. Discloses an acrylic AB block copolymer useful as a pigment dispersant and prepared by group transfer polymerization.
    公开号:KR20020033841A
    申请号:KR1020027004445
    申请日:2000-10-04
    公开日:2002-05-07
    发明作者:요세프 후이브레흐츠；다니엘 씨. 크라이터；로저 베르블로에트
    申请人:메리 이. 보울러；이 아이 듀폰 디 네모아 앤드 캄파니；
    IPC主号:
    专利说明:

    Acrylic Block Copolymer Pigment Dispersants Containing Heterocyclic Groups
    [1] The present invention comprises an acrylic block copolymer prepared by a pigment dispersant, more specifically by group transfer polymerization, in which one of the blocks is modified with a polar heterocyclic group to facilitate adhesion to the pigment surface. It relates to a pigment dispersant.
    [2] Acrylic block copolymer pigment dispersants prepared by group transfer polymerization (GTP) are known. Typically, such dispersants are of the AB, ABA or BAB type. All of these include at least one polar segment known as the A segment which facilitates adhesion to the pigment surface and at least one nonpolar segment known as the B segment which enhances steric stability of the pigment particles in the dispersion and prevents aggregation. . Block A may also be modified with a pendant polarity for increased efficiency, as taught, for example, in US Pat. No. 4,656,226 to Hutchins et al., Dated April 7, 1987. . Such compositions can also be prepared with hydroxyl functionality in the B segment to be crosslinked in the final thermosetting paint composition, making the dispersant part of the net structure, but can negatively affect the properties of the dispersant.
    [3] There is an ongoing effort to improve the performance of pigment dispersants and to find new classes of acrylic block copolymer dispersants which are particularly well suited for dispersing solid pigments in various liquid media, especially solvent based paint systems.
    [4] Summary of the Invention
    [5] The present invention is prepared by GTP polymerization, wherein at least one relatively polar A segment and at least one relatively polar B segment are bonded together, and the backbone of each segment comprises a polymerized methacryl monomer unit as a main component, Consisting of 5- and / or 6-membered rings of mononuclear or heteronuclear containing one or more nitrogen atoms and any oxygen and / or sulfur atoms as ring portions of the ring containing one or more nitrogen to which hydrogen is unbound Provided are compositions suitable for use as pigment dispersants comprising an acrylic block copolymer having at least one polar heterocyclic group selected from the group bonded to at least one A segment. Heterocyclic groups are provided as hanging groups that are attached directly to the A segment or are introduced through urethane and / or urea bonds. In addition, the block copolymer preferably contains hydroxyl functionality in one or both of the A and B segments. Moreover, it is preferable that a block copolymer is AB type.
    [6] The present invention incorporates the aforementioned heterocyclic groups into the A segment, even in the presence of hydroxyl functional groups on the polymer backbone, which are usually needed for crosslinking purposes and are required to improve compatibility with other binder components present in the final paint composition. It is found and based on excellent pigment dispersant properties provided for acrylic block copolymers.
    [7] Preferred heterocyclic groups are triazole, pyrimidine, imidazole, pyridine, morpholine, pyrrolidine, piperazine, piperidine, benzimidazole, benzothiazole and / or triazole. These heterocyclic groups may be unsubstituted or contain substituents such as, for example, alkyl, aryl, halogen and alkoxy groups.
    [8] GTP techniques can be used and are preferably used to produce the acrylic block copolymers of the present invention. GTP techniques are known to produce low molecular weight acrylic block copolymers whose molecular weight distribution and composition distribution are more precisely controlled and whose number average molecular weight (M n ) is generally between 1,300 and 20,000. This technique enables low polydispersity, uniform block formation, and provides more efficient dispersing action. GTP technology is well known and described in detail in US Pat. No. 4,656,226 to Hutschins et al., Issued April 7, 1987, which is incorporated herein by reference.
    [9] According to this technique, an unsaturated monomer is generally contacted with an initiator and a catalyst system containing silicon, tin or germanium, and under these conditions the polymerization proceeds in a controlled manner as opposed to the typical random manner of the polymerization reaction, resulting in a uniform and desired molecular weight. It is possible to produce substantially linear polymers with phosphorus polymer chains. In the present application, the desired molecular weight of the block copolymer is in the above-mentioned range, and in the present invention, less than 13,000 (M n ) is particularly preferred.
    [10] The acrylic block copolymers of the present invention produced by this technique are preferably at least one highly polar A segment, which functions as a moiety anchored to the surface of the pigment, and usually in a high molecular weight and preferably reaction in a thermosetting paint composition. One or more B segments, which are relatively nonpolar, containing functional groups for Polar A segments are designed to be absorbed on the surface of the pigment by acid-base interactions, while the B segment provides steric stability of the pigment particles against aggregation.
    [11] In general, the A segment should be (1) useful for interacting with the pigment surface and (2) large enough to provide irreversible absorption but large enough to completely cover the pigment surface or cause collapse of the B segment. Should not be (typically M n = 300-5,000). The B segment must be (1) of sufficient size to provide steric stability (typically, M n = 1,000 or greater), and (2) compatibility with liquid dispersion medium (solvent) and matrix binding polymer (prevents phase separation) Enough to be soluble).
    [12] All molecular weights mentioned herein are determined by GPC (gel permeation chromatography) using polystyrene standards.
    [13] In addition, as mentioned above, the B segment preferably provides crosslinking to the final thermosetting paint composition so that the dispersant is part of the net structure and to improve compatibility with other binder components, for example, It contains a functional group such as a hydroxyl group. In order for such groups to be present, the polar, fixed moiety (A segment) must not be replaced by other functional groups, because in that case the pigment dispersion becomes unstable.
    [14] The inventors have found that the introduction of heterocyclic groups into the acrylic block copolymers of the general type described above not only improves the performance of the copolymer as a pigment dispersant, but also unexpectedly other segments in which such heterocyclic groups can be competitively adsorbed onto the pigment surface. It has been found that it acts as an efficient fixer even in the presence of hydroxyl groups and polar solvents.
    [15] In the present invention, the basic acrylic block copolymer described above is first prepared by GTP technique, and then the required heterocyclic group is attached directly or indirectly through a functional group located in the fixed A segment using the technique described below. I found it easy.
    [16] In the preparation of the basic block copolymers, the blocks may be prepared in any order. That is, either the A segment or the B segment can be prepared first. In addition, although AB block copolymers are generally preferred, ABA and BAB triblocks can also be prepared if desired. In any case, the backbone of each segment comprises at least one polymerized methacrylate or acrylate ester as the main component, but methacrylate esters are most preferred. In the present invention, methacrylate and acrylate units are generally referred to herein as methacryl and acrylic monomer units.
    [17] More specifically, the B segment is preferably prepared from a blend of alkyl methacrylates or alkyl methacrylates such as methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethyl hexyl methacrylate and the like. If desired, hydroxyl functional groups may be introduced via hydroxylalkyl methacrylate monomers such as hydroxyl ethyl methacrylate (HEMA), hydroxyl propyl methacrylate, and the like. However, hydroxyl groups must be blocked before polymerization to avoid reaction with the initiator used in GTP. A possible way of blocking hydroxyl groups is by using trimethylsilyl or derivatives. Blocked hydroxyl groups can be unblocked by hydrolysis after block copolymer formation. Usually hydroxyl groups are needed in acrylic block copolymers. Acrylic block copolymers generally have a hydroxyl value of 5 to 120. On the other hand, the A segment must have a functional group for the attachment of the polar heterocyclic group. As described more fully below, epoxy functional methacrylates such as glycidyl methacrylate (GMA) and the like, hydroxyl functional methacrylates such as hydroxyl ethyl methacrylate (HEMA) and the like and t-butyl Amino functional methacrylates such as aminoethyl methacrylate (t-BAEMA) and the like can be used for this purpose.
    [18] In the present invention, the A segment generally comprises about 2 to 60% by weight, preferably about 10 to 30% by weight of the block copolymer, and the B segment is generally about 40 to 98% by weight of the block copolymer, preferably Comprises about 70 to 90 weight percent.
    [19] In addition, in the present invention, for optimum efficiency, at least about 2% by weight, most preferably at least 50% by weight, of the A segment (meth) acrylate monomer units are combined with heterocyclic groups. The heterocyclic group may be a mono or dinuclear five- and / or six-membered ring having at least one ring nitrogen atom and at least one ring nitrogen atom containing any ring oxygen and / or sulfur atoms and not containing hydrogen atoms have. As used herein, the term "mononuclear" refers to one 5- or 6-membered ring, and the term "binuclear" refers to a 5- or 6-membered ring fused with another 5- or 6-membered ring. Preferred heterocyclic groups are triazole, pyrimidine, imidazole, pyridine, morpholine, pyrrolidine, piperazine, piperidine, benzimidazole, benzothiazole and / or triazine groups. They may be unsubstituted or contain substituents such as, for example, alkyl, aryl, halogen and alkoxy groups. Particular preference is given to imidazole derivatives substituted with lower alkyl such as 2-methyl imidazole and 4-methyl imidazole.
    [20] Heterocyclic groups can be attached directly to the fixed A segment via reaction of the heterocyclic derivative with the functional group provided by the A segment. As an example given below, the heterocyclic group may be positioned as a group suspended to the fixed A segment through the reaction of the heterocyclic derivative with an epoxy functional group. The synthesis of block copolymers from polymerized (meth) acrylic monomer units, one of the resulting segments containing epoxy functionality, is well described in US Pat. No. 4,656,226 to Hutchins et al. Issued April 7, 1987. have. Epoxy groups can be obtained, for example, via copolymerization of glycidyl methacrylate (Example 1). Thereafter, in the subsequent reaction, the epoxy group can be reacted with a heterocyclic compound having active hydrogen atoms such as -NH-, -NH 2 , -COOH- and -SH. For compounds with two active hydrogens, such as —NH 2 , the amount of glycidyl functional groups should be adjusted to avoid crosslinking and gelling. Also, in this case, -NH 2 , the primary amino functional group, may first be modified through the reaction with a monoepoxy derivative -NH- group, which is a secondary amine. Examples of heterocyclic compounds having one active H atom are given below.
    [21]
    [22] Another possible way for the heterocyclic derivatives to be attached directly as a group suspended to the block copolymer is through the reaction of the carboxyl functional heterocyclic derivatives with the A segment of epoxy groups.
    [23] In addition, heterocyclic groups may be incorporated into the acrylic block copolymers indirectly through urethane and / or urea bonds. As an example given below, N- (3-aminopropyl) imidazole is an imidazole with one unreacted isocyanate functional group that is reacted on a molar basis with isophorone diisocyanate and subsequently reacted with an amino group in one of the segments. Functional urea intermediates may be formed. This amino functional group can be obtained, for example, by copolymerization of t-butylaminoethyl methacrylate (Example 2) or by reaction of an epoxy functional group with a monoamine or ammonia. Examples of monoamines are ethylamine, propylamine, laurylamine, ethanolamine, isopropanolamine and 2-amino butanol. In addition, isocyanate functional heterocyclic urea intermediates may react with hydroxyl groups in the backbone to form urethane bonds. In addition, the reaction of hydroxyl functional heterocyclic derivatives with di- and / or polyisocyanates can form heterocyclic functional intermediates with isocyanate functional groups. One example is 2-hydroxylethyl morpholine. Such hydroxyl functional intermediates are also formed by the reaction of amino functional heterocyclic derivatives with cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, glycerin carbonate Can be. Other examples of diisocyanates include, but are not limited to, toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI), hydrogenated MDI, trimethyl hexamethylene diisocyanate. Possible polyfunctional isocyanates are cyclotrimers and biurets, or reaction products of excess diisocyanates with polyol precursors.
    [24] A new class of heterocyclic acrylic block copolymers is used in addition to pigments and dispersants, such as binders or film formers, organic solvents (ie, liquid dispersion media), and conventional liquids, such as those used in liquid media, especially automotive finishing and refinishing. Excellent performance as a pigment dispersant in solvent-based paint systems containing other additives. Pigments and dispersants may be added to the liquid paint medium individually or in the form of the most preferred dispersion. If a dispersion is used, the dispersion generally contains a dispersion medium (solvent) which is compatible with pigments and liquid paint media.
    [25] The invention will now be described in more detail with specific examples. Parts and percentages are all by weight unless otherwise indicated.
    [26] In Examples 1 and 2 below, the procedure for preparing the basic AB block copolymer, to which various heterocyclic groups are attached, is described.
    [27] All monomers and solvents were passed through 4A molecular sieves to dryness and stored under nitrogen before use.
    [28] <Example 1>
    [29] Preparation of GMA / nBMA / MMA / HEMA 5 // 10/10/2 (molar ratio)
    [30] The 3-liter round bottom four-necked flask was equipped with a condenser / dry tube, digital thermometer probe and N 2 inlet, mechanical stirrer and monomer addition funnel. Thereafter, N 2 was purged into the flask and dried with a heat gun. While flowing N 2 into the flask, 1016.4 g of THF and 50.0 g of 1-methoxy-1-trimethylsiloxy-2-methyl propene were added through an addition funnel, and 2.5 g of mesitylene was added by syringe. The flask was cooled to 4.8 ° C. in an ice bath and 2.5 ml of a 1M solution of tetrabutylammonium m-chlorobenzoate in acetonitrile was injected. Glycidyl methacrylate (GMA) (203.8 g) was added through the addition funnel for 30 minutes. After 25 minutes, the temperature rose to 34 ° C. and cooling was resumed to keep the temperature below 35 ° C. while adding the remaining GMA. After 40 minutes from the start, the GMA conversion was 99.95% and the ice bath was removed and the second monomer (block B) was fed. The main components of block B are n-butyl methacrylate (nBMA) (407.8 g), methyl methacrylate (MMA) (287.4 g) and 2- [trimethylsiloxy] hydroxyl ethyl methacrylate (TMS-HEMA) ( 116.2 g). After 50 minutes, 0.6 ml of catalyst was injected to speed up the reaction. At the end of feed (after 85 minutes) the temperature rose to 70.2 ° C. After 208 minutes, monomer conversion (HPLC) was at least 99.6%. After 333 minutes from the start, 7.7 g of water were added and the flask was cooled to room temperature. The actual solid content of the polymer was 47.94%, M n = 4139 (theoretical value 3500) and D (dispersity) = 1.38.
    [31] <Example 2>
    [32] Preparation of nBMA / MMA / HEMA // t-BAEMA 10/10/2 // 3 (molar ratio)
    [33] The 3-liter round bottom four-necked flask was equipped with a condenser / dry tube, digital thermometer probe and N 2 inlet, mechanical stirrer and monomer addition funnel. Thereafter, N 2 was purged into the flask and dried with a heat gun. While flowing N 2 into the flask, 1100.9 g of THF and 50.0 g of 1-methoxy-1-trimethylsiloxy-2-methyl propene were added through an addition funnel, and 2.5 g of mesitylene was added by syringe. 4.8 mL of tetrabutylammonium m-chlorobenzoate 1 M solution (here called catalyst) in acetonitrile was injected at room temperature and the first monomer was fed. The main components of block B prepared for the first time in this example are n-butyl methacrylate (nBMA) (408.0 g), methyl methacrylate (MMA) (287.5 g) and 2- [trimethylsiloxy] hydroxyl ethyl meta It was methacrylate (TMS-HEMA) (116.7 g) and added for 45 minutes via an addition funnel. After 4 minutes, the temperature rose to 34.5 ° C. and the temperature was kept below 40 ° C. using a cooling bath. After 160 minutes from the start, the monomer conversion measured by HPLC was at least 99.6%. After 205 minutes, the ice bath was removed and the second monomer was fed. The main component of block A was t-butyl aminoethyl methacrylate (t-BAEMA) (160.1 g). Feed II ended after 235 minutes from the start and the temperature rose to 32.7 ° C. After 335 minutes from the start, water (32 g) was added and the reaction composition was cooled to room temperature. The actual solid content of the polymer was 44.81%, M n = 3996 (theoretical value 3300) and D = 1.81.
    [34] In Examples 3 to 6 below, AB block copolymers selected from the above examples were reacted with heterocyclic groups to form AB dispersants of the present invention. However, in Comparative Example 1, the AB block copolymer was reacted with a tertiary aliphatic amine to impart a suspended t-amine functional group to the copolymer instead of a heterocyclic functional group. In Comparative Example 2, no modifications were made to the AB block copolymers to provide a control.
    [35] <Examples 3, 4, 5>
    [36] Preparation of Heterocyclic Modified AB Block Copolymer by Modification of AB Block Copolymer of Example 1
    [37] In a two liter round bottom flask equipped with a condenser, 1000 g of the AB block copolymer solution of Example 1 was charged with 55.5 g of 2-methyl imidazole (Example 3), 55.5 g of 4-methyl imidazole (Example 4) and mor The reaction was allowed to reflux with 58.8 g of Pauline (Example 5) for 4 hours. Thereafter, the polymer solution was diluted to 40% solids with n-butyl acetate.
    [38] The AB block copolymer had a molecular weight (M n ) of 3800 (dispersity (D) = 1.48) in Example 3, 3700 (D = 1.48) in Example 4, and 5800 (D = 1.48) in Example 5.
    [39] Comparative Example 1
    [40] The procedures of Examples 3, 4 and 5 were repeated using 2-methyl ethanolamine instead of heterocyclic derivatives for comparison purposes. According to Hutchins et al. US Pat. No. 4,656,226, an AB block copolymer was produced having t-amine groups in one block.
    [41] Comparative Example 2
    [42] The unmodified AB block copolymer of Example 1 was used for comparison purposes.
    [43] <Example 6>
    [44] Preparation of Heterocyclic Modified AB Block Copolymers by Modification of the AB Block Copolymers of Example 2
    [45] In a 6 liter round bottom flask, 130 g (1 mol) of n-3-aminopropyl imidazole in 1000 g of n-butyl acetate was dissolved in 387 g of n-butyl acetate and 222 g (1 mol) of isophorone diisocyanate The reaction was carried out by stirring for 10 minutes at to form an isocyanate functional urea-imidazole intermediate. This intermediate was further reacted with 2300 g of the block copolymer of Example 2. An imidazole-urea modified AB block copolymer having a number average molecular weight of 5600 and a weight average molecular weight of 10200 was produced.
    [46] <Example 7>
    [47] Evaluation of Dispersant Properties
    [48] The quality of the dispersant is generally assessed by grinding the mixture of pigments, solvents and dispersant into sand and measuring the proportion of dispersant (if any) that produces a uniform dispersion that appears as stained glass at 250x optical magnification. In contrast, aggregated pigments appear as islands of pigments interspersed in a region of relatively transparent solvent. Any scale as provided below represents the degree of dispersion.
    [49] Bayer's perylene maroon r-6436, Sun Chemical's phthalocyanine green 264-0414, Clariant's phthalocyanine blue bt-617-d, Columbian Chemical Five pigments of carbon black 5000 ii powder of and quinacridone magenta rt-143-d from Ciba-giegy were evaluated. In the evaluation, 30 g of Ottawa sand was mixed with 3.38 g of a polymer solution of 40% solids (except 11.25 g for carbon black), 4.5 g of pigment and 40 g of n-butylacetate (non-polar organic solvent) in a rotary mixer. Pulverized for 15 min.
    [50] Thereafter, aggregation was observed under a microscope to evaluate aggregation of the pigment dispersion. In the grade of 0 to 10 (no agglomeration, 10 very agglomerated), the average score of the different AB block copolymers for the five pigments mentioned above was as follows.
    [51] result
    [52] AB dispersantCohesive grade Comparative Example 2 (No Modification)5.5 Example 30.5 Example 40.5 Example 52 Comparative Example 1 (t-amine group)3.5
    [53] The results show that the AB copolymer modified with heterocyclic groups shows better pigment wetting properties and thus improved dispersibility with reduced aggregation.
    [54] Without departing from the spirit and scope of the invention, various modifications, substitutions, additions and substitutions of the components of the compositions of the invention will be apparent to those skilled in the art. The invention is not limited by the exemplary embodiments presented herein but is defined by the following claims.
    权利要求:
    Claims (16)
    [1" claim-type="Currently amended] Relatively non-polar and relatively polar A segments containing heterocyclic groups selected from the group consisting of 5- and 6-membered rings of mononuclear and / or dinuclear containing one or more nitrogen atoms not bonded to hydrogen atoms A composition suitable for use as a pigment dispersant, comprising an acrylic block copolymer having a phosphorus B segment.
    [2" claim-type="Currently amended] The composition of claim 1, wherein the block copolymer is prepared by group transfer polymerization (GTP) technology.
    [3" claim-type="Currently amended] The composition of claim 1, wherein the block copolymer is formed from polymerized (meth) acrylic monomers.
    [4" claim-type="Currently amended] The composition of claim 1 wherein the block copolymer is formed from polymerized methacryl monomers.
    [5" claim-type="Currently amended] The composition of claim 1, wherein the segment containing the heterocyclic group is prepared by reaction of an epoxy functional group on the segment with a heterocyclic compound containing a -NH-, -NH 2 , -COOH or -SH functional group. .
    [6" claim-type="Currently amended] The composition of claim 1, wherein the heterocyclic group is linked to the A segment via urea and / or urethane bonds.
    [7" claim-type="Currently amended] The composition of claim 1 wherein the block copolymer has a hydroxyl value of 5 to 120 and a total number average molecular weight (M n ) of 1,300 to 13,000.
    [8" claim-type="Currently amended] The triazole, pyrimidine, imidazole, pyridine, morpholine, pyrrolidine, piperazine, piperidine, benzimidazole, benzothiazole and trisubstituted or unsubstituted heterocyclic groups according to claim 1. Composition selected from the group consisting of azine.
    [9" claim-type="Currently amended] The composition of claim 1 wherein the heterocyclic group is an imidazole derivative.
    [10" claim-type="Currently amended] The composition of claim 1 wherein the copolymer comprises only one A segment and one B segment bonded together.
    [11" claim-type="Currently amended] About 10 to 30 weight percent of a relatively polar A segment, based on the weight of the copolymer, and
    Comprising about 70 to 90% by weight of relatively nonpolar B segments, based on the weight of the copolymer, containing hydroxyl groups,
    The skeleton of each segment preferably contains polymerized methacrylic monomer units as a main component,
    Heterocyclic groups selected from the group consisting of five and / or six membered rings of mononuclear and / or dinuclear containing one or more nitrogen atoms not bonded to a hydrogen atom, either directly or via a urethane and / or urethane chain Characterized in that bound to at least 50% by weight of the methacryl residue of the A segment indirectly through urea bonds,
    Acrylic AB block copolymer compositions suitable for use as pigment dispersants.
    [12" claim-type="Currently amended] 12. The triazole, pyrimidine, imidazole, pyridine, morpholine, pyrrolidine, piperazine, piperidine, benzimidazole, benzothiazole and trisubstituted unsubstituted or substituted heterocyclic group. Composition selected from the group consisting of azine.
    [13" claim-type="Currently amended] The composition of claim 12, wherein the heterocyclic group is an imidazole derivative.
    [14" claim-type="Currently amended] The composition of claim 13, wherein the heterocyclic group is 2-methyl imidazole or 4-methyl imidazole.
    [15" claim-type="Currently amended] Pigment dispersion in an organic solvent dispersed by the composition of claim 1.
    [16" claim-type="Currently amended] A coating composition comprising the pigment dispersion of claim 15, a film former and a liquid medium.
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-10-07|Priority to US09/414,254
    1999-10-07|Priority to US09/414,254
    2000-10-04|Application filed by 메리 이. 보울러, 이 아이 듀폰 디 네모아 앤드 캄파니
    2002-05-07|Publication of KR20020033841A
    2005-04-08|Application granted
    2005-04-08|Publication of KR100481341B1
    优先权:
    申请号 | 申请日 | 专利标题
    US09/414,254|1999-10-07|
    US09/414,254|US6316564B1|1999-10-07|1999-10-07|Acrylic block copolymer pigment dispersants containing heterocyclic groups|
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