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    • 专利摘要:
    The present invention relates to linear or branched polymers and whole or partially modified polymers containing ester groups and at least one amide group in the main chain, having at least one hydroxyalkylamide end group and having a weight average molecular weight of at least 800 g / mol. As for The polymers according to the invention can be obtained by reaction of cyclic anhydrides with alkanolamines to form β-hydroxyalkylamides, after which the polyesteramides are obtained through polycondensation, The polymers according to the invention are characterized in that they can be used for thermosetting powder-paint compositions.
    公开号:KR20010030837A
    申请号:KR1020007003495
    申请日:1998-09-22
    公开日:2001-04-16
    发明作者:반벤템루돌푸스안토니우스테오도루스마리아；리이트베르그조한；스탄센스디르크아르만드빔
    申请人:윌리암 로엘프 드 보에르；디에스엠 엔.브이；
    IPC主号:
    专利说明:

    Condensation polymer containing a hydroxyalkylamide group {CONDENSATION POLYMER CONTAINING HYDROXYALKYLAMIDE GROUPS}
    The present invention relates to a linear or branched condensation polymer containing an ester group and at least one amide group in the main chain, having at least one hydroxyalkylamide end group, and having a weight average molecular weight of 800 g / mol or more.
    The polymer preferably contains at least two groups of the formula:
    (In Formula 1,
    Y = H, (C 1 -C 20 ) (cyclo) alkyl or (C 6 -C 10 ) aryl,
    B = (C 2 -C 24 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical,
    R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently the same or different and are H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals , And
    n = 1-4).
    More preferably, the polymer contains at least two groups of the formula
    (In Formula 2,
    Y = H, (C 1 -C 20 ) (cyclo) alkyl or (C 6 -C 10 ) aryl,
    B = (C 2 -C 24 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical, and
    R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , independently of one another, are the same or different and are H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals )
    According to another preferred embodiment, the polymer containing hydroxyalkylamide groups is a polymer of the formula
    (In Chemical Formula 3,
    Y = H, (C 1 -C 20 ) (cyclo) alkyl or (C 6 -C 10 ) aryl,
    A =
    B = (C 2 -C 24 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical,
    X 2 = H or X 1 , and
    R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , independently of one another, are the same or different and are H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals or CH 2 -OX 2 )
    In formulas (1), (2) and (3), the R groups together with one another or with neighboring carbon atoms form part of a cycloalkyl group.
    According to another preferred embodiment of the invention, the polymer containing β-hydroxyalkylamide groups is a polymer of the formula:
    (In Formula 4,
    Y = H, (C 1 -C 20 ) (cyclo) alkyl or (C 6 -C 10 ) aryl,
    B = (C 2 -C 20 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical,
    X 2 = H or X 1 ,
    R 3 = H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) alkyl radicals and
    R 6 = H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) alkyl radical)
    The weight average molecular weight of the polymers according to the invention is usually from 800 to 50,000, and preferably from 1000 g / mol to 25,000 g / mol.
    The number average molecular weight is usually 600 to 10,000, and preferably 700 to 4000.
    The hydroxyalkylamide functionality is usually 2 to 250, and preferably 5 to 50.
    The functionality is the average number of specific types of reactors per molecule in the polymer composition.
    According to another preferred embodiment of the invention, the polymer hydroxyalkylamide functionality of the polymer is at least 5 and the polymer containing β-hydroxyalkylamide groups is a polymer of the formula:
    (In Chemical Formula 5,
    B = (C 2 -C 12 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical,
    X 2 = H or X 1 ,
    R 3 = H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals, and
    R 6 = H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radical)
    R 3 and R 6 are preferably (C 1 -C 4 ) alkyl.
    According to another preferred embodiment of the invention, R 3 and R 6 are methyl or ethyl.
    B is saturated or not saturated.
    B is substituted, for example, with a (C 1 -C 26 ) alkyl group, which is saturated or not saturated; C 1 is preferably used.
    B is, for example, (methyl-) 1,2-ethylene, (methyl-) 1,2-ethylidene, 1,3-propylene, (methyl-) 1,2-cyclohexyl, (methyl-) 1, 2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,3-norbornyl, 2,3-norbornene-5-yl and / or (methyl-) 1,2-cyclo Hex-4-senyl radical.
    Depending on the starting monomer selected, the various B, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 in the molecule or molecular mixture may be selected equally or differently.
    The polymer composition according to the invention is usually a composition consisting of higher oligomers and lower oligomers, which usually contain up to 50 wt.%, Preferably up to 30 wt.% Of oligomers having a molecular weight of 600 or less.
    The polyesteramides according to the invention can be obtained, for example, by polycondensing mono- and / or bis-hydroxyalkylamides of divalent carboxylic acids.
    Monohydroxyalkylamides of divalent carboxylic acids usually have a structure of formula
    Bishydroxyalkylamides of divalent carboxylic acids can usually be represented by the formula:
    (In the formulas 6 and 7, R 1 , R 2 , R 3 and R 4 are each independently, the same or different, H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl Radicals)
    As a result, the linear polymer according to the invention consists of alternating amide groups and ester groups along the chain, such as
    E-A-E-A-A-E-A-E-A-E
    (Wherein the diamide is bonded to alternating ester (E) -amide (A) groups)
    The branched polymer according to the present invention is composed of alternating amide groups and ester groups along side and main chains as shown in the following structural formula:
    (Wherein the diamide is bonded to alternating ester (E) -amide (A) groups)
    In the branched polymer according to the present invention, the (β) -hydroxyalkylamide group is a terminal group;
    And may all exist as pendant side chains:
    In general, the molar amount of amide bonds in the chain is greater than the amount of ester bonds.
    The polymer according to the invention consists of at least 60% by weight of the product represented by formula 3-5.
    Due to side reactions during the preparation of the polymer, the composition according to the invention may consist of secondary amine groups of the formula
    (In Formula 8,
    R 1 , R 2 , R 3 and R 4 are independent of each other, are the same or different and are H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals)
    The polymers according to the invention can be obtained in one step by forming hydroxyalkylamide groups by reacting cyclic anhydrides with alkanolamines at temperatures of about 20 ° C. to about 100 ° C., and then at 120 ° C. to 250 ° C. Polyesteramides are obtained through polycondensation while removing water through distillation.
    The reaction can take place without a solvent, but can also occur in water or an organic solvent.
    Removal of water through distillation can take place in vacuum or azeotropically at a pressure of 1 bar or more.
    Preferably, the cyclic anhydride is an anhydride according to formula 9:
    (In Formula 9, B is defined as above)
    Examples of suitable cyclic anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, naphthalene dicarboxylic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornene-2,3-dicarboxylic acid Anhydride, naphthalene dicarboxylic acid anhydride, 2-dodecen-1-yl-succinic anhydride, maleic anhydride, (methyl) succinic anhydride, glutaric anhydride, 4-methylphthalic anhydride, 4-methylhexahydrophthalic anhydride, 4 Maleated alkylesters of methyltetrahydrophthalic anhydride and unsaturated fatty acids.
    Preferably, the alkanol is an alkanolamine of formula 10:
    (In Chemical Formula 10,
    Y = Or (C 1 -C 20 ) (cyclo) alkyl,
    R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independent of each other, are the same or different and are H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals or CH 2 OH and
    n = 1-4)
    n = 1 is more preferable. Alkanolamines are monoalkanolamines, dialkanolamines, trialkanolamines or mixtures thereof.
    If monoalkanolamines are used in one of the possible polymer synthesis, linear polymers having a functionality of 2 can be obtained. Depending on the desired use, linear or all or some branched polymer may be selected, in which case the branching may be set via the selected alkanolamine.
    If a highly branched structure with high functionality is desired, di- or trialkanolamines are used as starting compounds.
    Examples of suitable mono-β-alkanolamines are ethanolamine, 1- (meth) ethyl ethanolamine, n-butyl ethanolamine, 1- (meth) ethyl isopropanolamine, isobutanolamine, β-cyclohexanamine, n -Butyl isopropanolamine and n-propanolamine.
    Examples of suitable di-β-alkanolamines include 3-amino-1,2-propanediol, 2-amino-1,3-propanediol diisobutanolamine (bis-2-hydroxy-1-butyl) amine, Di-β-cyclohexanolamine and diisopropanolamine (bis-2-hydroxy-1-propyl) amine.
    Suitable trialkanolamines are tris (hydroxymethyl) aminomethane.
    Preferably, β-alkyl-substituted β-hydroxyalkylamides are used. Examples are (di) isopropanolamine, cyclohexyl isopropanolamine, 1- (meth) ethyl isopropanolamine, (di) isobutanolamine, di-β-cyclohexanolamine and / or n-butyl isopropanolamine.
    This results in a polymer composition having improved resistance to hydrolysis.
    Most preferred are diisopropanolamine and diisobutanolamine.
    Anhydride: alkanolamine equivalent ratios are usually from 1.0: 1.0 to 1.0: 1.8. Preferably, the ratio is 1: 1.05 to 1: 1.5.
    The compounds according to the invention can also be obtained by reacting such alkanolamines with compounds containing one acid group and one active acid group, after which the polyesteramide is obtained through polycondensation.
    Preferably, the compound containing an acid group and an active acid group is a compound of formula
    (In Chemical Formula 11,
    B is as defined above,
    -L = or Or OR 7 or SR 7 or Cl, wherein R 7 is a (C 1 -C 12 ) branched or linear alkyl group)
    Examples of suitable compounds containing one acid group and one active acid group are alkyl esters such as mono (meth) ethyl adipate and mono (meth) ethyl sebacate, anhydrides and thioesters.
    The compounds of the present invention can be obtained through the reaction between cyclic anhydrides and alcohols as described above, after which the reaction product is reacted with alkanolamines in situ and the polyesteramides are subjected to polycondensation Obtained.
    Examples of suitable alcohols are (C 1 -C 10 ) alcohols.
    Preference is given to using methanol or ethanol.
    In addition to the hydroxyalkylamide groups, the polymer also contains carboxyl groups in an amount of 0.01 to 2.0 mg per gram of polymer. The number of carboxylic acids present in the polymer can be controlled by the anhydride / alkanolamine ratio and conversion. If an excess of alkanolamine is used and the polycondensation reaction is (nearly) complete, up to 0.2 mg equivalent acid per gram of polymer is usually present. If carboxyl groups are present, they are reacted with compounds containing one or more groups which can react with carboxylic acids, for example epoxy groups or β-hydroxyalkylamide groups, in subsequent steps. The amount of carboxylic acid is preferably as small as possible in an amount of 0.01 to 0.2 mg per g polymer.
    The degree of branching and functionality of the polymer depends on the molecular weight and starting material of the polymer. By using a molecular weight of at least 2000 and di- and / or trialkanolamines, higher branched structures having at least 10 functionalities are obtained.
    The bis anhydride and dianhydride (in total amount in the anhydride) are present in an amount of 10% by weight or less instead of the anhydride of formula 9 so that the polymer may not consist solely of the product according to formula 3-5.
    The present invention also relates to all or some modified polymers.
    The modification may occur through a reaction between a monomer, oligomer or polymer containing a reactor capable of reacting with hydroxyalkylamide and a polymer of one of formulas 3, 4 or 5.
    Examples of suitable reactors include carboxyl groups, carboxylic acid esters, carboxylic anhydrides, epoxy groups, alkoxysilane groups, isocyanate groups, acid chloride groups, epoxychlorohydrin groups, amine groups, phenol groups, methylolated amide groups and combinations thereof There is this.
    The monomers, oligomers or polymers preferably contain only one group capable of reacting with hydroxyalkylamides, so that no crosslinking occurs through modification.
    The polymer of formula (3), (4) or (5) is preferably modified with a compound containing a carboxylic acid group.
    The modified polymer can be represented by any one of formulas 3, 4 or 5, wherein X 2 = H, X 1 or (here, Is a monomer, oligomeric or polymeric monofunctional carboxylic acid).
    Suitable carboxylic acids are, for example, saturated aliphatic (C 1 -C 26 ) acids, unsaturated (C 1 -C 20 ) fatty acids, aromatic acids and α, β-unsaturated acids.
    Examples of suitable α, β-unsaturated acids are (meth) acrylic acid, crotonic acid and monoesters or monoamides of itaconic acid, maleic acid, 12-hydroxystearic acid, polyether carboxylic acid and fumaric acid.
    Examples of suitable saturated aliphatic acids are acetic acid, propionic acid, butyric acid, 2-ethyl hexanoic acid, lauryl acid and stearic acid.
    Examples of suitable aromatic acids are benzoic acid and tertiary butyl benzoic acid.
    Z can be selected, for example, from saturated or unsaturated (C 1 -C 40 ) alkyl or aromatic groups, polymers or oligomers. Examples of suitable polymers are polyesters, polyethers and poly (capro) lactones.
    Z can be substituted, for example, with ester groups, ether groups, amide groups and alcohol groups.
    The modified polymer is composed of the same or different Z groups.
    The branched polymers according to the invention can also react with diisocyanates, after which the isocyanate-functional polymers are reacted with compounds which can react with isocyanates. Preference is given to using as diisocyanates compounds which contain two or more isocyanate groups having different reactivity. It is preferred to be an aliphatic diisocyanate having one steric less accessible isocyanate group bonded to the tertiary carbon atom and a steric better accessible isocyanate group bonded to the primary carbon atom.
    Examples of suitable diisocyanates are 1,4-diisocyanato-4-methyl-pentane, 1,5-diisocyanato-5-methylhexane, 3 (4) -isocyanatomethyl-1-methyl, respectively Cyclohexyl isocyanate, 1,6-diisocyanato-6-methyl-heptane, 1,5-diisocyanato-2,2,5-trimethylhexane and 1,7-diisocyanato-3,7- Dimethyloctane and 1-isocyanato-1-methyl-4- (4-isocyanatobut-2-yl) -cyclohexane, 1-isocyanato-1,2,2-trimethyl-3- ( 2-isocyanato-ethyl) -cyclopentane, 1-isocyanato-1,4-dimethyl-4-isocyanatomethyl-cyclohexane, 1-isocyanato-1,3-dimethyl- 3-isocyanatomethyl-cyclohexane, 1-isocyanatol-n-butyl-3- (4-isocyanatobut-1-tyl) -cyclopentane and 1-isocyanato-1,2 -Dimethyl-3-ethyl-3-isocyanatomethyl-cyclopentane.
    Preferred isocyanates are 3 (4) -isocyanato-methyl-1-methylcyclohexyl isocyanate (IMCI) and isophorone diisocyanate.
    Monomers, oligomers and polymers can all be used as compounds capable of reacting with isocyanate groups. The compound contains a reactor capable of forming chemical bonds with isocyanate groups.
    Examples of suitable reactors are alcohol and amine groups.
    Examples of suitable compounds include hydroxyethyl (meth) acrylate, hydroxy (C 2 -C 12 ) alkyl vinyl ether, 4-hydroxybutyl (meth) acrylate, aminopropyl vinyl ether, aminoalkyl vinyl ether, aminopropyl -Tri (meth) ethoxysilane and aminoalkyltrialkoxysilane.
    Preferably, diisocyanates such as IMCI are combined with the selective catalyst and as a result no chain extension or crosslinking will occur.
    Metal element-based ionogen metal complexes from any one of group 3, 4 or 7 of the periodic table with exchangeable counterions can be used as catalyst. Examples of suitable catalysts include titanium (IV) butoxide, zirconium (IV) acetylacetonate, zirconium (IV) butoxide, tin (IV) acetate, manganese (III) acetylacetonate, titanium (IV) isopropoxide, Zirconium (IV) 2-ethylhexanoate and tin (IV) chloride.
    Modified and unmodified polymers can be very widely used in technical, other applications, thermosetting and thermoplastic applications. Examples include powder-paint compositions, water or solvent-based coating systems, can- or coil-coating systems, radiation-curable coating compositions, alkyd resins for coatings, unsaturated resins for construction purposes (e.g. putty, sealants, castings, Compounds and molding compounds), inks, toners, film formers for glass fiber formulations, adhesives, hot melts and rubber compositions.
    Unmodified or partially modified polymers according to the present invention will usually be used in powder-paint systems, can- or coil-coating systems or solvent-based coating systems.
    If modifications are made by fatty acids, the polymers according to the invention can be used in airdrying systems.
    Modifications made with essentially curable compounds offer possibilities in the art of radiation-curable coatings and building resins.
    In view of the many possibilities for modifying the polymers according to the invention the modifications can be carried out for a wide range of technical uses.
    The polymers according to the invention can be used to thermoset powder-paint compositions. Preference is given to using polymers containing β-hydroxyalkylamide groups.
    Thermoset powder paints have better chemical resistance than thermoplastic powder paints. As a result, a long time intensive effort has been invested in developing crosslinking agents and polymers for thermosetting powder paints. There are still attempts to find binding compositions for thermosetting powder paints with good flow behavior, good storage stability and good reactivity. The thermosetting powder-paint bond composition usually contains at least 50 wt.% Of the polymer and up to 50 wt.% Of the crosslinking agent.
    The polymers according to the invention can be used as polymers and crosslinkers in powder-paint compositions.
    The glass transition temperature (Tg) of the polymer according to the invention is 0 ° C. to 150 ° C., preferably 50 ° C. to 110 ° C., depending on the starting material and molecular weight selected.
    Preferably, the compound according to one of the formulas 1, 2, 3, 4 or 5 is used in the powder-paint composition. It is also possible to use, for example, polymers in which hydroxyalkylamide groups of up to 50 wt.%, Preferably up to 30 wt.% Are modified.
    Finally, the coating obtained by powder paint has to meet many different conditions. Several systems are known. Some systems release volatiles during curing. The system has the disadvantage of forming a coating with bubbles and / or release of undesirable emitters. As far as the latter is concerned, volatile organics from the outset can cause undesirable environmental or health problems. And it has been found that not all the desired properties of powder paint or powder coating are always achieved.
    For example, a system composed of hydroxyalkylamide crosslinkers according to EP-A-322834 contains bubbles above the layer thickness limit of about 100 μm as a result of the release of the reaction water.
    In other systems, conventional crosslinkers and polyesters containing epoxy groups are used. No volatiles are usually released from the system. However, the use of bisphenol-A-epoxy resins in so-called hybrid systems results in coatings that exhibit a relatively high degree of yellowing and powdering when exposed to UV light, while triglycidyl isocyanurate is often used. (TGIC) crosslinkers are considered toxicologically.
    The use of the polymers of the present invention as crosslinking agents in bonding compositions for powder paints results in, for example, good flow behavior and good chemical resistance, desired gloss without bubbles on the surface, layer thickness of at least 120 μm, high resistance to scratching. A combination of very desirable properties such as resistance, good mechanical properties of the powder coating, good powder stability, good weather resistance and good color stability are obtained.
    It is surprising that crosslinking agents having at least 6 functionalities usually reduce the flow behavior and thus obtain good flow behavior using the highly functional crosslinkers according to the invention.
    According to the desired end use, the crosslinking agents according to the invention can be prepared by other crosslinking agents such as, for example, triglycidyl isocyanurate (TGIC), polybisphenol-A-epoxides, such as several epikote ) TM grade, compounds containing (isolated) isocyanate groups, such as caprolactam-shielded isophorone diisocyanate trimers, crosslinkers containing β-hydroxyalkylamide groups, such as Primid It can be used in combination with XL 522 TM (Rohm and Haas) and / or multifunctional oxazoline. The weight ratio between crosslinking agents can be selected depending on the end use.
    The crosslinking agent according to the present invention is preferably composed of at least one linear or branched aliphatic chain having 5 to 26 carbon atoms, and combined with a crosslinking agent having at least one epoxy functionality if the epoxy group is transported on at least one aliphatic chain. . The crosslinking agent is described in European Patent EP-A-600546, for example, the oil may be linseed oil, soybean oil, safflower oil, oticica oil, caraway seed oil, rapeseed oil, Castor oil, dehydrated castor oil, cottonseed oil, tung oil, vernonia oil (natural oil), sunflower oil, peanut oil, olive oil, soyleaf oil, corn oil, fish oil, for example herring or Epoxidized oils, which are sardine oils and non-cyclic terpene oils.
    The epoxidized oil is preferably epoxidized soybean oil and / or epoxidized linseed oil.
    As a crosslinking agent, the powder-paint-binding composition contains a polymer according to the present invention and includes a polymer containing a carboxyl group or an anhydride group as a polymer.
    Polyesters, polyacrylates, polyethers (e.g., bisphenol or phenol-aldehyde novolac-based polyethers), polyurethanes, polycarbonates, trifluoroethylene copolymers or pentafluoropropylene copolymers, poly Butadiene, polystyrene or styrene maleic anhydride copolymers may be selected as the polymer.
    Usually, polymers having an acid value of at least 40 mg / g resin (g) are used because the relatively high acid value indicates good reactivity with the polymer according to the present invention.
    Although the molecular weight (Mn) of the said polymer is 800 or more normally, it is preferable that it is 1500 or more. The polymer has a molecular weight (Mn) of about 10,000 or less, preferably about 7000 or less, because it must flow well at temperatures of 100 ° C to 200 ° C.
    The polymer has a viscosity of 8000 dPas or less at 158 ° C. The viscosity will usually be at least 100 dPas. The viscosity can vary from about 300 to about 5000 dPas. The viscosity used is Misev in Powder Coatings; Measurements were made according to the Emila method described in Chemistry and Technology, p. 287-288 (1991).
    The Tg of the polymer is usually at least about 20 ° C, preferably at least 30 ° C, and may be at least 40 ° C. Since the bonding composition is somewhat difficult to prepare, the Tg of the polymer is usually 120 ° C. or less. As already described, the choice of the Tg of the polymer may be based on the Tg for the bond composition.
    If a polymer having only terminal groups capable of reacting with hydroxyalkylamide functional groups is used, the polymer has an average functionality of at least 1.6, preferably at least 2 (which can react with hydroxyalkylamide groups). The polymer usually has an average functionality of 10 or less, preferably about 6 or less. If a polymer such as polyacrylate having a functionality is used, the average functionality will be at least about 1.6, preferably at least 2. The polymer usually has an average functionality of 8 or less, preferably 4 or less.
    Most suitable polymers are polyester and polyacrylate.
    Many properties can be obtained in the binder and in the powder coating itself by the polymer. Polyacrylates are resistant to yellowing and weather resistant. Polyacrylates that can be used as polymers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylic Latex, cyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, benzyl (meth) acrylate and hydroxyalkyl (meth) acrylates such as hydroxyethyl and hydroxypropyl ( Based on glycidyl esters or glycidyl ethers of meth) acrylates and / or alkyl (meth) acrylates.
    Polyacrylates can be obtained through known methods. In the process it is possible to use comonomers such as styrene, maleic acid or maleic anhydride and small amounts of ethylene, propylene and acrylonitrile. Other vinyl or alkyl monomers such as octene, triallyl isocyanurate and diallyl phthalate may be added in small amounts.
    Polyacrylates containing an acid group are obtained by copolymerizing a desired amount of acid, such as (meth) acrylic acid, maleic acid or fumaric acid.
    The viscosity of polyacrylates is usually between 100 dPas and 8000 dPas (measured at 158 ° C .; emila).
    Polyacrylates are described in US-A-3,752,870, US-A-3,787,340 and US-A-3,758,334, and UK 1,333,361, all of which are hereby incorporated by reference in their entirety.
    Polyurethanes that can be used as polymers that can react with β-hydroxyalkylamide groups include polyurethanes that terminate with acid groups and (shielded) isocyanate groups.
    Polyesters are based on residues of aliphatic polyalcohols and polycarboxylic acids.
    Polycarboxylic acids are selected from the group consisting of aromatic and cycloaliphatic polycarboxylic acids because they have a Tg-raising effect on the polyester. In particular, dibasic acids are used. Examples of polycarboxylic acids are isophthalic acid, terephthalic acid, hexahydroterephthalic acid 2,6-naphthalene dicarboxylic acid and 4,4-oxybisbenzoic acid, and their anhydrides, acid chlorides or lower alkyl esters such as dimethyl esters of naphthalene dicarboxylic acid. Can be used. Although not essential, the carboxylic acid component usually contains at least about 50 mole%, preferably at least about 70 mole%, of isophthalic acid and / or terephthalic acid.
    Examples of other suitable aromatic cycloaliphatic and / or acyclic polycarboxylic acids include 3,6-dichlorophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, hexahydroterephthalic acid, hexachloroendomethylene tetrahydrophthalic acid, phthalic acid, azelaic acid, sebacic acid, Decandicarboxylic acid, adipic acid, succinic acid, trimellitic acid and maleic acid. The other carboxylic acids may be used in an amount of up to 50 mol.% Of the total amount of carboxylic acids. The acids may also be used and may also be used in the form of their anhydrides, acid chlorides or lower alkyl esters.
    Hydroxycarboxylic acids and / or optionally lactones may also be used, examples being 12-hydroxystearic acid, hydroxypivalic acid and ε-caprolactone. If desired, monocarboxylic acids such as benzoic acid, tert.-butylbenzoic acid, hexahydrobenzoic acid and saturated aliphatic monocarboxylic acids can be used in small amounts.
    In particular polyhydric alcohols such as diols which can be reacted with carboxylic acids to obtain polyesters are aliphatic diols, for example ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1, 2-diol, butane-1,4-diol, butane-1,3-diol, 2,2-dimethylpropanediol-1,3 (= neopentyl glycol), hexane-2,5-diol, hexane-1, 6-diol, 2,2-bis- (4-hydroxy cyclohexyl) -propane (hydrogen bisphenol A), 1,4-dimethylolcyclohexane, diethylene glycol, dipropylene glycol and 2,2-bis [4 Hydroxypivalic acid esters of 2-hydroxyethoxy) -phenyl] propane and neopentyl glycol.
    Small amounts of trifunctional alcohols or acids up to about 4 wt.%, Preferably up to 2 wt.% May be used to obtain the branched polyester. Examples of suitable polyols and polyacids are glycerol, hexanetriol, trimethylolethane, trimethylolpropane, tris- (2-hydroxyethyl) -isocyanurate and trimellitic acid.
    Tetrafunctional monomers can cause excessive branching or gelling, which is usually undesirable but may be used in very small amounts. Examples of suitable polyhydric alcohols and acids are sorbitol, pentaerythritol and pyromellitic acid. However, trifunctional monomers are preferred for synthesizing branched polyesters.
    Coating properties can be influenced by selecting diols. For example, if good weather resistance is required, the alcohol component preferably contains at least 70 mol.% Of neopentyl glycol, 1,4-dimethylolhexane and / or hydrogenated bisphenol-A. If good weather resistance is required, caprolactone and hydropivalic acid can also be used.
    The polyesters are optionally prepared by conventional methods, for example via esterification or trans-esterification in the presence of conventional esterification catalysts such as, for example, dibutyl tin oxide or tetrabutyl titanate. The conditions of manufacture and the COOH / OH ratio may be chosen such that a final product having an acid value or hydroxyl value within the desired value range is obtained.
    The carboxylic acid-functional polyester is preferably produced in a continuous step. In the last step, the aromatic, or preferably aliphatic acid, is esterified such that an acid-functional polyester is obtained. As is known to those skilled in the art, terephthalic acid is reacted in the first step in the presence of excess diol. By this reaction, the hydroxy-functional polyester is actually obtained. In the first or subsequent steps, the acid-functional polyester is obtained by reacting another acid with the product of the first step. Examples of other acids are isophthalic acid, adipic acid, succinic anhydride, 1,4-cyclohexanedicarboxylic acid and trimellitic anhydride.
    Since trimellitic anhydride is obtained with a polyester having a relatively large number of trimellitic acid end groups, it is preferred to be used at a temperature of 170-200 ° C., as a result of which the reactivity of the binding system is increased to obtain better coating properties. Lose.
    Polyester is crystalline polyester, but amorphous polyester is preferred. Mixtures of crystalline and amorphous polyesters can also be used. Amorphous polyesters have a viscosity (measured at 158 ° C., emila) within 100 to 8000 dPas. Crystalline polyesters usually have a low viscosity of about 2 to about 200 dPas.
    If the polyester contains a group capable of reacting with the carboxylic acid, the acid value of the polyester is selected so that the desired amount of crosslinking agent can be used. The acid value is preferably 10 or more, more preferably 40 or more.
    The Tg of the polyester is selected such that the Tg of the polyester-crosslinker mixture is from 30 ° C. to 80 ° C., so that the powder paint or binder prepared therefrom is physically stable at room temperature. Combinations of low Tg crosslinking agents with polyesters can optionally be used to prepare powder coating compositions. To maintain powder stability, the powders are stored under cooling conditions.
    The choice of polymer: crosslinker weight ratio depends on the desired end use, and the ratio will usually be 60:40 to 90:10, preferably 75:25 to 85:15.
    If the polymers according to the invention are used as resins in powder-paint compositions, compounds containing two or more functional groups capable of reacting with β-hydroxyamide groups can be used as crosslinking agents. Examples of such groups are anhydrides, carboxylic acids, carboxylic esters, epoxides, isocyanates and alkoxysilanes. Preferably, anhydride groups, carboxylic acids and masked isocyanates are used. Examples include IPDI- optionally masked with adipic acid, decandicarboxylic acid, trimellitic anhydride, phthalic or phthalic anhydride, tetrahydrophthalic or tetrahydrophthalic anhydride, hexahydrophthalic or hexahydrophthalic anhydride and caprolactam or triazole Trimers or HDI-trimers.
    Preparation of thermosetting powder coatings and chemical reactions for curing powder paints to form curing coatings are described in Misev in Powder Coatings, Chemistry and Technology (1991, John Wiley) pp. 42-54, pp. 148, 224-226. Described. A thermosetting bond composition is defined as the resin portion of a powder paint composed of a polymer and a crosslinking agent.
    If desired, conventional additives such as pigments, fillers, degassers, flow agents and stabilizers can be used in the binder composition and in the powder-paint system according to the invention. Suitable pigments include, for example, inorganic pigments such as titanium dioxide, zinc sulfide, iron oxide and chromium oxide, and organic pigments such as azo compounds. Suitable fillers are, for example, metal oxides, silicates, carbonates and sulfates.
    Primary and / or secondary antioxidants, UV stabilizers, such as quinones, (sterically hindered) phenolic compounds, phosphonates, phosphates, thioethers and HALS compounds (hindered amine light stabilizers) can be used as stabilizers.
    Examples of degassing agents are benzoin and cyclohexane dimethanol bisbenzoate. Examples of flow agents are polyalkylacrylates, fluorohydrocarbons and silicone emulsions. Other suitable additives are additives for improving tribocharging, such as steric hindrance tertiary amines described in EP-B-371528.
    The powder paint according to the present invention can be applied in a conventional manner such as by electrostatic spraying powder on a ground substrate and curing the coating by exposure to heat at a suitable temperature for a sufficient time. The powder applied can be heated in a gas oven, in an electron oven or by infrared radiation.
    Thermosetting coatings of powder-paint (coating) compositions prepared for industrial use are further described in Powder Coatings, Chemistry and Technology, Misev, p. 141-173 (1991).
    The composition according to the invention can be used in powder paint for use in metal, wood and plastic substrates. Examples include industrial coatings, coatings for machines and tools, home use and construction. The coating is also suitable for use in the automotive industry for coated parts and accessories.
    German patent DE-A-19703952 discloses copolyesters containing β-hydroxyalkylamide groups as terminal groups. The polyester polymer main chain is not composed of amides. Copolyesters are prepared by a three-step process by mixing hydroxy polyesters with polycarboxylic acid dialkyl esters to form alkylester groups containing copolyesters by reaction with aminoalcohols. In contrast, the polymers according to the invention are polyesteramides having amide and ester groups along the main chain in addition to the β-hydroxyalkylamide end groups. The polyesteramide forms improved mechanical coating properties, improved crosslink density and improved hydrolysis resistance by forming excess hydrogen bonds.
    The present invention is described in detail by the following examples, which shall not be limited thereto.
    Example I
    Preparation of higher branched polymers composed of units of phthalic anhydride and diisopropanolamine
    384 g of phthalic anhydride and 415 g of diisopropanolamine were placed in a double walled glass reactor equipped with a mechanical stirrer, distillation head and nitrogen and vacuum connections, which could be heated by heat medium oil. The reaction mixture was gradually heated to about 70 ° C. with stirring and more slowly to 170 ° C. A vacuum was formed during the heating. The pressure in the reactor was adjusted by releasing the reaction water, which could be removed from the reactor through distillation. After 6 hours of total reaction time, the viscous polymer contained less than 0.1 meq / g of carboxylic acid (as measured appropriately) and water could no longer be removed by distillation. After cooling, the polymer was obtained in very pale yellow glassy mass. The concentration of the hydroxyl group was found to be 5.4 meq / g by titration. The number average molecular weight was measured by GPC (general calibration) and was 1500 g / mol; The weight average molecular weight was 7700 g / mol.
    Example II
    Preparation of higher branched polymers composed of units of phthalic anhydride and diisopropanolamine
    232 g of phthalic anhydride and 270 g of diisopropanolamine were placed in a double walled glass reactor equipped with a mechanical stirrer, distillation head and nitrogen and vacuum connection, which could be heated by heat medium oil. The reaction mixture was gradually heated to about 70 ° C. with stirring and more slowly to 170 ° C. A vacuum was formed during the heating. The pressure in the reactor was adjusted by releasing the reaction water, which could be removed from the reactor through distillation. After a total reaction time of 5 hours, the viscous polymer contained less than 0.2 meq / g carboxylic acid (as measured appropriately) and water could no longer be removed by distillation. After cooling, the polymer was obtained in very pale yellow glassy mass. The concentration of the hydroxyl group was found to be 5.8 meq / g by titration. The number average molecular weight was measured by GPC (general calibration) and was 1100 g / mol; The weight average molecular weight was 4900 g / mol.
    Example III
    Preparation of higher branched polymer composed of units of hexahydrophthalic anhydride and diisopropanolamine
    398 g of hexahydrophthalic anhydride and 408 g of diisopropanolamine were placed in a double walled glass reactor equipped with a mechanical stirrer, distillation head and nitrogen and vacuum connections, which could be heated by thermal oil. The reaction mixture was gradually heated to about 70 ° C. with stirring and more slowly to 160 ° C. A vacuum was formed during the heating. The pressure in the reactor was adjusted by releasing the reaction water, which could be removed from the reactor through distillation. After a total reaction time of 3.5 hours, the viscous polymer contained less than 0.2 meq / g carboxylic acid (measured as appropriate) and water could no longer be removed by distillation. After cooling, the polymer was obtained as an almost colorless glassy mass. The concentration of the hydroxyl group was found to be 5.2 meq / g by titration. The number average molecular weight was measured by GPC (general calibration) and was 1550 g / mol; The weight average molecular weight was 7000 g / mol.
    Example IV
    Preparation of higher branched polymer composed of units of hexahydrophthalic anhydride and diisopropanolamine
    378 g of hexahydrophthalic anhydride and 436 g of diisopropanolamine were placed in a double walled glass reactor equipped with a mechanical stirrer, distillation head and nitrogen and vacuum connections, which could be heated by thermal oil. The reaction mixture was gradually heated to about 70 ° C. with stirring and more slowly to 170 ° C. A vacuum was formed during the heating. The pressure in the reactor was adjusted by releasing the reaction water, which could be removed from the reactor through distillation. After a total reaction time of 5 hours, the viscous polymer contained less than 0.1 meq / g of carboxylic acid (as measured appropriately) and water could no longer be removed by distillation. After cooling, the polymer was obtained as an almost colorless glassy mass. The concentration of the hydroxyl group was found to be 6.1 meq / g by titration. The number average molecular weight was measured by GPC (general calibration) and was 1010 g / mol; The weight average molecular weight was 4600 g / mol.
    Example Ⅴ-Ⅷ
    Powder-paint composition composed of the polymer according to any one of Examples I-IV
    Powder-paint compositions according to Table 1 were prepared by mixing and extrusion (PRISM extruder, 120 ° C). Polyesters (Uralac 5040 ™ and Uralak 5261 ™ made of DSM resin) are composed of units of terephthalic acid, adipic acid, neopentyl glycol and trimellitic anhydride.
    The composition was ground in a conventional manner, sieved and electrostatically sprayed (Corona) on aluminum and steel test panels. After a curing cycle of 10 minutes at 200 ° C. or 15 minutes at 180 ° C. in a circulating oven, their appearance (visual) and flexibility (mm penetration according to Erichsen ISO 1520 / DIN 53156) for the panels. ), Reverse shock resistance (ASTM-2794 / 69 (inch-pound)), acetone resistance (rubbed twice with acetone), adhesion (cross hatch adhesion test), and hardness (Koenig (seconds)) ) Was tested. The test results are shown in Table 1.
    This example shows that a polymer having very good chemical, mechanical and optical properties and a high bubble limit (visual) is obtained by the polymer according to the invention.
    Composition and Coating Characteristics FurtheranceABCDEF Polyester resin: Ural lock P5261 TM Ural lock P5040 TM 155 g156 g162 g159 g160 g164 g Crosslinker of Example I Crosslinker of Example II Crosslinker of Example III Crosslinker of Example IV45 g44 g38 g43 g42 g36 g Adhesive: TiO 2 2160 Benzoin BYK 361100g3.0g1.5g100g3.0g1.5g100g3.0g1.5g100g3.0g1.5g100g3.0g1.5g100g3.0g1.5g Curing cycle10'200 ℃10'200 ℃10'200 ℃15'180 ℃15'180 ℃15'180 ℃ Hardness Impact Resistance 1) ESP 2) Adhesion 3) Gelation Time 4) Flow Behavior Bubble Limit235 s> 160 ip> 8 mm Gt0n.d. 5) OK120μ225s160ip> 8mmGt0151OK120μ215s〉 160ip〉 8mmGt080OK130μ215s> 160ip> 8mmGt0116OK140μ210s〉 160ip〉 8mmGt085OK140μ195s> 160ip> 8mmGt0100OK140μ
    1) reverse impact resistance; Steel ASTM-2794 / 69.
    Impact resistance is usually expressed in inches by pounds. If no crack appears in the coating at 160i.p., 160i.p. is cited as the result. The impact resistance of 160 i.p. is 1.84 m.kg.
    2) Ericsen slow penetration; ISO 1520 / DIN 53156
    3) cross-hatch adhesion; ISO 2409 / DIN 5315
    4) DIN 55990; Part B.
    5) Not measured
    权利要求:
    Claims (21)
    [1" claim-type="Currently amended] A condensation polymer containing an ester group and at least one amide group in the main chain, having at least one hydroxyalkylamide end group, and having a weight average molecular weight of 800 g / mol or more.
    [2" claim-type="Currently amended] The method of claim 1,
    The polymer is a condensation polymer characterized in that it contains at least two groups of the formula (1);
    (Formula 1)

    (In Formula 1,
    Y = H, (C 1 -C 20 ) (cyclo) alkyl or (C 6 -C 10 ) aryl,
    B = (C 2 -C 24 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical,
    R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently the same or different and are H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals , And
    n = 1-4).
    [3" claim-type="Currently amended] The method according to claim 1 or 2,
    The polymer comprises at least two groups of the formula
    (Formula 2)

    (In Formula 2,
    Y = H, (C 1 -C 20 ) (cyclo) alkyl or (C 6 -C 10 ) aryl,
    B = (C 2 -C 20 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical, and
    R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , independently of one another, are the same or different and are H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals )
    [4" claim-type="Currently amended] The method according to any one of claims 1 to 3,
    The polymer is a condensation polymer, characterized in that the polymer of formula
    (Formula 3)

    (In Chemical Formula 3,
    Y = H, (C 1 -C 20 ) (cyclo) alkyl or (C 6 -C 10 ) aryl,

    B = (C 2 -C 24 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical,

    X 2 = H or X 1 , and
    R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are H, (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals or CH 2 -OX 2 )
    [5" claim-type="Currently amended] The method according to any one of claims 1 to 4,
    The polymer is a condensation polymer, characterized in that represented by the polymer of the formula
    (Formula 4)

    (In Formula 4,
    Y = H, (C 1 -C 20 ) (cyclo) alkyl or (C 6 -C 10 ) aryl,

    B = (C 2 -C 24 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical,

    X 2 = H or X 1 ,
    R 3 = H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) alkyl radicals and
    R 6 = H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) alkyl radical)
    [6" claim-type="Currently amended] The method according to any one of claims 1 to 5,
    The polymer is a condensation polymer, characterized in that the polymer of formula:
    (Formula 5)

    (In Chemical Formula 5,

    B = (C 2 -C 12 ), optionally substituted, aryl or (cyclo) alkyl aliphatic diradical,

    X 2 = H or X 1
    R 3 = H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radicals, and
    R 6 = H or (C 6 -C 10 ) aryl or (C 1 -C 8 ) (cyclo) alkyl radical)
    [7" claim-type="Currently amended] The method according to any one of claims 2 to 6,
    B is (methyl-) 1,2-ethylene, (methyl-1) 1,2-ethylidene, 1,3-propylene, (methyl-) 1,2-cyclohexyl, (methyl-) 1,2-phenyl Ethylene, 1,3-phenylene, 1,4-phenylene, 2,3-norbornyl, 2,3-norbornene-5-yl and / or (methyl-) 1,2-cyclohex-4 A condensation polymer, characterized in that it is a cenyl radical.
    [8" claim-type="Currently amended] The method according to any one of claims 1 to 7,
    The weight average molecular weight is 800 to 50,000 g / mol, the number average molecular weight is 600 to 10,000, hydroxyalkylamide functionality is 2 to 250, characterized in that the condensation polymer.
    [9" claim-type="Currently amended] The method according to any one of claims 1 to 8,
    A condensation polymer, which can be obtained by polycondensation of mono- and / or bis-β-hydroxyalkylamide of divalent carboxylic acid.
    [10" claim-type="Currently amended] The cyclic anhydride reacts with an alkanolamine to form hydroxylalkylamide, and then the polymer is obtained through polycondensation.
    [11" claim-type="Currently amended] The process for producing a condensation polymer according to any one of claims 1 to 9, wherein the alkanolamine is reacted with a compound containing an acid group and an active acid group, and then the polymer is obtained by polycondensation.
    [12" claim-type="Currently amended] The condensation polymer according to any one of claims 1 to 9, wherein the cyclic anhydride reacts with alcohol, the reaction product obtained thereafter reacts with alkanolamine in situ, and the polymer is obtained by polycondensation. Manufacturing method.
    [13" claim-type="Currently amended] The method according to any one of claims 10 to 12,
    Alkanolamine is a production method, characterized in that β-alkyl-substituted β-hydroxyalkylamine.
    [14" claim-type="Currently amended] The method according to any one of claims 10 to 13,
    Alkanolamines are (di) isopropanolamine, 1- (meth) ethylisopropanolamine, (di) isobutanolamine, cyclohexylisopropanolamine, di-β-cyclohexanolamine and / or n-butylisopropanolamine Manufacturing method.
    [15" claim-type="Currently amended] Modified polymers obtainable by reacting a polymer according to any one of Formulas 3, 4 or 5 with a monomer, oligomer or polymer containing a reactor capable of reacting with hydroxyalkylamides.
    [16" claim-type="Currently amended] Modified polymers according to any one of Formulas 3, 4 or 5;
    (In the above three formulae, X 2 = H, X 1 or , Where Is derived from monofunctional carboxylic acids of monomers, oligomers or polymers).
    [17" claim-type="Currently amended] A powder-paint bonding composition containing the polymer according to any one of claims 1 to 9 or 15 to 16 or the polymer obtained according to any one of claims 10 to 14.
    [18" claim-type="Currently amended] The method of claim 17,
    A bonding composition comprising an crosslinking agent having at least one epoxy functional group, consisting of at least one linear or branched aliphatic chain having 5 to 26 carbon atoms, if the epoxy group moves on at least one aliphatic chain.
    [19" claim-type="Currently amended] Powder paint composition composed of the bonding composition according to claim 17.
    [20" claim-type="Currently amended] Powder coating obtained by curing the powder paint according to claim 19.
    [21" claim-type="Currently amended] Full or partial coated substrate, characterized in that the powder coating according to claim 20 is used as a coating.
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    同族专利:
    公开号 | 公开日
    EP1036106B1|2003-08-13|
    AU746623B2|2002-05-02|
    TW588069B|2004-05-21|
    US6392006B1|2002-05-21|
    DE69817216T2|2004-06-09|
    MY125719A|2006-08-30|
    CA2305364A1|1999-04-08|
    CA2305364C|2004-06-29|
    AU9190298A|1999-04-23|
    JP2001518539A|2001-10-16|
    NL1007186C2|1999-04-07|
    EP1036106A1|2000-09-20|
    IL135396A|2005-07-25|
    AT247143T|2003-08-15|
    WO1999016810A1|1999-04-08|
    CN1281478A|2001-01-24|
    ES2205543T3|2004-05-01|
    CN1158334C|2004-07-21|
    JP3643032B2|2005-04-27|
    DE69817216D1|2003-09-18|
    US6387496B1|2002-05-14|
    KR100524455B1|2005-10-26|
    US20020055609A1|2002-05-09|
    IL135396D0|2001-05-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-10-01|Priority to NL1007186A
    1997-10-01|Priority to NL1007186
    1998-09-22|Application filed by 윌리암 로엘프 드 보에르, 디에스엠 엔.브이
    1998-09-22|Priority to PCT/NL1998/000546
    2001-04-16|Publication of KR20010030837A
    2005-10-26|Application granted
    2005-10-26|Publication of KR100524455B1
    优先权:
    申请号 | 申请日 | 专利标题
    NL1007186A|NL1007186C2|1997-10-01|1997-10-01|ß-hydroxyalkylamide group-containing condensation polymer.|
    NL1007186|1997-10-01|
    PCT/NL1998/000546|WO1999016810A1|1997-10-01|1998-09-22|Condensation polymer containing hydroxyalkylamide groups|
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